WO1990000573A1

WO1990000573A1 - Ethersulphone polymers

Info

Publication number: WO1990000573A1
Application number: PCT/GB1989/000751
Authority: WO
Inventors: Ian David Henderson Towle
Original assignee: Raychem Limited
Priority date: 1988-07-05
Filing date: 1989-07-04
Publication date: 1990-01-25
Also published as: AU3980889A; GB8815976D0; JPH03505748A; KR900701887A; EP0423220A1

Abstract

A polymer or copolymer comprising (A) at least 5 mol % of aromatic ether sulphone backbone units of formula (I) -aryl-aryl-O-Ar-SO2-Ar-O-aryl-aryl-, wherein -O- is ether oxygen, each Ar independently is an arylene moiety or represents a number of arylene moieties linked together by -O- or -CO-, each aryl-aryl moiety independently comprises two or more aryl rings which are (a) fused together or (b) twice bonded together directly and/or through linking groups to form a cyclic linking structure between the said rings or (c) directly single-bonded together in the polymer backbone chain, and the units (I) are linked together or to other units in the polymer backbone by linking groups, preferably -O-, -CO-, or -SO2- groups.

Description

ETHERSULPHONE POLYMERS

This invention relates to ethersulphone polymers.

This invention provides a polymer comprising (A) at least 5 mol % of aromatic ether sulphone backbone units of formula

-aryl-aryl-O-Ar-SO₂-Ar-O-aryl-aryl- (I) wherein -O- is ether oxygen, each Ar independently is an arylene moiety or represents a number of arylene moieties linked together by -O- or -CO-, each aryl-aryl moiety independently comprises two or more aryl rings which are (a) fused together or (b) twice bonded together directly and/or through linking groups to form a cyclic linking structure between the said rings or (c) directly single-bonded together in the polymer backbone chain, and the units (I) are linked together or to other units in the polymer backbone by linking groups, preferably -O-, -CO-, or -SO₂- groups.

Preferred polymers according to the invention are partly crystalline, and preferably incorporate (B) aro matic ketone backbone units. These units (B) are preferably of formula

-Ar'-CO-(Ar'-O)_n-(Ar')_m- (II) wherein each Ar' independently is an arylene moiety or represents a number of arylene moieties linked together by -O- or -CO- or -SO₂- groups, and n and m independently are 0 or 1.

Preferably, the proportion of SO₂ groups is

controlled to prepare such polymers with a significant degree of crystallinity, contrary to the normal expectation that sulphones produce amorphous polymers.

Polymers can be produced according to the invention which have great potential as engineering polymers owing to their high glass transition temperatures (Tg), exceeding 200ºC in some cases, combined with conveniently low crystalline melting temperatures (Tm), preferably below 400ºC, more preferably below 385ºC.

Such Tm facilitates melt processing at temperatures safely below the limiting polymer decomposition temperatures and conveniently within the capabilities of existing processing equipment.

By "aromatic" backbone units is meant units having aromatic moieties which moieties form part of the polymer backbone chain (not merely pendant aromatic rings as in polystyrene), and preferably units having no two adjacent aliphatic carbon atoms in the backbone chain. Preferably, at least some of the aromatic ketone backbone units are incorporated in aromatic ether ketone repeat units, especially those of formula

-Ar-O-Ar-CO-Ar-O-Ar-CO-Ar-CO- (III) or -Ar-O-Ar-CO-Ar-CO- (III A) or -Ar-O-Ar-CO-naph-CO-Ar-O-Ar-CO-Ar-CO- (IV), wherein naph is a naphthylene moiety.

Particularly preferred polymers are those wherein substantially all of the ether ketone units are of those formulae.

Such ether ketone units are preferably derived (a) from copolymerisation of an ether ketone monomer of formula

H-Ar-O-Ar-CO-Ar-O-Ar-H (V) and a diacyl monomer of formula

X-CO-Ar'-CO-X (VI) or (b) from copolymerisation of an aryl ether monomer of formula

H-Ar-O-Ar-H (VII) and a diacyl monomer of formula

X-CO-Ar'-CO-X (VIII) or X-CO-naph-CO-X (VIII A) wherein X is halogen with one or more monomers providing the said ether sulphone backbone units, the diacyl monomer in each case being substantially in stoichiometric balance with the -H- terminated monomers (including the sulphone

monomer (s)).

The ether sulphone units may be derived from two or more monomers, but are preferably derived from polymerisation of a corresponding ether sulphone monomer of formula

H-aryl-aryl-O-Ar-SO₂-Ar-O-aryl-aryl-H (IX)

Promising polymers may be prepared comprising from 5 to 20 mol %, preferably from 10 to 15 mol %, of the said ether sulphone backbone units.

Especially desirable are polymers wherein those backbone units are incorporated in ether ketone sulphone repeat units of formula

-aryl-aryl-O-Ar-SO₂-Ar-O-aryl-aryl-CO-Ar-CO- (X) which are preferably derived from copolymerisation of an ether sulphone monomer of formula (IX) and a diacyl monomer of formula

X-CO-Ar'-CO-X (XI) wherein X is halogen with one or more other monomers providing the said ketone backbone units, the diacyl monomer (XI) being substantially in stoichiometric balance with the ether sulphone monomer and the other monomer (s).

Preferred polymers comprise from 10 to 45 mol %, more preferably from 20 to 40 mol %, and especially from 30 to 35 mol %, of the said ether ketone sulphone repeat units.

The ether ketone units may be pre-polymerised to form a polymer block which is copolymerised into the finished polymer together with the ether sulphone units. Such pre-blocking tends to reduce the crystallisation time of the molten copolymer (e.g., to 1/10 that of the corresponding random copolymers) and tends to increase Tg while maintaining the semi-crystalline nature of the copolymer.

The starting monomer of formula (IX) is advantageous in being relatively simple and economical to synthesise (as hereinafter described), while imparting highly desirable characteristics to the polymers in which it is incorporated. The use of this monomer to form repeat units in the molecular backbone of polymers is believed to be new per se, and the invention accordingly includes a polymer comprising in its molecular backbone aromatic ether sulphone backbone units derived from polymerisation of an ether sulphone monomer of formula

H-aryl-aryl-O-Ar-SO₂-Ar-O-aryl-aryl-H (IX) wherein -O- is ether oxygen each Ar independently is an arylene moiety, or represents a number of arylene moieties linked together by -O- or -CO-, and each aryl-aryl moiety independently comprises two or more aryl rings which are (a) fused together or (b) twice bonded together directly and/or through linking groups to form a cyclic linking structure between the said rings or (c) directly single-bonded together in the polymer backbone chain.

Preferably, each Ar group represented by or included in the foregoing formulae is a phenylene moiety and each arylene moiety represented by or included in Ar' is a phenylene moiety, p-phenylene moieties being preferable in some cases, although a proportion of m-phenylene moieties may usefully adjust the degree of crystallinity and/or the rate of crystallisation or other properties in the resulting polymers.

It is preferred that at least some (preferably substantially all) of the aryl-aryl moieties are biphe- nylene moieties, especially 4,4'-biphenylene moieties, but the invention includes polymers wherein at least some of the aryl-aryl moieties comprise terphenylene, polyphenylene, naphthylene, anthracylene, xanthylene, or O and/or N and/or S heterocyclic analogues thereof, for example phenoxanthiinylene suitably bonded

into the polymer backbone. Such aryl-aryl moieties may also be included as or in the Ar' moieties instead of the preferred phenylene moieties.

The novel polymer structures of this invention may be synthesised by any desired method, for example by the well-known nucleophilic reactions described in numerous patents in the name of ICI and others (assuming suitable starting monomers are obtainable). It is, however, very much preferable to use an improved electrophilic reaction of the kind described by Raychem Corporation in published European Patent Applications 0124276, 0178183, 0178185, and 0264194, using monomers with acyl groups and monomers with hydrogens attached to aromatic carbon atoms which are electrophilically condensable with the acyl groups. The invention thus specifically includes a method of making the polymers in question comprising condensing at least one ether sulphone monomer of formula (IX) with one or more appropriate aromatic ketone monomers and/or aromatic ether ketone monomers having acyl groups in the presence of a Lewis acid catalyst and a Lewis base. This improved electrophilic synthesis, derived from modifications of Friedel Crafts chemistry, is capable of producing superior aromatic ether ketone polymers, as explained in aforementioned European applications, the disclosures of which are incorporated herein by reference. Preferably, the ratio of Lewis base to Lewis acid and the total amounts of each are selected for the reactants concerned so as to produce a polymer of acceptably high molecular weight substantially free from chain branching or cross-linking, resulting in exceptionally good melt stability of the polymers. Commercially desirable molecular weight control can be achieved by slight variations in the molar proportions of the starting monomers, as known per se, and end capping of the polymers can be effected as usual with known capping reagents.

Appropriate starting materials to provide the desired repeat units in the copolymers can be selected without difficulty, and may be synthesised by known methods. For example, monomers V to VIII in which Ar is phenylene are available commercially. Monomer IX may be synthesised, for example, as follows:-

Synthesis of 4,4'-Bis(4-phenylphenoxy)diphenylsulphone

Ph-Ph-OH + NaOH - - - - - - - > Ph-Ph-ONa + H₂ O

2 Ph-Ph-ONa + Cl-Ph-S(0)2-Ph-Cl -> Ph-Ph-O-Ph -S(0)2-Ph-O- Ph-Ph + 2NaCl

To a 2 litre reaction vessel fitted with a nitrogen inlet, stirrer and a Dean-Stark head was added 1 litre of triglyme, 200 mls of toluene, 230 g (1.35 Mole) of 4-phenylphenol and 52 g (1.3 Mole) of sodium hydroxide dissolved in 125 mls of distilled water. The reactants were heated to boiling and the water removed using the Dean-Stark head. The water started to collect in the Dean-Stark head when the temperature of the reactants was 109ºC. After all the water had been removed (2 hours) the temperature of the reactants was 170ºC. The reactants were allowed to cool slightly (165ºC) and then 146 g (0.51 Moles) of 4,4'-dichlorodiphenylsulphone was added. The reaction mixture was brought back to reflux and sufficient solvent distilled off to bring the temperature of the reactants to 220ºC. This temperature was maintained for 4.5 hours (the extent of reaction was monitored by high performance liquid chromatography) and the reactants then allowed to cool to 100ºC. The crude product was precipitated by pouring into 5 litres of aqueous NaOH (10%) filtered and washed with a further 2 litres of the aqueous NaOH. The solid was slurried with 2 litres of methanol and heated to 50ºC for half an hour, filtered and the procedure repeated once. After washing the filter cake with 2 litres of methanol the solid was dried under vacuum at 150ºC overnight. After drying, the almost white solid was purified by

crystallising from toluene (180 g/litre) and decolourised with charcoal giving a product in the form of spheres of 0.5 mm in diameter. m.p. 203ºC, Mol. wt. 554.6

The crude yield was 275 g (97% with respect to

4,4* -dichlorodiphenylsulphone).

The yield from the crystallisation was 90+%. By HPLC the product was 99% pure, and by the DSC method used here 99.40%

Note: In order to obtain high quality monomer it is

necessary to use the highest purity feedstocks as isomeric impurities may not be removed by repeated crystallisations. The 4-phenylphenol and

4,4'dichlorodiphenylsulphone used in this experiment were both isomerically 99+% pure.

A similar procedure was used to prepare the novel ether ketone monomer 4,4'-Bis(4-Phenylphenoxy)benzophenone, with the modifications that the 4,4'-dichlorodiphenylsulphone was replaced with 128 g (0.51 M) of 4,4'-dichlorobenzophenone or 111.3 g (0.51 M) of

4,4'-difluorobenzophenone, the triglyme was replaced by dimethylacetamide, and the reagents were refluxed at 155ºC for five hours.

After drying, the crude product was crystallised from hot 1,2-dichlorobenzene (100 g/litre) and decolourised with charcoal. m.p. 280ºC, Mol. wt. 518.6

As with the corresponding sulphone monomer the all para-linked nature of this ketone monomer was confirmed by 'H and ¹³c N.M.R. spectroscopy.

The invention is further illustrated by the

following specific examples. Example 1

To a 1 litre jacketed reaction vessel, equipped with stirrer, gas inlet/outlet, and having been purged with dry nitrogen was added 300 mls of dry dichloromethane. After cooling to -20ºC, 264.3 g (1.98 M) of anhydrous aluminium trichloride was added. Having allowed the temperature of the slurry to cool back to -20ºC, 50.9 g (0.541 M) of dimethyl sulphone was added at a rate such that the temperature of the reactants does not rise above -15ºC. Also at -20ºC, 115.666 g (0.2222 M) of 2,6-bis(4-phenoxybenzoyl) naphthalene and 61.6194 g (0.1111 M) of 4,4'-bis(4-phenylphenoxy)diphenyl sulphone were added, again maintaining the temperature of the reactants below -15ºC. Residual monomer was rinsed into the reaction vessel with 50 mls of dichloromethane.

Also at -20ºC, 68.621 g (0.338 M) of terephthaloyl chloride was added to the reaction vessel and washed in with 50 mls of dichloromethane. Finally 2.5786 g

(0.0094 M) of 4-phenoxybenzophenone (end-capper) was added and washed in with 20 mls of dichloromethane. The temperature of the reagents was then increased to +10ºC over 25 minutes and maintained for 30 minutes, and then increase to +20ºC and maintained for 6 hours .

The complexed polymer gel was decomplexed by

breaking it up in a high speed blender in ice/water.

After blending the polymer was filtered off as a white fiberous solid. The polymer was transferred to a 5 litre flask containing a solution made up from 1.4 litres of deionised water, 200 mls concentrated hydrochloric acid and 400 mls of methanol, and the slurry stirred for 6 hours at room temperature. After

filtering off the polymer fluff it was returned to the flask containing a fresh solution of the above and the whole heated to remove residual dichloromethane. After refluxing for 3 hours the polymer was filtered and washed with 3 × 2 litres of deionised water. The polymer was then refluxed twice for 3 hours each in 2 litres of deionised water, washing in between with 3 × 2 litres of deionised water and after the second reflux the polymer fluff was dried at 125ºC overnight and then at 250ºC for a further 10 hours.

The resultant polymer had an inherent viscosity of 1.31 dl/g, measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the copolymer was 205ºC

(measured by DMTA on a crystalline sample) and Tm 350ºC.

The Tg measured by DSC on an amorphous sample was 198ºC.

The structure of the copolymer was confirmed by *H and 1³c N.M.R. spectroscopy.

Ph = p-phenylene.

Example 2

Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. Anhydrous aluminiumchloride 113.34 g 0.85 M

Dimethyl sulphone 23.5 g 0.25 M

1,4-Bis(4-phenoxybenzoyl)benzene 39.52 g 0.084 M

4,4'-Bis(4-phenylphenoxy)diphenylsulphone 19.967 g 0.036 M

Terephthaloyl dichloride 24.81 g 0.1222 M

4-Phenoxybenzophenone 1.2180 g 4.44 × 10^-3 M

Dichloromethane 250 mls The resultant copolymer had an inherent viscosity of 1.12 dl/g, measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the copolymer was 200ºC

(measured by D.M.T.A. on a crystalline sample) and Tm 357ºC.

The Tg measured by D.M.T.A. on an amorphous sample was 184ºC.

The structure of the copolymer was confirmed by 'H and 1³C N.M.R. spectroscopy.

Ph = p-phenylene

Example 3

Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. Anhydrous aluminiumtrichloride 51.83 g 0.389 M

Dimethyl sulphone 11.19 g 0.12 M

4,4'-Diphenoxybenzophenone 16.2837 g 0.0444 M

4,4'-Bis(4-phenylphenoxy)diphenylsulphone 12.3239 g 0.0222 M

Terephthaloyl dichloride 13.7918 g 0.06793 M

4-Phenoxybenzophenone 0.7297 g 2.66×10^-3M

Dichloromethane 105 mls

The resultant copolymer had an inherent viscosity of 1.18 dl/g, measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the copolymer was 204ºC

(measured by D.M.T.A. on a crystalline sample) and Tm 327ºC.

The Tg measured by DSC on an amorphous sample was 192ºC.

The structure of the copolymer was confirmed by 'H and ¹³C N.M.R. spectroscopy.

Ph = p-phenylene '

Example 4

Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. Anhydrous aluminiumtrichloride 176.69 g 1.32 M

Dimethyl sulphone 33.60 g 0.357 M

2,6-Bis(4-phenoxybenzoyl)naphthalene 78.0825 g 0.15 M

4,4'-Bis(4-phenylphenoxy)diphenylsulphone 27.7315 g 0.05 M

Terephthaloyl dichloride 41.41& g 0.204 M

4-Phenoxybenzophenone 2.1946 g 8×10^-3M

Dichloromethane 320 mls

The resultant copolymer had an inherent viscosity of 1.32 dl/g, measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the copolymer was 194ºC

(measured by DSC on an amorphous sample) and Tm 362ºC.

The structure of the copolymer was confirmed by 'H and ¹³C N.M.R. spectroscopy. Ph = p-phenylene

Example 5

Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. Anhydrous aluminiumtrichloride 177.59 g 1.33 M

Dimethyl sulphone 33.69 g 0.358 M

1,4-Bis(4-phenoxybenzoyl)benzene 63.05 g 0.134 M

4,4'-Bis(4-phenylphenoxy)diphenylsulphone 36.6056 g 0.066 M

Terephthaloyl dichloride 41.5176 g 0.2045 M

4-Phenoxybenzophenone 2.4689 g 9×10^-3 M

Dichloromethane 425 mls

The resultant copolymer had an inherent viscosity of 1.17 dl/g, measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the copolymer was 205ºC

(measured by D.M.T.A. on a crystalline sample) and Tm 357ºC.

The Tg measured by DSC on an amorphous sample was 184ºC.

Ph = p-phenylene

This experiment was repeated except that the

dimethylsulphone was replaced by 0.358 M, 43.72 g of benzoic acid and 900 mls of dichloromethane was used, thus enabling the polymer gel to be dispersed as small spheres in the liquid phase. The resulting polymer was very similar to that obtained using dimethylsulphone.

Example 6

Following the basic experimental procedure outlined in Example 1 a block copolymer was prepared using the same ratios of reagents as in Example 3. Anhydrous aluminiumtrichloride 103.67 g 0.778 M

Dimethyl sulphone 22.38 g 0.238 M

4,4'-Diphenoxybenzophenone 32.5674 g 0.0888 M

4,4'-Bis(4-phenylphenoxy)diphenylsulphone 24.6478 g 0.0444 M

Terephthaloyl dichloride 27.583 g 0.1359 M

4-Phenoxybenzophenone 1.4813 g 5.4×10^-3M

Dichloromethane 300 mis

The polyetherketone block was preformed utilizing all of the aluminium trichloride, dimethylsulphone, 4 ,4'-diphenoxybenzophenone, 24.059 g of terephthaloyl dichloride and 250 mls of dichloromethane. These reagents were reacted at +15ºC for 2 hours before the remaining reagents were added at 0ºC. Polymerisation was then continued at +20ºC for 8 hours. The polymer was worked up as in Example 1.

The resultant block copolymer had an inherent viscosity of 1.13 dl/g, measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the block copolymer was 205ºC (measured by D.M.T.A. on a crystalline sample) and Tm 354ºC. The crystallisation rate of this block copolymer was ten times faster than that of the random copolymer (Example 3).

The Tg measured by DSC and D.M.T.A. on an amorphous sample was 186ºC, on a fully annealed sample the Tg by D.M.T.A. was at 205ºC. Compared to the equivalent random copolymer (Example 3) this block copolymer was found to crystallise up to 10 times faster.

The structure of the block copolymer was confirmed by 13c N.M.R. spectroscopy, the polyether ketone block having a molecuar weight of approximately 2000.

Example 7

Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. Anhydrous aluminiumtrichloride 40.46 g 0.303 M

Dimethyl sulphone 7.67 g 0.082 M

1,4-Bis(4-phenoxybenzoyl)benzene 14.3298 g 0.03045 M .

4,4'-Bis(4-phenylphenoxy)diphenylsulphone 8.3195 g 0.015 M

4,4'-Biphenyldicarboxylic acid chloride 13.0037 g 0.0-466 M

4-Phenoxybenzophenone 0.6309 g 2.3×10^-3M

Dichloromethane 100 mls

The resultant copolymer had an inherent viscosity of 0.80 dl/g, measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the copolymer was 197ºC

(measured by DSC on an amorphous sample) and Tm 403ºC.

The structure of the copolymer was confirmed by 'H and 13c N.M.R. spectroscopy.

Ph = p-phenylene

Example 8

Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. Anhydrous aluminiumtrichloride 31.32 g 0.235 M

Dimethyl sulphone 6.75 g 0.071S M

4,4'-Bis(4-phenylphenoxy)diphenylsulphone 22.1862 g 0.04 M

4,4'-Biphenyldicarboxylic acid chloride 11.4435 g 0.041 M

4-Phenoxybenzophenone 0.5486 g 2×10^-3 M

Dichloromethane 100 mls

The resultant copolymer had an inherent viscosity of 0.76 dl/g, measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the polymer was 246ºC

and the polymer was essentially amorphous.

Ph = p-phenylene

Replacing the 4,4'-biphenyldicarboxylic acid

chloride with terephthaloyl dichloride gave an essentially amorphous polymer of Tg 236ºC. Example 9

Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. Anhydrous aluminiumtrichloride 17.41 g 0.1306 M

Dimethyl sulphone 4.26 g 0.045 M

4,4'-Diphenoxybenzophenone 5.423 g 0.0148 M

4,4'-Bis(4-phenylphenoxy)diphenylsulphone 4.1043 g 0.0074 M

2,6- Naphthalenedicarboxylic acid chloride 5.7196 g 0.0226 M

4-Phenoxybenzophenone 0.2195 g 8 × 10^-4 M

Dichloromethane 50 mls

The resultant copolymer had an inherent viscosity of 0.85 dl/g, measured as in a 0.1% solution in concentrated sulphuric acid. The Tg of the polymer was 198ºC (measured by DSC on an amorphous sample) and Tm 340ºC.

The structure of the copolymer was confirmed by 'H and 13c N.M.R. spectroscopy.

Ph = p-phenylene

Example 10

Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. Anhydrous aluminiumtrichloride 17.2 g 0.13 M

Dimethyl sulphone 4.51 g 0.048 M

2,6-Bis(4-phenoxybenzoyl)naphthalene 6.607 g 0.0127 M

4,4'-Bis(4-phenylphenoxy)diphenylsulphone 1.7599 g 3.173 × 10^-3 M

2,6- Naphthalenedicarboxylic acid chloride 4.00 g 0.0159 M

Dichloromethane 75mls

The resultant copolymer had an inherent viscosity of 0.95 dl/g, measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the copolymer was 203ºC

(measured by DSC on an amorphous sample) and Tm 377ºC.

The structure of the copolymer was confirmed by 'H and 13c N.M.R. spectroscopy.

Example 11

Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. Anhydrous aluminiumtrichloride 7.33 g 0.055 M

Dimethyl sulphone 2.175 g 0.023 M

4,4'-Bis(4-phenylphenoxy)benzophenone 2.00 g 3.8567 × 10^-3 M

4,4'-Bis(4-phenylphenoxy)diphenylsulphone 2.139 g 3.8567 × 10^-3 M

Terephthaloyl dichloride 1.5659 g 7.713×10^-3 M

Dichloromethane 50 mls

The resultant copolymer had an inherent viscosity of 1.96 dl/g, measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the copolymer was 223ºC

(measured by DSC on an amorphous sample) and Tm 418ºC.

The structure of the copolymer was confirmed by 'H and 13c N.M.R. spectroscopy.

Ph = p-phenylene

Notes: Where measured, the copolymers were found to

exhibit exceptional melt stability at both 380ºC and 400ºC. Typically the rate of increase in melt viscosity over half an hour at 400ºC was less than 1%.

Where measured the copolymers were found to be between 10% - 30% crystalline.

The compound 4,4'-Bis(4-phenylphenoxy)benzophenone is believed to be new per se, and its use as a monomer for polymerisation is also new. These aspects are accordingly claimed independently of the sulphone units as well as with the sulphone units. Example 12

A block copolymer was prepared as follows:-

Firstly a polyaryletherketone block having an average molecular weight of 2856 was prepared from, Terephthaloyl chloride 0.2499 M 50.75 g

4,4'-Diphenoxybenzophenone 0.3000 M 109.93 g

Dimethyl sulphone 0.44M 41.36 g

Anhydrous aluminiumtrichloride 1.94 200g

Dichloromethane 360g

using the procedure in Example 1. The inherent viscosity of the oligomer was 0.19dl/g.

After isolating and drying this oligomer it was further polymerised with the reagents specified below, again using the procedure in Example 1.

Oligomer from above 28.48g

Terephthaloyl chloride 0.0540M 10.96g

4,4'-Bis(4-phenylphenoxy)diphenylsulphone 0.04 M 22.18g

4-Phenoxybenzophenone 7.524×10^-3M 2.064g

Dimethyl sulphone 0.1824 17.13g

Anhydrous aluminiumtrichloride 0.6M 80g

Dichloromethane 200mls

The resultant polymer had an inherent viscosity of

0.8dl/g., measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the block copolymer was 184ºC (measured by DSC on an amorphous sample) and the Tm was 362ºC. On a fully annealed sample the Tg by D.M.T.A. was 210ºC.

By contrast a random copolymer comprising the same overall ratios of reagents was found to be amorphous.

Example 13

To a 10 litre "Hastelloy" reaction vessel, equipped with agitator and nitrogen inlet was added 2500 mls of dry dichloromethane. After cooling the reactor to -13ºC the agitator was started and 2070.7g (15.53M) of

anhydrous aluminium trichloride was added. After the slurry had cooled to -11ºC 445.2g (4.73M) of

dimethylsulphone was added in portions, keeping the temperature of the slurry below -5ºC. After the slurry had again cooled to -11ºC terephthaloyl chloride 548.69g (2.703M) was added to the reactor and the residues washed in with 100mls. of dry dichloromethane. This addition did not result in much of a temperature rise. The remaining monomers, 4,4'-diphenoxybenzophenone

666.55g (1.819M), 4,4'bis(4-phenylphenoxy)diphenylsulphone 432.39g. (0.78M) and the end capper

4-phenoxybenzophenone 57.03g (0.208M) were mixed

together and then added to the reactor. The rate of addition was controlled such that the temperature of the reactants did not exceed -5ºC. The residues were washed into the reactor with a total of 400 mls of dry dichloromethane. When the additions were complete the reactor was sealed and pressurised to 50 p.s.i. with

nitrogen. The reactants were then heated to +15ºC over 20 minutes, and then allowed to rise more slowly up to +18ºC. When the reactants had reached +18ºC, 30 minutes from initial heating, the reading from the torque meter attached to the agitator had increased by about 10%. At this stage the viscous polymer solution was transferred. via a flexible coupling, from the "Hastelloy" reactor to a 4 inch P.T.F.E. lined steel tube fitted with a hydraulic piston. Polymerisation was allowed to continue in the tube for 6 hours at +22ºC. After this time the polymer was decomplexed from its aluminium trichloride by pushing the complex gel out of the tube, using the hydraulics, into a hammer mill that was continuously flooded with cold deionised water. After decomplexing, the white polymer fluff was filtered and washed, on the filler, with 3×15 litres of deionised water. The fluff was then allowed to soak overnight in 25 litres of deionised water after which it was heated in order to remove remaining dichloromethane. The slurry was then refluxed for 3 hours. After allowing the slurry to cool slightly the white polymer fluff was filtered and washed, on the filter with 3x15 litres of deionised water.

The polymer was dried at 125ºC overnight, followed by further drying at 250ºC overnight. The yield of aryl-ether-ketone-sulphone copolymer was 1300g.

The copolymer had an inherent viscosity of 0.7 dl/g., measured as a 0.1% solution in concentrated sulphuric acid. The Tg of the polymer was 200ºC

(measured by D.M.T.A. on a fully annealed sample) and the Tm was 350ºC.

The apparent initial melt viscosity measured at 400ºC and at 85Hz was 1150 poize and after 30 minutes was 1400 poise.

Claims

CLAIMS :

1. A polymer comprising (A) at least 5 mol % of aromatic ether sulphone backbone units of formula

-aryl-aryl-O-Ar-SO₂-Ar-O-aryl-aryl- (I) wherein -O- is ether oxygen, each Ar independently is an arylene moiety or represents a number of arylene moieties linked together by -O- or -CO-, each aryl-aryl moiety independently comprises two or more aryl rings which are (a) fused together or (b) twice bonded together directly and/or through linking groups to form a cyclic linking structure between the said rings or (c) directly single-bonded together in the polymer backbone chain, and the units (I) are linked together or to other units in the polymer backbone by linking groups.

2. A polymer according to claim 1 which is partly crystalline.

3. A polymer according to claim 1 or 2 which incorporates (B) aromatic ketone backbone units of formula

-Ar'-CO-(Ar'-O)n-(Ar')_m- (II) wherein each Ar' independently is an aryl-aryl moiety as defined in claim 1 or an arylene moiety or represents a number of arylene moieties linked together by -O- or -CO- or -SO₂- groups, and n and m independently are 0 or 1.

4. A polymer according to claim 3, wherein at least some of the aromatic ketone backbone units are aromatic ether ketone units.

5. A polymer according to claim 4, wherein at least some of the ether ketone backbone units are incorporated in repeat units of formula

-Ar-O-Ar-CO-Ar-O-Ar-CO-Ar-CO- (III) or -Ar-O-Ar-CO-Ar-CO-Ar-O-Ar-CO-Ar-CO- (III A) or -Ar-O-Ar-CO-naph-CO-Ar-O-Ar-CO-Ar-CO- (IV), wherein naph is a naphthylene moiety.

6. A polymer according to claim 5, wherein the said ether ketone repeat units are derived (a) from copolymerisation of an ether ketone monomer of formula

H-Ar-O-Ar-CO-Ar-O-Ar-H (V) and a diacyl monomer of formula

H-Ar-O-Ar-H (VII) and a diacyl monomer of formula

monomer (s)).

7. A polymer according to any of the preceding claims, wherein the ether sulphone backbone units are derived from polymerisation of a corresponding ether sulphone monomer of formula

H-aryl-aryl-O-Ar-SO₂-Ar-O-aryl-aryl-H (IX)

8. A polymer according to any of the preceding claims, comprising ether ketone sulphone repeat units of

formula

-aryl-aryl-O-Ar-SO₂-Ar-O-aryl-aryl-CO-Ar-CO- (X)

9. A polymer according to claim 8, wherein the said ether ketone sulphone repeat units are derived from copolymerisation of an ether sulphone monomer as defined in claim 7 and a diacyl monomer of formula

X-CO-Ar'-CO-X (XI) wherein X is halogen with one or more other monomers optionally providing the said ketone backbone units, the diacyl monomer (XI) being substantially in stoichiometric balance with the ether sulphone monomer and the other monomer(s) if present.

10. A polymer according to claim 9 comprising from

10 to 45 mol % of the said ether ketone sulphone repeat units.

11. A polymer according to claim 10, comprising from 20 to 40 mol % of the said ether ketone sulphone repeat units.

12. A polymer according to claim 11, comprising from 30 to 35 mol % of the said ether ketone sulphone repeat units.

13. A polymer comprising in its molecular backbone ether sulphone units derived from polymerisation of an ether sulphone monomer of formula

H-aryl-aryl-O-Ar-SO₂-Ar-O-aryl-aryl-H (IX) wherein -O- is ether oxygen each Ar independently is an arylene moiety or represents a number of arylene moieties linked together by -O- or -CO-, and each aryl-aryl moiety independently comprises two or more aryl rings which are (a) fused together or (b) twice bonded together directly and/or through linking groups to form a cyclic linking structure between the said rings or (c) directly single-bonded together in the polymer backbone chain.

14. A polymer according to any of the preceding claims, incorporating aromatic ether ketone polymer blocks together with the ether sulphone units.

15 A polymer according to any of the preceding claims, wherein each arylene moiety represented by Ar is a phenylene moiety and each arylene moiety represented by Ar' is a phenylene moiety.

16. A polymer according to any of the preceding claims, wherein at least some of the aryl-aryl moieties are biphenylene moieties.

17. A polymer according to claim 16, wherein at least some of the biphenylene moieties are 4,4'-biphenylene moieties.

18. A polymer according to any of the preceding claims, wherein at least some of the aryl-aryl moieties comprise terphenylene, polyphenylene, naphthylene, anthracylene, xanthylene, or 0 and/or N and/or S heterocyclic analogues thereof.

19. A method of making a polymer according to any of the preceding claims, comprising condensing at least one ether sulphone monomer as defined in claim 7 with at least one aryl diacyl compound in the presence of a Lewis acid catalyst and a Lewis base.

20. A polymer having the same repeat units as the

polymer prepared in any one of the foregoing Examples 1 to 11.

21. The compound 4,4'-Bis(4-phenylphenoxy)benzophenone.

22. A polymer comprising in its molecular backbone ether ketone units derived from polymerisation of a monomer compound according to claim 21.

23. A polymer according to claim 22 and any of claims 1 to 18.

24. A polymer according to any of claims 1 to 18, wherein the SO₂ groups in formula (I) or (IX) is

replaced by a CO group.