METHOD FOR MAKING POLYARYLALIPHATICETHERKETONE POLYMERS AND COPOLYMERS THEREOF

Abstract

The present disclosure provides a process for producing a polymer, said process comprising polymerising a monomer system comprising a compound of formula: Ar—O—Ar—C(═O)—X—C(═O)—Ar—O—Ar in a reaction medium comprising a Lewis acid where: X is an aliphatic moiety and Ar is an aromatic moiety.

Claims

1. A process for producing a polymer, said process comprising polymerizing a monomer system comprising a compound of formula: Ar—O—Ar—C(═O)—X—C(═O)—Ar—O—Ar in a reaction medium comprising a Lewis acid, wherein: X is an aliphatic moiety, and Ar is an aromatic moiety.

2. The process as claimed in claim 1, wherein the reaction medium further comprises a dielectrophile.

3. The process as claimed in claim 2, wherein said dielectrophile is a compound of formula: L-(O═)C—Ar—C(═O)-L, wherein L is a leaving group.

4. The process as claimed in claim 1, wherein X is selected from cyclohexyl (Cy) and —{CH.sub.2}.sub.n—, wherein n is an integer from 1 to 100, preferably 2 to 50, most preferably 2 to 22, preferably 2 to 18 or 2 to 12, especially, 3 to 10, e.g. 3, 4, 5, 6, 8 or 10.

5. The process as claimed in claim 1, wherein the compound of formula: Ar—O—Ar—C(═O)—X—C(═O)—Ar—O—Ar is polymerized in presence of a controlling agent.

6. The process as claimed in claim 5, wherein the controlling agent is a Lewis base (e.g. an aprotic Lewis base).

7. The process as claimed in claim 5, wherein the controlling agent is an aromatic carboxylic acid, aromatic sulphonic acid or a derivative thereof.

8. The process as claimed in claim 7, wherein the controlling agent is selected from the group consisting of: (i) Ar(COOG).sub.y; (ii) Ar(SO.sub.3G).sub.y; (iii) (ArCOO.sup.−).sub.z(Met).sup.z+; and (iv) (ArSO.sub.3.sup.−).sub.z(Met).sup.z+ wherein Ar is an aromatic group compatible with the remaining components of the reaction medium; each G independently is a hydrogen atom or an organic group (R); each y independently is 1, 2 or 3; each (Met) independently is a metal ion; and each z independently is an integer equal to the charge on the metal ion (Met).sup.z+.

9. The process as claimed in claim 7, wherein the controlling agent is benzoic acid.

10. The process as claimed in claim 5, wherein an amount of the controlling agent is from 0.25 to 4 equivalents, especially 1 to 2 equivalents, especially 2 equivalents, per equivalent of acid halide groups.

11. The process as claimed in claim 1, wherein the aromatic moiety (Ar) is independently selected from the group consisting of substituted and unsubstituted mononuclear aromatic moieties (e.g. phenyl or phenylene) and substituted and unsubstituted polynuclear aromatic moieties such as naphthyl.

12. The process as claimed in claim 1, wherein the compound of formula: Ar—O—Ar—C(═O)—X—C(═O)—Ar—O—Ar is polymerized with a comonomer.

13. The process as claimed in claim 1, wherein the compound of formula: Ar—O—Ar—C(═O)—X—C(═O)—Ar—O—Ar is polymerized in the presence of a capping agent comprising —NR.sub.2, —NRH or a protected amine group.

14. A polymer or oligomer obtainable by the process of claim 1.

15. A polymer or oligomer comprising a repeat unit —Ar—O—Ar—C(═O)—X—C(═O)—Ar—O—Ar—C(═O)—Ar—C(═O)—, wherein X is an aliphatic moiety, Ar is an aromatic moiety, or copolymer thereof.

16. The polymer or oligomer as claimed in claim 15 consisting essentially of the repeat unit —Ar—O—Ar—C(═O)—X—C(═O)—Ar—O—Ar—C(═O)—Ar—C(═O)—.

17. The polymer, oligomer or copolymer as claimed in claim 15, wherein said polymer, oligomer or copolymer is amine functionalised.

18. The polymer, oligomer or copolymer as claimed in claim 14, wherein the polymer, oligomer or copolymer is in a form of a particle, fluff or flake.

19. A compound of formula Ar—O—Ar—C(═O)—X—C(═O)—Ar—O—Ar, wherein X is an aliphatic moiety, Ar is an aromatic moiety.

20. A process for preparing a compound of formula Ar—O—Ar—C(═O)—X—C(═O)—Ar—O—Ar (EKXKE), said process comprising reacting diphenyl ether with a dicarboxylic acid halide of X in presence of a Lewis acid, wherein a molar concentration of diphenyl ether are in excess with respect to a molar concentration of the dicarboxylic acid halide of X, wherein X is an aliphatic moiety.

21. A process for preparing a compound of formula Ar—O—Ar—C(═O)—X—C(═O)—Ar—O—Ar (EKXKE), said process comprising reacting a dicarboxylic acid halide of X with excess halobenzene (e.g. fluorobenzene) in presence of a Lewis acid to produce Hal-Ph-C(═O)—X—C(═O)-Ph-Hal, and subsequently reacting Hal-Ph-C(═O)—X—C(═O)-Ph-Hal with a phenate salt, preferably in a dipolar aprotic solvent, preferably at elevated temperature, wherein X is an aliphatic moiety.

22. The process as claimed in claim 20, wherein said dicarboxylic acid halide is a compound of formula ClC(═O)—X—C(═O)Cl.

23. A composition or article comprising the compound as claimed in claim 19.

Description

EXAMPLE 1—SYNTHESIS OF PEK(10)KEKK (GEL METHOD): ALL ISOPHTHALOYL, 2% OOB

[0219] -[-Ph-O-Ph-CO—(CH.sub.2).sub.10—CO-Ph-O-Ph-CO-Ph-CO—]—

[0220] A 5 L jacketed reaction vessel fitted with an efficient stirrer, thermometer, nitrogen inlet and gas outlet, containing 1.5 L of anhydrous dichloromethane was cooled to −20° C. under a nitrogen purge. To the cold stirred dichloromethane was added 458.35 g (3.44 moles) of anhydrous aluminium trichloride. During this addition the temperature of the dichloromethane rose to −12° C. After re-cooling to −15° C., 70.5 g (0.75 moles) of dimethyl sulphone was slowly added to the slurry keeping the temperature of the slurry below −5° C. At −10° C., 101.51 g (0.5 moles) of Isophthaloyl chloride was added to the reaction mixture. Care was taken to ensure that all Isophthaloyl residues from the beaker and that caught on the addition funnel were completely washed into the reaction vessel using 100 ml of fresh dichloromethane. The temperature rise during this addition was minimal. Again at −15° C., 272.68 g (0.51 moles) of 1,10-bis(4-phenoxybenzoyl)decane (EK10KE) was slowly added to the slurry while maintaining the reaction temperature below −10° C. Residual EK10KE was carefully washed into the reaction vessel using 100 ml 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. 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.

[0221] 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 snow white. The white polymer fluff was filtered and washed on the filter with 2×2 L of deionised water. After sucking the fluff dry it was slurried overnight in 4 L of deionised water at room temperature. After filtering the fluff was slowly added to 4 L of hot (70° C.) deionised water in portions to minimise foaming as the dichloromethane was removed. The white slurry was then refluxed for 2 hours to ensure complete removal of the dichloromethane. The fluff was then filtered again and the fluff washed on the filter with 2×2 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 2×2 L of deionised water the fluff was finally again refluxed in 4 L of deionised water, filtered and washed.

[0222] The polymer fluff was dried overnight (16 hours) at 100° C. followed by a further drying at 140° C. for 8 hours under vacuum.

[0223] Optionally the polymer can be end capped using benzoyl chloride.

[0224] The above synthesis give a polymer with phenoxy end groups as the synthesis was carried out 2% out of balance.

[0225] The IV of the polymer was 1.29 gl/g measure as a 0.1% solution in concentrated sulphuric acid.

[0226] The T.sub.g of the polymer was at 76° C., T.sub.c at 153° C. and T.sub.m 197° C. measure using DSC from a fully quenched amorphous sample.

[0227] The TGA of the polymer in air showed a 1% weight loss at 330° C.

[0228] The polymer was shown to be 38% crystalline by XRD.

[0229] Melt viscosity of the polymer measured at 71 Hz at 250° C. showed the polymer to have a viscosity of 5100 Pa.Math.s after 10 mins and 6000 Pa.Math.s after 30 mins.

[0230] The flexural modulus of the polymer at 23° C. was 2.78 GPa.

[0231] The yield strength of the polymer was 70 MPa at 23° C., elongation to yield was 4.9% and elongation to break was 24% at 23° C.

[0232] The polymer was fully characterised by .sup.1H and .sup.13C NMR spectroscopy and found to be linear.

EXAMPLE 2—SYNTHESIS OF PEK-10-KEKK ALL TEREPHTHALOYL

[0233] Carried out as in example 1 using terephthaloyl chloride in place of isophthaloyl chloride 1.5% out of balance. IV=1.4 dl/g

[0234] T.sub.g 74.5° C.; T.sub.c1 92.8° C.; T.sub.c2 221° C.; T.sub.m 276.5° C.

EXAMPLE 3—SYNTHESIS OF PEK-10-KEKK ALL TEREPHTHALOYL

[0235] As in example 2 using dimethylacetamide in place of dimethylsulphone. IV=1.22 dl/g

[0236] T.sub.g 75° C.; T.sub.c1 93.5° C.; T.sub.c2 221° C.; T.sub.m 276° C.

EXAMPLE 4—SYNTHESIS OF PEK-4-KEKK ALL TEREPHTHALOYL

[0237] As in example 1 where the monomer EK-10-KE was replaced by the monomer EK-4-KE. Isophthaloyl chloride was replaced by terephthaloyl chloride.

[0238] IV=0.92 dl/g

[0239] T.sub.g 119° C.; T.sub.c1 143° C.; T.sub.c2 232° C.; T.sub.m1 305° C.; T.sub.m2 328° C.

EXAMPLE 5—SYNTHESIS OF PEK-CYCLOHEXYL-KEKK ALL TEREPHTHALOYL

[0240] As in example 1 where the monomer EK-10-KE was replaced by the monomer EK-cyclohexyl-KE and Isophthaloyl chloride was replaced by terephthaloyl chloride. IV=1.83 dl/g

[0241] T.sub.g 172° C.; T.sub.c 220° C.; T.sub.m 350° C.

EXAMPLE 6—SYNTHESIS OF PEK-CYCLOHEXYL-KEKK ALL ISOPHTHALOYL

[0242] As in example 5 where the terephthaloyl chloride was replaced by Isophthaloyl chloride. IV=0.87 dl/g

[0243] T.sub.g 157° C.; T.sub.c 276° C.; T.sub.m1 268° C.; T.sub.m2 303° C.

EXAMPLE 7—SYNTHESIS OF PEK-3-KEKK ALL TEREPHTHALOYL

[0244] As in example 1 where the monomer EK-10-KE was replaced by the monomer EK-3-KE and isophthaloyl by terephthaloyl chloride. IV=1.59 dl/g

[0245] T.sub.g 127° C.; T.sub.c 220° C.; T.sub.m 280° C.

EXAMPLE 8—SYNTHESIS OF PEK-5-KEKK ALL TEREPHTHALOYL

[0246] As in example 1 where the monomer EK-10-KE was replaced by the monomer EK-5-KE and isophthaloyl by terephthaloyl chloride. IV=0.88 dl/g

[0247] T.sub.g 114° C.; T.sub.c1 148° C.; T.sub.c2 236° C.; T.sub.m 285° C.

EXAMPLE 9—SYNTHESIS OF PEK-8-KEKK ALL TEREPHTHALOYL

[0248] As in example 1 where the monomer EK-10-KE was replaced by the monomer EK-8-KE and isophthaloyl by terephthaloyl chloride. IV=0.98 dl/g

[0249] T.sub.g 89° C.; T.sub.c 228° C.; T.sub.m 285° C.

EXAMPLE 10—SYNTHESIS OF COPOLYMER PEK-4-KEKK-EK-10-KEKK

[0250] As in example 1 where the monomer EK-10-KE was replaced by the monomers EK-10-KE and EK-4-KE in the ratio 1:2 and isophthaloyl by terephthaloyl chloride. IV=1.01 dl/g

[0251] T.sub.g 99° C.; T.sub.c1 126° C.; T.sub.c2 229° C.; T.sub.m 298° C.

EXAMPLE 11—SYNTHESIS OF PEK-8-KEKK, ISOPHTHALOYL TEREPHTHALOYL

[0252] As in example 1 where the monomer EK-10-KE was replaced by the monomer EK-8-KE and the monomer isophthaloyl chloride was replaced by the mixed monomers terephthaloyl and isophthaloyl chloride in the ratio 2:3. IV=0.95 dl/g

[0253] T.sub.g 83° C.; T.sub.c1 147° C.; T.sub.m1 200° C.; T.sub.c2 211° C.; T.sub.m2 230° C.

EXAMPLE 12—SYNTHESIS OF PEK-6-KEKK ISOPHTHALOYL TEREPHTHALOYL

[0254] As in example 1 where the monomer EK-10-KE was replaced by the monomer EK-6-KE and the monomer isophthaloyl chloride was replaced by the mixed monomers terephthaloyl and isophthaloyl chloride in the ratio 2:3. IV=1.03 dl/g

[0255] T.sub.g 96° C.; T.sub.c1 180° C.; T.sub.m1 208° C.; T.sub.c2 211° C.; T.sub.m2 254° C.

EXAMPLE 13—SYNTHESIS OF THE CO-POLYMER PEK10KEKK-PEKK

[0256] As in example 1 where the monomer EK10KE was replaced by a mixture of the monomers EK10KE and 1,4-bis(4-phenoxybenzoyl)benzene (EKKE) in the ratio 3:1. IV=1.31 dl/g.

[0257] The polymer was amorphous with a T.sub.g at 91° C.

EXAMPLE 14—SYNTHESIS OF PEK8KEKK ISOPHTHALOYL TEREPHTHALOYL

[0258] As in example 1 where the monomer EK10KE was replaced by the monomer EK8KE and the monomer isophthaloyl chloride was replaced by the mixed monomers terephthaloyl and isophthaloyl chloride in the ratio 3:2. IV=1.00 dl/g

[0259] T.sub.g 90° C.; T.sub.c 142° C.; T.sub.m1 212° C.; T.sub.m2 255° C.

EXAMPLE 15—DISPERSION SYNTHESIS OF THE COPOLYMER PEK10KEKK-PEKK

[0260] As in example 13 where the ratio of EK10KE to EKKE was 7:3, the ratio of terephthaloyl to isophthaloyl chlorides was 1:1 and where the dimethyl sulphone was replaced by benzoic acid where the ratio of benzoic acid to total terephthaloyl and isophthaloyl chlorides was 4:1. The product was isolated as a fine orange powder which was white after decomplexing. The first stage of the work up was to heat to reflux the white slurry in 10% aqueous hydrogen chloride for one hour. The same work up procedure was then followed as in example 1. IV=1.12 gl/g

[0261] T.sub.g 78° C.; T.sub.c 114° C.; T.sub.m very broad 265° C.

EXAMPLE 16—DISPERSION SYNTHESIS OF THE POLYMER PEK-10-KEKK ISOPHTHALOYL TEREPHTHALOYL

[0262] As in example 1 where the terephthaloyl to isophthaloyl ratio was 1:1 and where the dimethyl sulphone was replaced by benzoic acid where the ratio of benzoic acid to total terephthaloyl to isophthaloyl chlorides was 1:4. The product was isolated as a fine orange powder which was white after decomplexing. The first stage of the work up was to heat to reflux the white slurry in 10% aqueous hydrogen chloride for one hour. The same work up procedure was then followed as in example 1. IV=0.82 dl/g

[0263] T.sub.g 76° C.; T.sub.c1 105° C.; T.sub.c2 212° C.; T.sub.m 255° C.

EXAMPLE 17—DISPERSION SYNTHESIS OF THE COPOLYMER PEK10KEKK-PESEKK

[0264] As in example 13 where the ratio of EK10KE to 4,4′-diphenoxydiphenylsulphone (ESE) was 2:1, the acid chloride was 100% terephthaloyl chloride and where the dimethyl sulphone was replaced by benzoic acid where the ratio of benzoic acid to terephthaloyl chloride was 4:1. The product was isolated as a fine orange powder which was white after decomplexing. The first stage of the work up was to heat to reflux the white slurry in 10% aqueous hydrogen chloride for one hour. The same work up procedure was then followed as in example 1. IV=0.74 gl/g

[0265] T.sub.g 100° C.; T.sub.c1 152° C.; T.sub.c2 207° C.; T.sub.m 249° C.

EXAMPLE 18—DISPERSION SYNTHESIS OF THE COPOLYMER PEK10KEKK-PEIEIEKK

[0266] As in example 13 where the ratio of EK10KE to imide monomer (EIEIE) was 4:1, the acid chloride was 100% terephthaloyl chloride and where the dimethyl sulphone was replaced by benzoic acid where the ratio of benzoic acid to terephthaloyl chloride was 4:1. The product was isolated as a fine orange/red powder which was white after decomplexing. The first stage of the work up was to heat to reflux the white slurry in 10% aqueous hydrogen chloride for one hour. The same work up procedure was then followed as in example 1. IV=0.66 dl/g

[0267] T.sub.g 84° C.; T.sub.c 213° C.; T.sub.m 266° C.

EXAMPLE 19—SYNTHESIS OF PH-O-PH-CO—{CH.SUB.2.}N-CO-PH-O-PH (EKXKE) MONOMERS SYNTHESIS OF 1,10-BIS(4-PHENOXYBENZOYL)DECANE; PH-O-PH-CO—{CH.SUB.2.}.SUB.10.—CO-PH-O-PH

[0268] To a 5 litre jacketed reaction vessel fitted with a mechanical stirrer, thermometer and nitrogen inlet/gas outlet was added 1500 ml of dry dichloromethane (DCM). All additions were carried out under a dry nitrogen atmosphere. After cooling the DCM to −20° C. anhydrous aluminium chloride (208 g; 1.56M) which was added accompanied by a slight exotherm. After allowing the temperature of the slurry to fall back to −20° C., diphenyl ether (208 g; 1.56M) was added slowly to the slurry whilst maintaining the temperature of the slurry below −10° C. When the diphenyl ether had been added, dodecanedioyl dichloride (174 g; 0.65M) dissolved in 500 ml of dry DCM, was added whilst maintaining the reaction of the slurry below −15° C. Upon completion of the addition of the dodecanedioyl dichloride the temperature of the slurry was raised to 0° C. over 1 hour and the nitrogen purge replaced by a gas outlet attached to an acid gas scrubber. During this time the solution became dark orange and hydrogen chloride gas was evolved. After gas evolution had ceased, about 3 hours, the reaction temperature was raised to +20° C. over another 2 hours. The crude product was isolated from the dark orange reaction mixture by carefully pouring the mixture into 5000 ml of ice/water with stirring. Care needs to be taken as this step is highly exothermic. After complete decomplexation the mixture consisted of a white paste and water. After decanting off the aqueous layer the paste was slurried in 2500 ml of methanol with stirring. The white product was separated from the methanol by filtration. The white product was returned to another 2000 ml of methanol and re-filtered to ensure complete removal of excess diphenyl ether. After rinsing the product on the filter with 1000 ml of fresh methanol the white powder was dried overnight at +50° C. The product was purified to polymerisation grade by crystallisation from methylcyclohexane (125 g/litre) to give a pure white crystalline product that was dried overnight under vacuum at +50° C.

[0269] Yield of crude product: 347 g; Yield of pure product: 322 g (92%)

[0270] The purity of the product was 99.93M/% as determined by DSC. Melting point: 104-105° C.

[0271] The structure of the product was confirmed by .sup.1H, .sup.13C NMR spectroscopy and mass spectrometer.

[0272] Other EK-{CH.sub.2}n-KE monomers were prepared in a similar fashion, see table below.

TABLE-US-00006 Melting Monomer Point/° C. DSC Purity/% Yield/% EK-3-KE 100   99+ ~90+ EK-4-KE 125.5 99+ ~90+ EK-5-KE 79 and 82.2 Gave high molecular ~90+ weight polymer EK-6-KE 124   99+ ~90+ EK-8-KE 107.5 99+ ~90+ EK-10-KE 105.3 99+ ~90+ EK-Cyclohexyl-KE 182.5 (major); Gave high molecular ~90+ 217.3 (minor) weight polymer Possible cis/trans isomers EK-12-KE 99+ ~90+ EK-18-KE