Method for making particulate amine-functionalized polyaryletherketone polymers and copolymers thereof

Abstract

The present invention provides a method of preparing an amine-functionalized (e.g. amine-terminated) polyaryletherketone polymer, or imide- or sulphone-copolymer thereof and amine-protected analogs thereof, said method comprising the step of polymerizing a monomer system in a reaction medium comprising a capping agent comprising NR.sub.2, NRH or a protected amine group.

Claims

1. A method of preparing an amine-functionalized polyaryletherketone polymer, an imide- or sulphone-copolymer thereof or an amine-protected analogues thereof, said method comprising: polymerizing a monomer system in a reaction medium comprising a Lewis acid, a controlling agent and a capping agent comprising NR.sub.2, NRH or a protected amine group, wherein each R is independently an aliphatic group or an aromatic group.

2. The method of claim 1, wherein said controlling agent comprises an aromatic carboxylic acid, an aromatic sulphonic acid, or a derivative thereof.

3. The method of claim 1, wherein said controlling agent comprises a Lewis base.

4. The method of claim 1, wherein said monomer system comprises an imide and/or sulphone monomer.

5. The method of claim 1, wherein said capping agent is an agent represented by formula (Z).sub.aAr(X).sub.b wherein: each X is independently selected from the group consisting of OAr, C(O)Cl, C(O)ArOAr and OAr[C(O)ArOAr].sub.cH, wherein each Ar is independently an aromatic group; c is an integer; Z is a protected amine group; a is 1 to 5; and b is 1 to 5.

6. The method of claim 1, wherein said controlling agent is one or more of (i) Ar(COOX).sub.y; (ii) Ar(SO.sub.3X).sub.y; (iii) (ArCOO.sup.).sub.zM.sup.z+; or (iv) (ArSO.sub.3.sup.).sub.zM.sup.z+; wherein Ar is an aromatic group compatible with the remaining components of the reaction medium; each X independently is a hydrogen atom or an organic group (R); each y independently is 1, 2 or 3; each M independently is a metal ion, and each z independently is an integer equal to charge on the metal ion (M.sup.z+).

7. The method of claim 1, wherein said polyaryletherketone is a homopolymer or copolymer of one or more of the following repeat units: ArOArC(O) ArOArC(O)ArC(O) ArOArOArC(O) ArOArOArC(O)ArC(O) ArOArC(O)ArOArC(O)ArC(O) wherein each Ar is independently an aromatic moiety.

8. The method of claim 7, wherein each Ar is independently selected from the group consisting of substituted and unsubstituted mononuclear aromatic moieties and substituted and unsubstituted polynuclear aromatic moieties.

9. The method of claim 7, wherein Ar is phenylene.

10. The method of claim 1, wherein said polyaryletherketone is a homopolymer.

11. The method of claim 1, wherein said polymer is PEKK or an imide or sulphone copolymer thereof.

12. The method of claim 1, wherein the Lewis acid is added to the reaction medium prior to the controlling agent.

13. The method of claim 12, wherein the components are added to the reaction medium in the following order: (i) the Lewis acid (ii) the controlling agent (iii) the monomers and the capping agent.

14. The method of claim 1, wherein the amine-functionalized polyaryletherketone polymer is an amine-terminated polyaryletherketone polymer.

15. The method of claim 5, wherein each Z is independently selected from the group consisting of NHL, NRL and NL.sub.2, each L is a leaving group independently selected from the group consisting of an acetyl, haloacetyl, sulphonyl, halosulphonyl, SO.sub.2R, c is 1 to 10, each R is independently an aliphatic or aromatic group.

16. The method of claim 5, wherein a is 1, 2 or 3.

17. The method of claim 5, wherein b is 1, 2 or 3.

18. The method of claim 15, wherein Z is NHL, L is trifluoroacetyl, SO.sub.2CH.sub.3 or SO.sub.2CF.sub.3, c is 1 to 4, a is 1, and b is 1.

19. The method of claim 7, wherein Ar is an unsubstituted phenylene.

20. A method of preparing an amine-functionalized polyaryletherketone polymer, an imide- or sulphone-copolymer thereof or an amine-protected analogues thereof, said method comprising: polymerizing a monomer system in a reaction medium comprising a Lewis acid and a capping agent represented by formula (Z).sub.aAr(X).sub.b wherein: each X is independently selected from the group consisting of OAr, C(O)Cl, C(O)ArOAr and OAr[C(O)ArOAr].sub.cH, wherein each Ar is independently an aromatic group; c is an integer; Z is a protected amine group; a is 1 to 5; and b is 1 to 5.

21. The method of claim 20, wherein said reaction medium further comprises a controlling agent.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The present disclosure will now be further described by the following non-limiting examples and figures.

(2) FIG. 1 shows the produced functionalized PEKK particles with different tere:iso (T:I) ratios, produced according to Examples 1 (100:0), 2 (80:20) and 4 (60:40).

(3) FIG. 2 shows co-polymer backbone PEKK imide and cross-linked versions produced according to Examples 9 and 5 at different magnifications showing size, shape, and surface features

(4) FIGS. 3 and 4 are scanning electron micrograph (SEM) images of amine reactive end cap PEKK polymer particles produced according to Example 2 with T:I ratio of 80:20 at 500 and 2000 magnification, respectively. These images show spherical particles that are on average 50-60 m in diameter with some agglomeration of the particles as shown in FIG. 3. The surface features of the spherical particle as shown in FIG. 4 have characteristics similar to a raisin that the crevices and ridges were formed possibly due to contraction of the particle upon precipitating from solution.

(5) FIG. 5 shows an Infra-Red spectrum of the polymer of Example 1, showing NH.sub.2 groups.

(6) Table 1 shows the key information for the unfunctionalised (i.e. without amine end caps, prepared according to the method of WO 2011/004164) and amine end cap functionalized PEKK particles obtained according to the present invention. The inherent viscosities of both polymers were similar indicating similar molecular weights. The functionalized PEKK particle used the trifluoroacetyl protection route which was removed by treating the particles with a strong base to remove the trifluoroacetyl protecting group to obtain the reactive amine end group.

(7) TABLE-US-00002 TABLE 1 Inherent Viscosity Particle ID (dl/g) Capping agent Unfunctionalised 0.31 None Functionalized 0.28 CF.sub.3-EC

Example 1: Method for the Production of all 1,4-(100:0) PEKK with Terminal NH2 Functionality, 5% Out of Balance

(8) The reaction vessel was a glass, round bottomed, jacketed five liter reaction vessel with a bottom outlet and four baffles. Dichloromethane (2500 ml) was placed in the reaction vessel which was fitted with an overhead stirrer with an anchor head plus two intermediate paddles set at 90, a solids inlet, a nitrogen inlet and a thermocouple. The temperature of the vessel was controlled by a Julabo external cooler/heater unit and was logged using Julabo EasyTemp software.

(9) The vessel was purged with nitrogen and the dichloromethane cooled to 20 C. with stirring at 200 rpm, this stirring rate was used throughout the addition of all the reactants. The nitrogen purge was removed during the solid additions but reconnected during longer cooling periods. Aluminium chloride (AlCl.sub.3) (764.8 g, 5.74M) was added to the cooled dichloromethane resulting in a small temperature increase. On cooling back to 20 C., benzoic acid (292.96 g; 2.399M) was added slowly to the AlCl.sub.3 slurry such as to maintain the temperature of the slurry bellow 10 C. The dichloromethane slurry developed a yellow colour due to the aluminium chloride; the majority of it remained at the bottom of the vessel. The reaction mixture was then allowed to cool back to 20 C.

(10) Maintaining the reaction mixture below 5 C. 1,4-bis(4-phenoxybenzoyl)benzene (EKKE) 265.99 g; 0.5653M) was carefully added in portions. At this point the mixture turned bright opaque orange. The remaining monomer was transferred by washing with approximately 450 ml (200 ml) portions of dichloromethane. Terephthaloyl chloride (TPC) (120.81 g; 0.5951 M) was carefully added at a rate so as not to allow the mixture to rise above 10 C. The terephthaloyl chloride residues were transferred into the vessel by washing with approximately 200 ml dichloromethane in three portions.

(11) Lastly the end-capper (CF.sub.3-EC), 2,2,2-Trifluoro-N-(4-phenoxyphenyl) acetamide (16.69 g, 0.0596M) obtainable from Chem Bridge Corporation, San Diego, USA and purified prior to use was added with its washings, together with the remaining 100 ml of dichloromethane. The stirrer speed was increased to 500 rpm and maintained over the reaction time. The reaction mixture was slowly warmed to 5 C. then after 10 minutes to 20 C., where it was kept constant throughout the reaction time. After approximately 30 minutes all of the solids had dissolved forming an orange-red solution. After this point, dispersed polymer particles began to form. The reaction mixture was stirred rapidly for five hours. Sometimes it is necessary to add an additional 500 ml of dichloromethane to replace material that evaporates during the reaction. If the reaction is carried out in a pressurised vessel this will not be necessary. During this phase the nitrogen purge was replaced with a trap to collect and neutralise the hydrogen chloride evolved during the reaction.

(12) The reaction mixture was removed from the vessel via the bottom outlet.

(13) The reaction mixture is removed from the reaction vessel and isolated by vacuum filtration through a sinter. The orange solid was transferred to and decomplexed in approximately three liters of iced deionised water with stirring to produce a white particulate product. During decomplexing, the mixture should not reach greater than 5 C. The filtrate is also poured into iced water for decomplexing and disposal. The polymer remains in deionised water until workup. Prior to workup, the polymer particles should be entirely white, with no orange residues.

(14) Workup procedures are typically carried out using a stirrer hotplate. Constant stirring is achieved with a large magnetic stirrer bar. A representative workup procedure for a PEKK polymerisation carried out in a one liter reactor is as follows: Stand/stir in deionised water overnight at room temperature. Filtered and slowly added to 1.5 liters of stirred, hot deionised water to remove the residual dichloromethane 100 ml concentrated hydrochloric acid added, boiled for 1 hour, filtered, washed with 500 ml deionised water, filtered Slurry in 2 liters of deionised water, boiled for 1 hour, filtered, washed with 500 ml deionised water, filtered Repeat the above. Slurry in 2 liters of deionised water made to pH13 with ammonia solution (30 ml), boiled for 1 hour, filtered, washed with 500 ml deionised water, filtered Slurry in 2 liters deionised water, boiled for 1 hour, filtered, washed with 500 ml deionised water, filtered Pale cream PEKK powder isolated

(15) During this process the trifluoroactetyl protecting groups are removed from the end-capper leaving free terminal amine functionality.

(16) The powder was first dried at 120 C. overnight, or until dry, in an air oven. The powder was then re-dried at 200 C. overnight in a vacuum oven where the oven was continuously evacuated.

(17) Dry yield 270 g: 80% yield. The process produces a reasonable quantity of very fine particles and much of this is lost during the filtration steps.

(18) The IV of the resultant polymer was 0.85 dl/g. T.sub.g 182 C.; T.sub.m 396 C. The presence of the primary amine group was confirmed by using the Nihydrin test and the Infra-Red spectrum of FIG. 5.

Example 1A: Comparison of IV Values for Functionalised and Unfunctionalised Polymers

(19) As in Table 1 above, the IV value for the polymer of Example 1 (0.85 dl/g) was found to be comparable to that found for an unfunctionalised (i.e. non-amine terminated) analogue, the latter being capped using a benzoyl group and having an IV value of 0.91 dl/g. The unfunctionalised polymer was prepared according to a method similar to that of Example 2 of WO 2011/004164 (this method being 3.5% out of balance whereas Example 2 of WO 2011/004164 was 2.24% out of balance).

(20) The reagents used to produce the unfunctionalised PEKK were:

(21) 1,4-bis(4-phenoxybenzoyl)benzene0.1063M-50 g

(22) terephthaloyl chloride0.08204M-16.655 g

(23) isophthaloyl chloride0.02051 M-4.163 g

(24) Benzoic acid0.41 M-50 g

(25) Aluminium trichloride1.002M-133.64 g

(26) Benzoyl chloride0.003754M-0.5277 g

(27) Dichloromethane 450 ml

(28) To a 700 ml reaction flask equipped with a mechanical stirrer, having been purged with dry nitrogen, was added the 1,4-bis(4-phenoxybenzoyl)benzene along with 300 ml of dichloromethane. Having cooled the slurry to 20 C., the anhydrous aluminium trichloride was slowly added so as not to raise the temperature of the slurry above 10 C. and to minimise any splashing up the walls of the reactor. After cooling back to 20 C., a mixture of isophthaloyl chloride and terephthaloyl chloride was added to the slurry along with a further 100 ml of dichloromethane. Also at 20 C., the benzoic acid was added, followed by the benzoyl chloride as a capping agent.

(29) Whilst stirring at 100 rpm the reaction mass was allowed to warm towards room temperature without additional heating. During this period, the colour of the reaction mass changed from yellow to pale orange. As the mass showed signs of phase separating, the speed of the stirrer was raised to 350 rpm and this speed was maintained for the duration of the synthesis. During the polymerisation, hydrogen chloride was evolved which was trapped and disposed of safely.

(30) After stirring at room temperature for 6 hours the reaction mass was poured into 5 liters of iced water (care must be taken to avoid the temperature of the decomplexing mixture rising above room temperature). The aqueous mass was then stirred at room temperature for 4 hours or until all of the orange colouration had disappeared leaving a snow white mass.

(31) Having transferred the white mass to a suitable vessel, the vessel was heated and the dichloromethane distilled off. Having removed all of the dichloromethane, the mass was brought to reflux and refluxed for 1 hour whereupon the suspension was filtered whilst hot. While the filtrate was left to cool the white polymer solid was added to a further 3 liters of deionised water and brought to reflux. This was repeated a further two times and in each case the filtrate was added to the initial filtrate and allowed to cool. The polymer powder was then dried overnight at 150 C. under a partial vacuum. On cooling, benzoic acid crystallised from the combined filtrates. The yield of benzoic acid was enhanced by chilling the filtrates to 5 C.

Example 2: Method for the Production of 1,4:1,3(80:20) PEKK with Terminal NH2 Functionality, 5% Out of Balance

(32) This was carried out in exactly the same manner as example 1 but where the quantities of terephthaloyl (TPC) and Isophthaloyl (IPC) chlorides were 73.69 g, 0.3630M and 47.12 g 0.2321M respectively.

(33) The IV of the resultant polymer was 0.81 dl/g. T.sub.g 165 C.; T.sub.m 355 C.

Example 3: Method for the Production of 1,4; 1,3-(70:30) PEKK with Terminal NH2 Functionality, 5% Out of Balance

(34) This was carried out in exactly the same manner as example 1 but where the quantities of TPC and IPC chlorides were 50.13 g, 0.2470M and 70.68 g 0.3481M respectively.

(35) IV of the resultant polymer was 0.79 dl/g. T.sub.g 160 C., T.sub.m 338 C.

Example 4: Method for the Production of 1,4; 1,3(60:40) PEKK with Terminal NH2 Functionality 5% Out of Balance

(36) This was carried out in exactly the same manner as example 1 but where the quantities of TPC and IPC chlorides were 26.58 g, 0.1309M and 94.23 g 0.4642M respectively.

(37) The IV of the resultant polymer was 0.83 dl/g. T.sub.g 158 C.

Example 5: Method for the Production of 1,4; 1,3(80:20) PEKK with Terminal NH2 Functionality 5% Crosslinked, 5% Out of Balance

(38) This was carried out using the procedure in example 1 using the following reagents:

(39) TABLE-US-00003 EKKE 267.88 g (0.5693M) TPC 68.39 g (0.3369M) IPC 45.67 g (0.2249M) 1,3,5 Benzenetricarbonyl chloride 5.25 g (0.025M) Benzoic acid 289.16 g (2.37M) Aluminium trichloride 750.43 g (5.63M) CF.sub.3-EC 16.84 g (0.0599M)

(40) Note: This is on the basis of end group concentration.

(41) Total acid chloride end group conc. is (0.3369+0.2249)2+0.0253=1.1986

(42) 5% Out of balance is 0.951.1986=1.1387 or 0.5693M of EKKE=267.88 g

(43) Required CF.sub.3-EC is 1.1986-1.1387=0.0599M=16.85 g

(44) The IV of the resultant polymer was 1.5 dl/g. T.sub.g 166 C.; T.sub.m 352 C.

Example 6: Method for the Production of a PEKK-Imide (70:30), all Terephthaloyl with Terminal NH2 Functionality 5% Out of Balance

(45) This was carried out using the procedure in example 1 where some of the EKKE is replaced by the bis-imide monomer 5,5-Oxybis(2-(4-phenoxyphenyl)isoindoline-1,3-dione) EIEIE.

(46) ##STR00027##

(47) TABLE-US-00004 EKKE 139.64 g, (0.2968) EIEIE 81.99 g, (0.1272M) TPC 90.62 g, (0.4463M) Benzoic acid 218 g, (1.785M) Aluminium trichloride 612.38 g, (4.593M) CF.sub.3-EC 12.54 g, (0.0446M)

(48) The IV of the resultant polymer was 0.78 dl/g. T.sub.g 178 C.; T.sub.m 342 C.

Example 7: Method for the Production of NH2 End-Capped 80:20 PEKK; 5% Out of Balance

(49) The reaction vessel was a glass, round bottomed, jacketed two liter reaction vessel. Dichloromethane was placed in the reaction vessel fitted with an overhead stirrer with an anchor head, a solids inlet, a nitrogen inlet and a thermometer.

(50) Dichloromethane (500 mL) was added to the vessel which was purged with dry nitrogen cooled to 20 C. with stirring at 200 rpm. The mixture in the reaction vessel was stirred constantly at a rate of approximately 200 rpm during the following additions. The nitrogen purge was removed during the additions but reconnected during longer cooling periods. Aluminium chloride (80.56 g, 0.6042M) was added, followed by dimethyl sulphone (15.25 g, 0.162M), not allowing the mixture to rise above 10 C. due to the exotherms. The dichloromethane developed a yellow colour due to the aluminium chloride, the majority of it remained at the bottom of the vessel. The reaction mixture was then allowed to cool back to 20 C.

(51) A mixture of terephthaloyl chloride (9.6657 g; 0.0476M) and isophthaloyl chloride (6.7305 g; 0.03315M) was carefully added at a rate so as not to allow the mixture to rise above 10 C. The remaining acid chlorides were transferred by washing with approximately 50 ml dichloromethane in three portions. 1,4-Bis(4-phenoxybenzoylbenzene) (40 g; 0.085M) was carefully added at a rate so as not to allow the mixture to rise above 5 C. At this point the mixture turned bright opaque orange. The remaining monomer was transferred by washing with approximately 50 ml dichloromethane in three portions.

(52) Lastly, (CF.sub.3-EC) 2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide (2.3849 g; 0.00848M) was added with its washings (50 ml) of dichloromethane. The stirrer speed was maintained at 200 rpm and maintained over the reaction time. The reaction mixture was slowly warmed to 5 C. then after 10 minutes to 20 C., where it was kept constant throughout the reaction time. Upon warming, the nitrogen purge was removed and evolved hydrogen chloride captured using an aqueous solution of sodium bicarbonate. After approximately 30 minutes all of the solids had dissolved forming an orange-red solution. After this point the reaction mixture phase separated and eventually formed a gel. After full gellation the stirrer was stopped and the mixture maintained at +20 C. for between 4 and 5 hours. At the end of the reaction time the gel was removed from the vessel. The polymer complex was decomplexed in iced water using a 4 L Waring blender giving a snow white solid. When fully decomplexed the polymer was filtered off and washed with 1.5 L of deionised water. The polymer fluff was re-slurried in 2 L of deionised water and left stirring overnight under a flow of filtered air to remove most of the dichloromethane.

(53) Prior to workup, the polymer particles should be entirely white, with no orange parts remaining.

(54) Work up procedure: Stand in deionised water overnight Filtered and slowly added to 1.5 liters of stirred, hot deionised water to remove the residual dichloromethane 100 ml concentrated hydrochloric acid added, boiled for 1 hour, filtered, washed with 500 ml deionised water, filtered 1.5 liters of deionised water, boiled for 1 hour, filtered, washed with 500 ml deionised water, filtered 1.5 liters deionised water, boiled for 1 hour, filtered, washed with 500 ml deionised water, filtered 1.5 liters deionised water made to pH 13 with ammonia solution (30 ml), boiled for 1 hour, filtered, washed with 500 ml deionised water, filtered 1.5 liters deionised water, boiled for 1 hour, filtered, washed with 500 ml deionised water, filtered Off-white PEKK powder isolated

(55) The polymer was dried overnight under vacuum at 125 C. followed by further drying at 200 C. under vacuum also overnight.

(56) The resulting polymer had an IV of 0.6 dl/g. The polymer structure and the presence of free (unprotected) secondary amine groups were confirmed by .sup.1H, .sup.13C NMR and FT-IR spectroscopy. The secondary amine groups were also indicated using ninhydrin. DSC studies showed the polymer to have a T.sub.g at 160 C. and T.sub.m between 355-362 C.

(57) Other examples at 3%, 4% and 7% out of balance were similarly prepared and characterised, together with examples where the terephthaloyl to isophthaloyl ratios were 100:0, 90:10, 70:30 and 60:40.

(58) Similar results were obtained using N-acetyl-4-phenoxyaniline in place of 2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide (CF.sub.3-EC). However the work-up times needed to be extended to ensure complete removal of the less reactive protecting group.

Example 8Synthesis of Amine Terminated 70:30 PEKK

(59)
H.sub.2N-Ph-O-Ph-[-CO-Ph-CO-Ph-O-Ph-].sub.n-NH.sub.2

(60) A 2 L jacketed reaction vessel fitted with an efficient stirrer, thermometer, nitrogen inlet and gas outlet, containing 1 L of anhydrous dichloromethane was cooled to 20 C. under a nitrogen purge. To the cold stirred dichloromethane was added 113.6 gg (0.852 moles) of anhydrous aluminium trichloride. During this addition the temperature of the dichloromethane rose to 12 C. After re-cooling to 15 C., 20.19 g (0.2145 moles) of dimethyl sulphone was slowly added to the slurry keeping the temperature of the slurry below 5 C. At 10 C., 9.65 g (0.0475 moles) of Isophthaloyl chloride and 6.0779 g (0.0299 moles) of terephthaloyl chloride were added to the reaction mixture. Care was taken to ensure that both acid chloride residues were from the beakers and that caught on the addition funnel were completely washed into the reaction vessel using 100 cc of fresh dichloromethane. The temperature rise during this addition was minimal. Again at 15 C., 38.3686 g (0.0816 moles) of 1,4-bis(4-phenoxybenzoyl)benzene (EKKE) was slowly added to the slurry while maintaining the reaction temperature below 10 C. Residual EKKE was carefully washed into the reaction vessel using 100 cc of fresh dichloromethane. After connecting the reaction vessel to an acid gas scrubber, the temperature of the reaction mixture was increased to +20 C. over 45 minutes. Finally the protected end-capper N-acetyl-4-phenoxyaniline 1.9316 g (0.00851 moles) was added to the reaction mixture and any residues washed into the reaction vessel with 50 cc of fresh dichloromethane. During this time all of the reaction solids dissolved to give a clear orange solution and hydrogen chloride was seen to be evolved. The temperature of the reaction vessel was maintained at +20 C. for 6 hours. During the first 1.5 hours the viscosity of the orange solution increased until a gel was formed stopping the stirrer. At this point the stirrer was switched off.

(61) The polymer complex was decomplexed by blending the orange rubbery mass in a Waring blender in the presence of ice and water, the blending mixture being kept below +20 C. During this process the polymer turned from orange to show white. The white polymer fluff was filtered and washed on the filter with 21 L of deionised water. After removing the majority of the water by vacuum filtration, the polymer was slurried overnight in 4 L of deionised water at room temperature. After filtering, the fluff was slowly added to 3 L of hot (70 C.) deionised water in portions to minimise foaming as the dichloromethane was removed. To the hot slurry was then added 150 mL of concentrated hydrochloric acid and the slurry refluxed for 3 hours to ensure complete removal of the dichloromethane and removal of the protecting group. The fluff was then filtered again and the fluff washed on the filter with 22 L of deionised water. This process was then repeated. After the repeat the fluff was further refluxed for 1 hour in 4 L of deionised water containing 100 mL of 0.88 ammonia. After filtering and washing with 22 L of deionised water the fluff was finally again refluxed in 4 L of deionised water, filtered and washed.

(62) The polymer fluff was dried overnight (16 hours) at 100 C. followed by a further drying at 200 C. for 8 hours under vacuum.

(63) Optionally the polymer can be end capped using trifluoroacetyl protected end-capper CF.sub.3-EC (2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide) in place of N-acetyl-4-phenoxyaniline (CH.sub.3CONH-Ph-O-Ph).

(64) The IV of the polymer was 0.85 dl/g measure as a 0.1% solution in concentrated sulphuric acid. T.sub.g 164 C., T.sub.m 338 C.

Example 9Method for the Production of NH2 End Capped 100:0 PEKK-EIEIEKK 10% Random Copolymer

(65) The reaction vessel was a glass, round bottomed, jacketed five liter reaction vessel with a bottom outlet and four baffles. Dichloromethane (DCM) was placed in the reaction vessel fitted with an overhead stirrer with an anchor head and additional agitation vanes up the length of the stirrer shaft, a solids inlet, a nitrogen inlet and a thermocouple. The temperature of the vessel was controlled by a Julabo external cooler/heater unit and was logged using Julabo EasyTemp software.

(66) The vessel was purged with nitrogen and the dichloromethane (DCM) allowed to cool to 20 C. with stirring at 200 rpm. The mixture in the reaction vessel was stirred constantly at a medium rate of approximately 200 rpm during the following additions. The nitrogen purge was removed during the additions but reconnected during longer cooling periods. Aluminium chloride (609.64 g. 4.572M)) was added, followed by benzoic acid (218.24 g, 1.787M)), not allowing the mixture to rise above 10 C. due to the exotherms. The dichloromethane (DCM) developed a yellow colour due to the aluminium chloride, the majority of it remained at the bottom of the vessel. The reaction mixture was then allowed to cool back to 20 C.

(67) Terephthaloyl chloride (90.60 g) was carefully added at a rate so as not to allow the mixture to rise above 10 C. The remaining acid chloride was transferred by washing with approximately 100 ml dichloromethane (DCM) in three portions. (EIEIE) (82.20 g) was carefully added at a rate so as not to allow the mixture to rise above 10 C., causing the mixture to turn bright opaque orange. The remaining monomer was transferred by washing with approximately 50 ml dichloromethane (DCM) in three portions. EKKE (1,4-bis(4-phenoxybenzoylbenzene) (140.00 g, 0.2975M) was carefully added at a rate so as not to allow the mixture to rise above 5 C. The remaining monomer was transferred by washing with approximately 50 ml dichloromethane (DCM) in three portions.

(68) Lastly, CF.sub.3-EC (2,2,2-Trifluoro-N-(4-phenoxyphenyl) acetamide)(11.96 g, 0.0426M)) was added with its washings, together with the remaining dichloromethane (DCM). The stirrer speed was increased to 500 rpm and maintained over the reaction time. The nitrogen purge was removed and replaced with a water pump fitted with an air vent so as not to place the reaction system under vacuum. This was to trap and remove the hydrogen chloride evolved from the polymerisation. The reaction mixture was slowly warmed to 5 C. then after 10 minutes to 20 C., where it was kept constant throughout the reaction time. After approximately 30 minutes all of the solids had dissolved forming an orange-red solution. After this point, dispersed polymer particles began to form. The reaction mixture was stirred rapidly for five hours. The reaction mixture was removed from the vessel via the bottom outlet.

(69) The reaction mixture is removed from the reaction vessel and isolated by vacuum filtration through a sinter. The orange solid is decomplexed in approximately three liters of iced deionised water with stirring to produce a white particulate product. During decomplexation, the mixture should not reach greater than 5 C. The filtrate is also poured into iced water for decomplexation and disposal. The polymer remains in deionised water until workup. Prior to workup, the polymer particles should be entirely white, with no orange parts remaining.

(70) A representative workup procedure for a PEKK polymerisation carried out in a one liter reactor is as follows: Stand in deionised water overnight Filtered and slowly added to 1.5 liters of stirred, hot deionised water to remove the residual dichloromethane (DCM) Made up to 5 L with hot deionised water, 100 ml concentrated hydrochloric acid added, boiled for 1 hour, filtered, washed with 1 L deionised water, filtered 5 liters deionised water made to pH 13 with sodium hydroxide pellets, boiled for 1 hour, filtered, washed with 1 L deionised water, filtered 5 liters of deionised water, boiled for 1 hour, filtered, washed with 1 L deionised water, filtered 5 liters of deionised water, boiled for 1 hour, filtered, washed with 1 L deionised water, filtered 5 liters of deionised water, boiled for 1 hour, filtered, washed with 1 L deionised water, filtered Off-white PEKK powder isolated

(71) The IV of the resultant polymer was 0.75 dl/g.

Example 10Preparation of Capping AgentN-(4-Phenoxyphenyl)Acetamide

(72) ##STR00028##

(73) 4-Phenoxyaniline (20.4 g, 0.110 mol) was dissolved in glacial acetic acid (200 ml) with stirring. To the very dark brown solution was added decolourising charcoal (3 g) and the resulting suspension stirred for 15 minutes. The suspension was filtered through a Soxhlet thimble into a conical flask. On drainage of the thimble, further glacial acetic acid (200 ml) was filtered into the conical flask via the thimble. After cooling the conical flask in an ice bath to 5 C., acetic anhydride (11.1 cm.sup.3, 0.109 mol) was added to the aniline solution. An exothermic reaction occurred, raising the temperature to 30 C. After stirring for 30 minutes the solution was poured into water (1000 ml) and stirred for 10 minutes. After collecting the product by filtration the crude product was dried in an air over overnight at 80 C. The crude product was purified by crystallisation from hot methylcyclohexane (300 ml) and decolorised using activated charcoal. The pale pink product was collected by filtration, washed with 50 ml of methanol and dried under vacuum at 80 C. overnight. The product N-(4-phenoxyphenyl)acetamide was isolated as a pink crystalline solid (21.0 g, 85%); purity 99.99 mol % (DSC), m.p. 131.2 C. {lit. 130-131 C.}. Structure confirmed by FT-IR, .sup.1H NMR, .sup.13C NMR and mass spectrometry.

Example 114-Phenoxyaniline by the Hydrolysis of CF3-EC, 2,2,2-Trifluoro-N-(4-Phenoxyphenyl)Acetamide

(74) ##STR00029##

(75) A portion of CF.sub.3-EC (2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide), purified prior to use, (100 mg, 0.36 mmol), was placed in a beaker with deionised water (25 ml) and IPA (25 ml), and made up to pH 13 with a single sodium hydroxide pellet, which caused CF.sub.3-EC (2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide) to dissolve. The mixture was heated at 85 C. for 1.5 hours, during which time a white suspension was produced. The solid was isolated by filtration and, washed with deionised water and dried in an air oven to yield 4-phenoxyaniline as a white crystalline solid (47 mg, 71%), mp 85.1 C. {lit. 85-86 C.}; purity 99.95 mol % (DSC).

(76) Structure confirmed by FT-IR, .sup.1H NMR, .sup.13C NMR and mass spectrometry.

(77) Model CompoundsLinear

Example 12Synthesis of Model Compound 3

(78) ##STR00030##

(79) DCM (50 ml) was added to a conical flask with a magnetic stirrer, and cooled in ice to 5 C. Aluminium chloride (5.03 g, 37.7 mmol) was added, with stirring, together with the DCM washings. Between each of the subsequent additions and washings, the mixture was cooled in ice to below room temperature with stirring. Next, CF.sub.3-EC (2,2,2-trifluoro-N-(4-phenoxyphenyl) acetamide) (4.17 g, 14.8 mmol) was added, followed by TPC (1.51 g, 7.44 mmol), including the DCM washings (100 ml total). The mixture was stirred at room temperature for 1.5 hours, during which time the orange-brown solution became yellow. The reaction mixture was poured into stirring iced water, yielding a white precipitate in the DCM layer. This mixture was heated on a hotplate to remove the DCM. The cream precipitate 3 was isolated by filtration, was washed with deionised water (350 ml) and dried in an air oven. The cream product was recrystallised in dimethylacetamide, washed with acetone and dried in an air oven, yielding 5 as a grey solid (4.72 g, 92%); mp 325.0 C.; purity 98.85 mol % (DSC); Structure confirmed by FT-IR, .sup.1H NMR, .sup.13C NMR and mass spectrometry.

Example 13Synthesis of Model Compound 4

(80) ##STR00031##

(81) DCM (50 ml) was added to a conical flask with a magnetic stirrer and cooled in ice to 5 C. Aluminium chloride (4.84 g, 36.3 mmol) was added, with stirring, together with the DCM washings. Between each of the subsequent additions and washings, the mixture was cooled in ice to below room temperature with stirring. Next, CF.sub.3-EC (2,2,2-Trifluoro-N-(4-phenoxyphenyl) acetamide)(4.16 g, 14.8 mmol) was added, followed by TPC (1.51 g, 7.44 mmol), including the DCM washings (100 ml total). The mixture was stirred at room temperature for 1.5 hours, during which time the orange-brown solution became bright orange. The reaction mixture was poured into stirring iced water, yielding a white precipitate in the DCM layer. This mixture was heated on a hotplate to remove the DCM. The cream precipitate 4 was isolated by filtration, was washed with deionised water (350 ml) and dried in an air oven. The cream product was recrystallised in dimethylacetamide, washed with acetone and dried in an air oven, yielding 4 as a grey solid (4.76 g, 92%); m.p. 231.0 C.; purity 97.42 mol % (DSC); Structure confirmed by FT-IR, .sup.1H NMR, .sup.13C NMR and mass spectrometry.

Example 14Synthesis of Model Compound 5 by the Deprotection of 3

(82) ##STR00032##

(83) A portion of 3 (130 mg, 0.188 mmol), was placed in a beaker with deionised water (25 ml) and propan-2-ol (25 ml), and made up to pH 13 with a single sodium hydroxide pellet, which caused 3 to dissolve. The mixture was heated at 85 C. for 1.5 hours, during which time a cream suspension was produced. The solid was isolated by filtration, washed with deionised water and dried in an air oven to yield 5 as a beige crystalline solid (76 mg, 85%); mp 199.5 C., purity 97.63 mol % (DSC).

(84) Structure confirmed by FT-IR, .sup.1H NMR, .sup.13C NMR and mass spectrometry.

Example 15Synthesis of Model Compound 6 by the Deprotection of 4

(85) ##STR00033##

(86) A portion of 4 (113 mg, 0.164 mmol), was placed in a beaker with deionised water (25 ml) and IPA (25 ml), and made up to pH 13 with a single sodium hydroxide pellet, which caused 4 to dissolve. The mixture was heated at 85 C. for 1.5 hours, during which time a white suspension was produced. The solid was isolated by filtration, washed with deionised water and dried in an air oven to yield 6 as a white crystalline solid (62 mg, 80%); m.p. 165.2 C.; purity 98.74 mol % (DSC).

(87) Structure confirmed by FT-IR, .sup.1H NMR, .sup.13C NMR and mass spectrometry.

(88) Model CompoundsTrifunctional

Example 16Synthesis of Model Compound 1

(89) ##STR00034##

(90) DCM (100 ml) was added to a conical flask with a magnetic stirrer and cooled in ice to 5 C. Aluminium chloride (5.11 g, 38.3 mmol) was added, with stirring, together with the DCM washings. Between each of the subsequent additions and washings, the mixture was cooled in ice to below room temperature with stirring. Next, 1,3,5-benzenetricarbonyl chloride (1.52 g, 5.73 mmol) was added, followed by 2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide (6.00 g, 21.3 mmol), including the DCM washings (100 ml total). The addition of 2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide caused the solution to turn green. The mixture was stirred at room temperature for 1.5 hours. After 5 minutes the solution became orange, then after a further 15 minutes a dark viscous liquid formed at the bottom of the flask. The resulting orange solution and dark orange viscous solid was poured into iced water, and was stirred at a moderate speed for 1 hour, resulting in a small amount of a white precipitate in the aqueous layer and an orange organic layer. This mixture was heated on a hotplate to remove the DCM. A green sticky solid was isolated by decanting the aqueous layer. This solid was dissolved in acetone (100 ml) and decolourising charcoal added (1 g). After stirring for 10 minutes, the solution was filtered, yielding a pale brown solution. On evaporation of the acetone, a brown sticky solid remained. This solid was stirred in methanol (100 ml), causing the precipitation of a white solid. The solid was isolated by filtration and dried in an air oven, yielding 1 as a pale grey solid (0.78 g, 32%); m.p. 172.3 C.; purity 97.82 mol % (DSC).

(91) Structure confirmed by FT-IR, .sup.1H NMR, .sup.13C NMR and mass spectrometry.

Example 17Synthesis of Model Compound 2

(92) ##STR00035##

(93) A portion of 1 (153 mg, 0.153 mmol), was placed in a beaker with deionised water (25 ml) and propan-2-ol (25 ml), and made up to pH 13 with a single sodium hydroxide pellet, which caused 1 to dissolve. The mixture was heated at 85 C. for 1.5 hours, during which time a yellow suspension was produced. The solid was isolated by filtration, washed with deionised water and dried in an air oven to yield 2 as a pale yellow solid (0.0771 g, 71%); mp 167.4 C., purity 97.72 mol % (DSC).

(94) Structure confirmed by FT-IR, .sup.1H NMR, .sup.13C NMR and mass spectrometry. The protected amine had been deprotected.

Example 18Sulphone Copolymer (Random)

(95) As in example 1 where the reagents used were:

(96) Reaction run 3% out of balance to give a random copolymer.

(97) TABLE-US-00005 4,4-diphenoxybenzophenone (EKE) 22.7547 g (0.0621M) 4,4-diphenoxydiphenylsulphone (ESE) 24.9934 g (0.0621M) Terephthaloyl chloride (TPC) 26 g (0.1281M) CF.sub.3-EC 2.1936 g (7.8 10.sup.3M) Dimethyl sulphone (Lewis base) 23.17 g (0.2462M) Aluminium trichloride (Lewis acid) Dichloromethane (DOM)

(98) The polymer gel was decomplexed in ice/water using a Waring blender. The polymer fluff was worked up as in example 1.

(99) IV of the resultant polymer was 1.13 dl/g. T.sub.g was 183 C., the polymer was amorphous.

Example 19Suphone Copolymer (Block)

(100) As in example 18 but the resultant polymer was a block co-polymer.

(101) In this instance the ESE was first reacted with 9.4556 g (0.04657M) of TPC and after 1 hour at 20 C the remainder of the TPC plus the EKE was added followed by the CF.sub.3-EC. The polymer gel was worked up as in example 18.

(102) The IV of the resultant polymer was 1.08 dl/g. The T.sub.g of the product was 180 C. and the T.sub.m 362 C. The polymer was semi-crystalline.