ETHERSULPHONE POLYMERS

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-0-Ar-S02-Ar-0-aryl-aryl- (I) wherein -0- is ether oxygen, each Ar independently is an arylene moiety or repre¬ sents 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 -0-, -CO-, or -SO2- groups. Preferred polymers according to the invention are partly crystalline, and preferably incorporate (B) aro- atic ketone backbone units. These units (B) are pre¬ ferably of formula -Ar*-C0-(Ar'-0) n -(Ar* ) m - (II) wherein each Ar* independently is an arylene moiety or represents a number of arylene moieties linked together by -0- 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 expec¬ tation 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 200 β C in some cases, combined with con¬ veniently low crystalline melting temperatures (Tm) , preferably below 400°C, more preferably below 385°C. Such Tm facilitates melt processing at temperatures safely below the limiting polymer decomposition tem¬ peratures 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 for¬ mula 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 polymeri¬ sation of a corresponding ether sulphone monomer of for¬ mula H-aryl-aryl-0-Ar-S02-Ar-0-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-0-Ar-S02-Ar-0-aryl-aryl-C0-Ar-C0- (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 polymerisa¬ tion of an ether sulphone monomer of formula H-aryl-aryl-0-Ar-S02-Ar-0-aryl-aryl-H (IX) wherein -0- is ether oxygen each Ar independently is an arylene moiety, or represents a number of arylene moieties linked together by -0- 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 0 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 reac¬ tion 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 for¬ mula (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 appli¬ cations, 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 substan¬ tially 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 + H2O 2 flrfh-Qfe + α* h-S(0)2-fl α > + 2tfcCL To a 2 litre reaction vessel fitted with a nitrogen inlet, stirrer and a Dean-Stark head was added 1 litre of triglyme, 200 mis of toluene, 230 g (1.35 Mole) of 4-phenylphenol and 52 g (1.3 Mole) of sodium hydroxide dissolved in 125 mis 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 109°C. After all the water had been removed (2 hours) the temperature of the reactants was 170°C. The reactants were allowed to cool slightly (165°C) 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 tem¬ perature of the reactants to 220°C. 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 100°C. 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 50°C 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 150°C overnight. After drying, the almost white solid was purified by crystallising from toluene (180 g/litre) and deco¬ lourised with charcoal giving a product in the form of spheres of 0.5 mm in diameter. m.p. 203°C, 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 experi¬ ment were both isomerically 99+% pure. A similar procedure was used to prepare the novel ether ketone monomer 4,4'-Bis(4-Phenylphenoxy)benzo- phenone, with the modifications that the 4,4'-dichloro¬ diphenylsulphone 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 155°C for five hours. After drying, the crude product was crystallised from hot 1,2-dichlorobenzene (100 g/litre) and deco¬ lourised with charcoal. m.p. 280°C, 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 mis of dry dichloromethane. After cooling to -20°C, 264.3 g (1.98 M) of anhydrous aluminium trichloride was added. Having allowed the temperature of the slurry to cool back to -20°C, 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 -15°C. Also at -20°C, 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 -15°C. Residual monomer was rinsed into the reaction vessel with 50 mis of dichloromethane. Also at -20°C, 68.621 g (0.338 M) of terephthaloyl chloride was added to the reaction vessel and washed in with 50 mis of dichloromethane. Finally 2.5786 g (0.0094 M) of 4-phenoxybenzophenone (end-capper) was added and washed in with 20 mis of dichloromethane. The temperature of the reagents was then increased to +10°C over 25 minutes and maintained for 30 minutes, and then increase to +20°C 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 mis concentrated hydroch¬ loric acid and 400 mis 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 125°C overnight and then at 250°C 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 205°C (measured by DMTA on a crystalline sample) and Tm 350°C. The Tg measured by DSC on an amorphous sample was 198°C. The structure of the copolymer was confirmed by *H and 13 c 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. Madras »__luπ__niι_πιch x±fe Dutet±yl s-jlξfons l,4-^i≤(4-^i]__n___^b__n____γl)b-=n___i_ne 4,4 * ***-____3(4*** __ry:_£h___^^ 19.967 g 0.036 M Ta ε&ti±Bkyl dirhlcririp 24.81 g 0.1222 M πi-iilcrσiel±ane 250 mis 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 200°C (measured by D.M.T.A. on a crystalline sample) and Tm 357°C. The Tg measured by D.M.T.A. on an amorphous sample was 184°C. The structure of the copolymer was confirmed by Η and 13c N.M.R. spectroscopy. Ph = p-phenylene 0 0 0 /I II « - -Ph-O-Ph-C-Ph-C-Ph-O-Ph-C-Ph-C- 2 . 3 Example 3 Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. Mξ rαus ώ ium trichlocide 5L.83 g 0.389 M Duiefctyl siiliirne 11.19 g 0.12 M 4,4'HDi Hrι>5tøι_iϊtøxne 16.2837 g 0.0444 M 4,4'-BJ≤(4-*pharιylghEn3y)d_jtø^ 12.3239 g 0.0222 M TAfc- iL kyl rϋ ilrridf*? 13.7918 g 0.06793 M DidΛ_xσiEthane U35 mis 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 204°C (measured by D.M.T.A. on a crystalline sample) and Tm 327°C. The Tg measured by DSC on an amorphous sample was 192°C. The structure of the copolymer was confirmed by 'H and 13c N.M.R. spectroscopy. Ph = p-phenylene 0 0 II II -Ph-O-Ph-C-Ph-O-Ph-C-Ph-C- Example 4 Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. MξdrαE -aluiάniuri trictilαride 176.69 g 1.32 M DU-Efctyl sulξtane 33.60 g 0.357 M 2,6-Bi≤(4^tsϊϊζten2Eyl)rBgtt als^ 78.0825 g 0.15 M tøc ha yl rHrhlrride 41.41& g 0.204 M Dic-ril xπEthane 320 πfl-s 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 194°C (measured by DSC on an amorphous sample) and Tm 362°C. 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. alumnitm t_t±±__orid≥ DiiiEtiyl sulphcne 4,4 * **-B_s(4*** a_γ:__ph___r^ 36.6056 g 0.066 M T re^ akyl .τirtτlrriri=* 41.5176 g 0.2045 M nichl-X itdLhane 425 mis 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 205°C (measured by D.M.T.A. on a crystalline sample) and Tm 357°C. The Tg measured by DSC on an amorphous sample was 184°C. The structure of the copolymer was confirmed by Η and 1 c N.M.R. spectroscopy. Ph = p-phenylene 0 0 0 I. u » •Ph-0-Ph-C-Ph-C-Ph-O-Ph-C-Ph-C- This experiment was repeated except that the dimethylsulphone was replaced by 0.358 M, 43.72 g of benzoic acid and 900 mis 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. Mξdrcus alurrinium trichkride 103.67 g 0.778 M Diπethri suOphcne 22.38 g 0.238 M 4,4 , ***Bi≤(4*** _sψ:__r_h___rx^ 24.6478 g 0.0444 M ichlrrid-. 27.583 g 0.1359 M ' 1.4813 g 5.4xLCr i DJ-dΛaOTB-±ane 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 mis of dichloromethane. These reagents were reacted at +15°C for 2 hours before the remaining reagents were added at 0°C. Polymerisation was then continued at +20°C for 8 hours. The polymer was worked up as in Example 1. The resultant block copolymer had an inherent visco¬ sity of 1.13 dl/g, measured as a 0.1% solution in con¬ centrated sulphuric acid. The Tg of the block copolymer was 205°C (measured by D.M.T.A. on a crystalline sample) and Tm 354°C. 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 186°C, on a fully annealed sample the Tg by D.M.T.A. was at 205°C. Compared to the equivalent ran¬ dom 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. _ ty_kcus alurinium tri(±kride 40.46 g 0.303 M DiπBttyl sulj me 7.67 g 0.082 M l, ^is( ^tι_3 ϊ^bena_yl)ba_2HK 14.3298 g 0.03045 M . 4,4'***Bis(4-*-p ecyl )ax^)dighary 8.3195 g 0.015 M 4,4'***Bi Hy1 iπ**ιrfacgylic arid dil ridp 13.0037 g 0.0-466 M A-øn ca enχj>±stx>s 0.6309 g 2.3xlO-***M Dir- Lα _τ___tharιe 100 mis 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 197°C (measured by DSC on an amorphous sample) and Tm 403°C. 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. Mξdrσjs aluτimiun toichloride 31.32 g 0.235 M Diitethyl SLQphcπe 6.75 g 0.071S M 4,4'*-*Bi≤(4***EharylfhaiQ^)difte^ 22.1862 g 0.04 M f A'- syld Bάxiy± : arid d lcride 11.4435 g 0.041 M i ch iuiKit Bne lOO nύ-s 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 246°C and the polymer was essentially amorphous. The structure of the copolymer was confirmed by 'H and 13c N.M.R. spectroscopy. Ph = p-phenylene 0 0 0 H u i) 'Ph-Ph-0-Ph-S-Ph-O-Ph-Ph-C-Ph-Ph-C— ■ H 0 Replacing the 4,4*-biphenyldicarboxylic acid chloride with terephthaloyl dichloride gave an essen¬ tially amorphous polymer of Tg 236°C. Example 9 Following the basic experimental procedure outlined in Example 1 a copolymer was prepared from the following reagents. M^droB alumniαn trijdilαride 17.41 g 0.1306 M Dmsthyl SLϋfim≥ 4.26 g 0.045 M A, '-&s( -^^^}^n3^)di≠τer^^riχre 4.1043 g 0.0074 M arid -ch1.rr.rif-*. 5.7196 g 0.0226 M DJ-chlmnreLhane 50 πϋs The resultant copolymer had an inherent viscosity of 0.85 dl/g, measured as in a 0.1% solution in con¬ centrated sulphuric acid. The Tg of the polymer was 198°C (measured by DSC on an amorphous sample) and Tm 340°C. 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. aluranLun tr hlcride 17.2 g 0.13 M D-πettyl s Qphcne 4.51 g 0.048 M 4,4'**-Bi≤(4- s_yl =noy,^^ 1.7599 g 3.173 x ID -3 M arid dύ Afe 4.00 g 0.0159 M 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 203°C (measured by DSC on an amorphous sample) and Tm 377°C. 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. P kcυs aluraniun txio ____ri_te 7.33 g 0.055 M Dmetiyl sulphcne 2.175 g 0.023 M 4,4'***Bi^(4-fhay_^teri3y) iphgyl^ 2.139 g 3.8567 x KT 3 M Iferep haloyl dichlfrirfr 1.5659 g 7.713x10-3 M Didil-Ttjre hans 50 mis 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 223°C (measured by DSC on an amorphous sample) and Tm 418°C. 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 380°C and 400°C. Typically the rate of increase in melt viscosity over half an hour at 400°C 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, Terep±ta yl dύ de 0.2499 M 50.75 g f '-€ά Ξna sur sr πe 0.3000 M 109.93 g artξd ous aluπiniun tridil itfe 1.94 200g Did kxuiHAlBne 360g using the procedure in Example 1. The inherent visco¬ sity 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. C-Lig-.ii._-3- frαn abcwe 28.4θg Ter ±telogl dilcride 0.0540M U3.96g 4- haxsςtena5teπcre 7.524X1D-3M 2.064g Ddπel±ylsulEhDne 0.1824 17.13g alumnium tr iikxiάa 0.6M -90g πidilcrαiBl±ane 20 ri3_s 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 184°C (measured by DSC on an amorphous sample) and the Tm was 362°C. On a fully annealed sample the Tg by D.M.T.A. was 210°C. 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 mis of dry dichloromethane. After cooling the reactor to -13°C the agitator was started and 2070.7g (15.53M) of anhydrous aluminium trichloride was added. After the slurry had cooled to -11°C 445.2g (4.73M) of dimethylsulphone was added in portions, keeping the tem¬ perature of the slurry below -5°C. After the slurry had again cooled to -11°C terephthaloyl chloride 548.69g (2.703M) was added to the reactor and the residues washed in with lOOmls. 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)diphe- nylsulphone 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 -5°C. The residues were washed into the reactor with a total of 400 mis of dry dich¬ loromethane. When the additions were complete the reac¬ tor was sealed and pressurised to 50 p.s.i. with nitrogen. The reactants were then heated to +15°C over 20 minutes, and then allowed to rise more slowly up to +18°C. When the reactants had reached +18°C, 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 con¬ tinue in the tube for 6 hours at +22°C. After this time the polymer was decomplexed from its aluminium trich¬ loride 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 3x15 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 125°C overnight, followed by further drying at 250°C 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 200°C (measured by D.M.T.A. on a fully annealed sample) and the Tm was 350°C. The apparent initial melt viscosity measured at 400°C 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 aroma¬ tic ether sulphone backbone units of formula -aryl-aryl-0-Ar-S02~Ar-0-aryl-aryl- (I) wherein -0- is ether oxygen, each Ar independently is an arylene moiety or repre¬ sents a number of arylene moieties linked together by -0- 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 incor¬ porates (B) aromatic ketone backbone units of formula -Ar'-C0-(Ar'-0)n-(Ar' ) m - (II) wherein each Ar' independently is an aryl-aryl moiety as defined in claim 1 or an arylene moiety or repre¬ sents a number of arylene moieties linked together by -0- or -CO- or -SO2- groups, and n and m inde¬ pendently 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-0-Ar-CO-Ar-O-Ar-CO-Ar-CO- (III) or -Ar-0-Ar-C0-Ar-C0-Ar-0-Ar-C0-Ar-C0- (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 copoly¬ merisation of an ether ketone monomer of formula H-Ar-0-Ar-CO-Ar-0-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) ) . 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-0-Ar-Sθ2-Ar-0-aryl-aryl-H (IX) 8. A polymer according to any of the preceding claims, comprising ether ketone sulphone repeat units of formula -aryl-aryl-0-Ar-S02-Ar-0-aryl-aryl-C0-Ar-C0- (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 pre¬ sent. 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-0-Ar-S02-Ar-0-aryl-aryl-H (IX) wherein -0- is ether oxygen each Ar independently is an arylene moiety or repre¬ sents a number of arylene moieties linked together by -0- 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 phe¬ nylene 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 analo¬ gues 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. * * * ** * *

Inventors: TOWLE IAN DAVID HENDERSON, TOWLE, IAN, DAVID, HENDERSON
Applicants: RAYCHEM LTD, RAYCHEM LIMITED
Application year: 1989
Main classification: C08G61
IPC codes: C08G61, C08G67, C08G75