SE407070B - MELTABLE AROMATIC POLYKETONE TERMINATED WITH RESIDUES OF A TERMINATING AGENT - Google Patents

Description

72b1a71 # 6 2 compounds in which a representative is heated with a representative belonging to a second group consisting of aliphatic and aromatic diacyl chlorides. The main reactions can be summarized as follows: ouin-o-Ru) + o (c1-A-c1) i, oncl + n - (- R-ø-xA -) - nc1 and oumu) + o (c1-A_c1) - -> n fl cz. + c1 44-5 -yn n dir HBK denotes a polynuclear aromatic hydrocarbon, e.g. naphthalene, phk-O-RH and ether, e.g. diphenyl ether, and C1-A-Cl a diacyl chloride, i.e .: terephthaloyl chloride or phosgene. In the reaction of the compound and diphenyl ether, the polymer formed will contain the recurring unit: Another possible route has been proposed in British Patent Specification 1,978,234 (Union Carbide Corporttion), according to which Ipolyarylene polyethers "are prepared by reacting an alkali metal double salt of The dihydric phenol may contain a keto group, and thus it is stated, for example, that 4,4I-dihydroxybenzophenone gives rise to a polyketone.

British Patent Specification 971,227 (Imperial Chemical Industry) states that the same recurring moiety is formed by the reaction of diphenyl ether with phosgene, by the polycondensation of diphenyl ether-4-carbonyl chloride, and by the unsaturation of diphenyl ether with diphenyl ether-4,4'-dicarbonyl chloride.

Since then, a number of patents on improved methods of producing polyketones have been published. According to the two U.S. Pat. Nos. 3,441,538 (du Pont) and 3,442,858 (du Pont), both from 1969, for example, hydrofluoride-boron trifluoride catalysts, a system previously described in Topchiev et al. , "Baron Fluoride and its Compounds _ as Catalystsl, Pergamon Press (1959), p. 122; J. Org. Chem. 26, 2401 (1961), and Ind.Eng. Chem. 43, 746 (1951). A further patent which relates to an improved process is British Patent 1,086,021 (Imperial Chemical Industries Ltd.) from 1967. Example 10 of British Patent Specification 971,227 describes a process for the preparation of a polyner with the recurring unit Q-Û íQ- CO 7201871 -6 5 It is stated that the product showed no signs of flowing at temperatures of up to 55000 and apparently required spinning from solutions for fiber formation. The product is also described in various ways in Example 1 of U.S. Patent No. 5,441,558 where it is said to give a polymer with little elongation and tough, opaque films, while in British Patent Specification 1,153,527 it is characterized as highly crystalline and unstretchable, i.e. not available for melt processing. It therefore appears that this polymer, despite its inherent suitability for use at high temperature, is unsuitable for melt processing due to its extensibility. Thus, there has been a need for melt processable polyketones with the recurring unit: o-O-oaïo In order for a polymer to be melt processable, its viscosity at the processing temperature must remain substantially constant for at least about 5 minutes, preferably for up to 30 minutes. The polymer must also not be degraded to a lower molecular weight to such an extent that the final product loses its inherent physical properties, e.g. the elongation, nor so that it becomes thermally crosslinked to such an extent that it becomes unstretchable.

The polymeric product of the invention is characterized in that the polymer or polymers have an intrinsic viscosity of about 0.8 to about 1.65 dl / g (measured on a solution of 0.1 g of polymer in 100 ml of solution of concentrated H 2 SO 4 at 25 ° C), has an elongation at break at room temperature of at least about 501% and is terminated with residues of a terminating agent, the reactivity of which towards acetylation compared to benzene is greater than about 150, which polyketone can be processed into shaped articles in the molten state. In this description, the average intrinsic viscosity has been consistently determined according to that of Sorenson et al. indicated method, which is described in Preparative Methods of Polymer Chemistry, Interscience (1968), p. 44 (0.1 g polymer in 100 ml solution of concentrated H 2 SO 4 at 25 ° C). The elongation at break at a strain rate of 200% per minute at 25 ° C is generally referred to in the description as "strain" for the sake of simplicity.

According to the invention there is also provided a process for the preparation of the polymer by polymerizing one or more monomers of the formula © -.- 0-- CO X, where X represents one with 7 L? hydrogen-cleavable group, by Friedel-Craft-catalysis in the presence of an aromatic terminating agent whose reactivity to acylation compared to benzene is greater than about 150. The polymerization is preferably catalyzed by boron trifluoride. In a preferred embodiment, the resistance of the polymer to attack by certain solvents is improved by extracting from the polymer substantially all polymer chains with an intrinsic viscosity of less than about 0.6.

The polymers according to the invention are, and the new processes by means of which they are produced provide polymers with good high temperature properties, which polymers are melt processable to give an extrudable product useful for wire and cable insulation. The polymers according to the invention can also be fabricated into shaped objects by injection molding. The basic reaction conditions for the preparation of the polymer are described in detail in the above-mentioned patents and will not be repeated here. In the following description, only the features from which the advantages of the invention are derived will be discussed.

It has been found that the average intrinsic viscosity must be adjusted so that it comes within a range of about 0.80 - 1.65. Below about 0.80 the elongation can be reduced due to insignificant deviations in the polymerization process, while a polymer with an average internal viscosity higher than about 1.65 has such a high melt viscosity that under normal working conditions it at most gives a coarse extrudate instead of the even, cohesive coating required for wire insulation. The average intrinsic viscosity can be suitably maintained in the range of 1.0 - 1.55, preferably in the range of 1.20 - 1, b0, and preferably at about 1.30. When extruding a polymer, the internal viscosity of which is greater than about 1, h, on a narrow wire which is fed at a speed of 900 '- 1200 m / min, temporary melt fractures occur. However, a higher viscosity polymer is suitable for extrusion on thicker wire or for rods for thermoforming or fiber drawing.

The intrinsic viscosity can be controlled by means of selected aromatic determinants. The terminating agent is believed to terminate the polymerization by Friedel-Craft catalyzed acylation reaction with an active polymer chain. The boron trifluoride-catalyzed polymerization of monomers to produce poly (benzophenone ethers) appears, for example, to proceed over the formation of a highly reactive intermediate compound containing a carboxonium ion, e.g. a tetrafluoroborate in the case where the monomer is an acyl fluoride: '5' 7201871-6 <3., - @ _ cšl | r © _o __ @ _ §ß.š;>; QWQCM.,: - ° - C¶TE 0- _ CO-F + BF3 ---) H ___.) H H Q eQ- el: m ®_ ° _ © __§? B.§>, m.

The chain avllutal of the ternination joint and the boron trifluoride remove: då-. after, for example on the following sit: -11j- @ ~ «~ <:> C¶ fl - @ - ~ -® @» @ + @ - ~ -® ~ H í ~ ® ° ~ © ~ ° šif © ~ ° - ® - ~ == T The terinogenation moiety has a purity relative to acetylation which is at least of the same ether cleavage as that of the nononer, and it has been found that the terinination moiety for a nnlltable processable polyner (which is believed to have been produced by zero molecular weight control) should have a reenactivity gene acetylation (relative to the bone), which is about 150. In the literature (cf. Kinoto, J. Pharn. Soc. Japan 75 (1955): P-727 and Bruun et al., J An.Chen._Soc. 81 (1959), P- 5929) nngee ~ exelpel- vis the following care for the relative degree of acetylation in the lyethylene cu3coc1 / A1ci3 = Table I owned; Relative degree of acetylation Benlene 1.00 Biphenyl 205 4-Ethyl-diphenyl ether 448 Diphenyl ether 1 11,600 4-Methyldiphenyl ether 81,000 The enlylined erolating terinylene moiety is preferably non-nil-tinted pig and preferably non-ring-nubtitated, e.g .: of nitro, nethyl, hydroxy, netoxy, netoxycarbonyl or acetyl, in case a polymer with good high temperature properties is desired. In such a case, it is readily appreciated that agents which are subject to oxide rigid or thermal degradation must be avoided as they give rise to a discolored polymer. In general, any condensed polynuclear aromatic system or aryloxy- or aryl-substituted benzene with sufficient resilience to acylation and solubility in the resection medium can be used, i. diphenyl, diphenyl ether, 4-phenoxybenzophenone or 4,4'-diphenoxybenzophenone.

In the range of internal viscosity required for processability, log (internal viscosity) appears to have a linear relationship with log (mole percent terminating agent). In the polymerization of p-phenoxybenzoyl chloride in the HF / BF3 system, in which the mononer concentration was 1 m ° 1/1, at 0 ° C during 6 01-Mar and then for 15 hours at 0 ° C, at a 7 BF 3 pressure of 0.35 kp / cm 2, for example, the following correlations were obtained: Table II Termination fraction Molecular percentage Average internal vis-. kggitet goa nrodnkteg ßifenyl 9 "'0,2s 2,25 J 0,35 0 1,80 0,50' 1,40 0,75 1,05 1,00 _ 0,87 Diphenylether 0,36 2,34 0 0 .77 1.12 1.14 1.04 2.01 fl "0.56 4.01 '0.30 In the case where a diseyl fluoride monomer, t, e :. diphenyl ether (4,4I-dicarbonyl fluoride) is used together with diphenyl ether, the latter in excess, the reactive intermediates before and during the polymerization can apparently be characterized as: _00 4 Ne i | _§_ @ ï_ø _ @ _ c @ 0, .. i [låi_ © ..., _ @ __, ¶.n___@_¿, __ @ 1 i 7201871 -6 In this case, the electrolyte polymer will become a termination unit or a reet dlrav at each end. In the example given, it is of course the excess of the diphenyl ether which serves as a terminating agent, although a separate agent such as biphenyl could of course just as well be used.

The end group-derived polymers of the invention can then be represented in the following manner: I! R-E-Ön 'dlr RI denotes the termination agent- and R denotes fine. When the polymer is prepared from a diacyl fluoride ionomer and suitably aromatically carbonated aleone disenyl ether, the group-derived polymers according to the invention can repreenterae in the following manner: - 11 "4} -O ° © - °° ~ © - ° - © ~ °° ¶- * ' dir RI denotes the termination reagent.

If the diaeyl fi fluoride monomer used in a zero Uverekott in relation to the aromatic piston, the terminated polynene monitors according to the invention can repreeenterae on the following bit: 'R- wa> - ~ o- <> __ wii-n of your R and R' denotes the termination means. R and R 'may: ivetvie the will different, draw mixtures of termination ring may usee.

It has also rested ei; that the polymer action, if a polymer having an average intrinsic viscosity in the required range is to be obtained with the polymer despite having such an elongation at break of 50% minetaca, must be repeated in such a way as to prevent contamination of the polymer with transition metals; .ex. Fe, Cr, Co and Ni, since these are believed to give rise to a premature tY§rhindnin§_0ch in which case eom the whole give a polymer inside; the area indicated for the internal viacoity but with much li; elongation at break. According to Example 1 of U.S. Pat. No. 3,441,53 I polymerize, for example, p-phenoxybenzoyl chloride in the HF / DF3 atom using; of a reactor of_poetless atål. It is stated that a material with an intrinsic viscosity of 1.18 is obtained, in which case one of the films obtained from the polymer does not show an elongation at break of 7.2% and is therefore completely unsuitable for trellium diolation.

Wfo fi ïn * auAurv I; _ ~ v2ø1a? 1-6 'kr 8 "The reaction must thus be carried out in an environment that is practically free from transitional metals, eg in plastics, for example polyethylene tetrafluoroethylene (PTFE), polyethylene, polychlorotrifluoroethylene (PCTFE ) ', plate-coated vessels or aluminin vessels, etc. From the above-mentioned reaction mechanism ooh of the recurring unit> f ~ @ ~ - @ - fl ~ í + it appears that different mononers and mononer combinations can be used, eg phenoxybenoyl fluoride enaaa, or diphenyletpr ( 4,4'-Dicarbonyl fluoride) 'an excess of diphenylates. P-Phenoxybenzoyl fluoride is the preferred nononera and is usually obtained by treatment with the corresponding non-fluorine-containing halide (preferably p-phenoxybenzoyl chloride). Alternatively, the acyl fluoride formed may be eluted from hydrogen fluoride by deatillation or the like for subsequent polyneration. In the latter case, those of hydrogen fluoride are retained. In the reaction, the colored aubatans formed into other impurities which are usually present in a commercial grade acyl chloride. p-Phenoxybenzoic acid or those C 1 -C 3 alkyl ethers may use allolomers in the atom of the acyl halides. The acid ajllv can be prepared, for example, by ganonlullane condensation of phenol and p-chlorotoluene and subsequent cobalt acetate-catalyzed oxidation to the ayran. The ethers can, for example, franatillaa by alcoholia of the ayra chloride or by pre-etherification of the ayra. I I Hydrogen fluoride is usually used as a solvate moiety for the polynerate formed and may also participate in the polymerization reaction. The reaction nuclei according to which the ayra chloride polyneriaera aynea will all examples- via include lononerenanone filtration to an ayrafluoride as nellan compound. To initiate the polymerization, boron trifluoride may be added to a white fluoride solution containing about 3 to 30 microns, preferably about 15 to 25 microns, by weight. As an alternative to the use of HF alone, BF3 can be added to a solution of the monomer in fl F and liquid dehydrogen dioxide, which will be described in more detail below.

When the polyarrieration is ganoafore 1 UF only keep the polynariaation temperature at a temperature between about 0 ° C and 50 ° C, all halate: all about 0 ° C and crude temperature. Polyneria ionization temperatures of 10000 and above should be avoided, below temperatures below 0 ° C the polyneria ionation rate will decrease. The preferred option, however, is to ganoa- PÛÛR nvALrn / ee 9 7201871-6 conduct the polyneration in the presence of exenpelvie 50 volyn percent vltakefor- fu; soz, 1 vain: nu camp-returen han. vid e. o ° c fa »m; søz .nu is kept in a volatile state at the pressure prevailing in the reactor. SO 2 aynee deprotonate the polyneric ketone moieties so that BF 3 is not ionically bound thereto but more loosely in the form of a donor-acceptor complex. SO2 entaa in a similar way affect the degree to which water and alcohol, which form: lol by-products at acid- resp. etherpolyleration ion, binds VBF3. Since the treatment during the preferred work-up by apray drying (ao: akall beakrivae below) also helps to release bound BF3, the beneficial effect of SO 2 in this respect has not yet been quantified. However, the use of SO 2 has been advantageous in a number of other respects. In the case where the polymer is recovered by precipitation in a relatively non-solvent, e.g. Acetone, methyl ethyl ketone, dimethyl furuanide, dimethylacetanide, N-methylpyrrolidone, acetic acid or chlorinated acetic acid, the liquid avalanche dioxide increases the unacceptable temperature rise due to the released diluent in the solution. when worked up on wet surfaces, however: the polymer for nucleophilic solution components must be able to interact with the polymer to introduce thermal instability into it.

K It has been found that the resistance of the polymer to attack by ketonic and similar solvents is improved if the polymer is extranated with et§M¿Qaniag¿æ¿d @ l, wZåggtrß fi peïia.en alißl fi i fi ß Ég fi gn, e.g. acetone, or led chlorinated aliphatic hydrocarbons, e.g. the trichloroethene. The extraction is carried out at temperatures in the range of about 30 to 50 ° C and allowed for a period of time to be sufficient to extract about 4 to 10% by weight of the polymer. The resulting polymer has an average internal viability that is within the range required for all machinability and is substantially free of chains down an internal viability other than about 0.6, and is more noticeable when formed during tensile plating. for vieaa löaningaaedel. Any extraction required before the polymer is brought to a temperature above the free glacial conversion temperature (about 160 ° C for poly (beneophenone ethers) -hoao- polyls), as the crystalline action occurs, reduces the extractability of the clay molecules of the solvent. origin of apricot formation.

It should be borne in mind that aetone may characterize a "non-payable neddal" under the relatively nil conditions of the precipitating process, and may believe this to be used for leaching the lignolecular parts during the longer periods of time aoa are combined down an extract. Even if aeeton is used lol a "non-payable unit fl in the case of filling in / lñlíï uuAuTv 7201: 71-6 10 one of the rla pe1ymerer {it can admittedly also affect the geneas- ing internal viscosity to a measurable extent. A 20-weight percent. solution of poly (benzene phenon ether) in HF which was pitted to SX with SO 2 and poured into a stirred SO 2 -aetone mixture gave, for example, the following relationship between the acetone concentration and the gene average internal viscosity: Table III Present acetone in Internal viscosity of gzgll / dioxide golzger 1.57 17, 5 1, 56 20 1, 55 25 1.51 100 1.50 The extracted polymer shows a markedly superior tensile strength and elongation under tensile stress and the simultaneous action of the working part. Even if leaching of a genqa reprocessing.on the wet road erhlllen plyaer gives a satisfactory product, it would be advantageous to avoid this step, so it is preferable to spray-dry the polyneria- tion product instead of reprocessing it by precipitation by means of a Üicke solution media The polymer can be spray-dried in vltellnorid only with the use of vessels whose walls are duly lined down with an anti-corrosion coating. However, it has been found that hydrogen peroxide gives the polymer a lighter color than can be obtained by spray drying from hydrogen fluoride alone. 0: S02 is used instead of HF for flushing out the solid constituents used for spray drying clay, the corrosion of the spray dryer walls is reduced and significant economic savings are achieved due to the relatively low costs of the sulfur dioxide. Although a detailed description of the aperture coating of liquid SO2 can be found in our co-pending patent application 1873/72, the preferred method in the cap is to dilute the polymer solution to a solids content of about 1-2%, i.e. so that a solution containing a predominant amount of SO 2, preferably 90-99% by volume. The dissolved solution is fed at -6 ° C under a pressure of, for example, 1.4 etho to a two-component solution, from which it is inoculated and briquetted in contact with product air or gaseous SO 2. Temperatures dpi the incoming gas of 190 - 220 ° C give powdered polymer sed only about 2 - 5 wt% volatile fluorine compounds. The fluorine content of the spray-dried product is then preferably reduced to less than 100 pn in a wake, which, for example, operates at a temperature of 14000.

The salt-workable polymer according to the invention can easily strlg- * Tïïílíw fl UÅUTV_ ni va7v? ° 1 ° 71aavfv5aiv aprmtaa pd elektrikaka conduder, oftent nlr it grid threads in the form of layers with thicknesses of about 0.1 - 0.3 m. The coated wire vlr. »Lae foretrldeavia, e.g. 2 minutes at about 220 ° C, to give an overall abrasion-resistant, strong and dimene ionatable insulation layer. After the heat treatment, the preferred polymer has an elongation at break of about 125 ° C. It has also been found that the polymer can be thermally crosslinked after fabrication to improve solvent resistance and dimensional stability over the melting point. If, for example, a poly (henaophenone ether) coated wire in an inert atmosphere consumed about 0.25 - 2 l for a temperature of about 120006, the reactant product tvirhund dt- minntone on the surface and viar under the influence of wage means a good he - resistance to apricot formation even before extraction with acetone or other extraction medal. The polymers can generally be inert at temperatures between about 300 ° C and about 600 ° C. The time required for obtaining a fine degree of either heat treatment or thermal bonding is in inverse proportion to the temperature used, and suitable times and temperatures for each polymer may, from the foregoing, be readily apparent to those skilled in the art, depending on the complex working conditions and the like. nande hlnayn.

The polymers according to the invention can be formed into objects, which can be reinforced, e.g. with glafiberber. The invention includes, for example, films and fibers. The invention is hereinafter referred to as a series of embodiments, in which parts and percentages are by weight, and not by any other means. §!:! 2: ll A 6-liter PIFE flask, preceded by a PIPE inlet, magnetic stirrer and a PTFE-apiral cooler, cooled by a bath of torria and aeetone, aataadae mad l822 g (5,096 nol) -p- phenoxybanaoyl chloride and 4,132 g (0.027 nol; 0.525 mol%) of biphen11. Four liters of anhydrous volte fl fluoride condensed air into the reactor at -78 ° C. The reaction mixture was preheated to room temperature to evaporate hydrochloric acid, then cooled to -78 DEG C. and dried under low pressure to 535 g (7.1 ml) of hydrogen fluoride. When all the hortrifluoride was allowed, the reaction mixture was allowed to warm to room temperature and poured for 20 hours under an overpressure of hortriiluride. The polymer slurry is purged with anhydrous hydrofluoride and poured into vigorously stirred acetone, in which the polymer is precipitated. The polymer was washed with acetone and water and then vacuum dried at 150 DEG-160 DEG C., 72 DEG-72 DEG-71 DEG-12 DEG-12 DEG C. to give 900 .mu.l (90 DEG C.) of a fluorine polymer having an internal fluidity of 1.45 and an elongation at break. over 125 5. The Polynesian had a cryatal count. point of 36500, nltt pl colorinetric vl3.

Era 2 - _ a) Fralat ll of phenoxibenao lflu at set 50 a1 reukeorror of rcrrs aazaaaaa -aa 23,25 3 (o, 1o flour) p- phenoxibanaoyl chloride and f8ral3a nad a na3netiak inrörin3aatav. Rbrit analogous particles to a PCIFE vacuunalan3 (toho Kaaai Co., Ltd., Oaaka, Japan), and 10 nl of anhydrous hydrogen fluoride condanaeradaa into the reactor well by 19606. Stir until 006 and pour for 4 hours at this temperature. Excess hydrofluoride, tillaannana down hydrochloride, avll3anadaa dlrafter 3enol deatillation. The solid ateratodane is dissolved in 20 .mu.l of ethylene chloride, to which is added 1 .3 ml of sodium fluoride as a solvent for the removal of the remaining HF. Löanin3en oarördaa overnight, filtered: alr- eftar, and indunatadea to dry hat to give an ava3t 3ul kriatallin aaaaa. By datillation at 100 - 110 ° C (bath) / 0.1 dry arhölla 20.00 3 (0.0926 nal; 93 X) of a flr3löa vltaka, aon atelnade at rulatelperatuq allltpunkt 39 - 4096. Gaakronato3rafiak analya rested audaat_en kompo- nent. Hetanolia 3 of ala lotyl ether ao: obtained: from p-phenoxibanaoyl chloride. Infrared / apectrone (KBr) rested on a strong band at 1803 oa'1, aon resting the free carbonates of acyl fluorides.

Ib) Polggeriaation of lzlgnoxibenol fluoride A S0 al for by PC !!! aataadaaed 5.50 3 (25.55 lIol) _g-phenoxybengx aoylfluggid, 0.0ll8 3 (0.0694alo1;, 0.27l lol percent) diphenyl ether and ¶öraå3a led an onröraratav. The tube is analogous to a PCTFE vacuuaalan3 and apoladea nad kvlv3aa. Thereafter condensed 20 nl of anhydrous vlteflaoride ein 1 »avec via -196 ° c and -.aan z, 6o 3 (38, z9 anal) b ° fcr1f1u ° f1a. newer vIrnnin3 to room temperature onrßrdea reaction mixture 1 h. üvarakot- tet av'bortrifluorid utapoladaa dlfter frin raaktorayatenat nad kvlv- 3aa. The oran3a3u1a, viaköaa polynerlöanin3en utaplddaa down anhydrous vltailuorid and hllldea in krafti3t oarßrt acetone, in which polyaaren utfllldea. The plyliner washes down acetone and water and vacuuator damages at zoo ° c, whereby .rnu11a 4.80 3 (95 1) of att: | f; 1aae knowledgeable:, a1v. » down an internal viacoaitat of 1.56 and an intrinsic fraction over 125%. ! §:! Nel_1 Sn hlandnin3 av 0, l305 3 (0, $ 667 naol) diphenyl ether och 21,45 3 (99,77 aeøl) pf.n ° = 1bana ° y1f1u ° ria varna-a unnar oavoring till en so - 60 ° C for arhlllanda of a complaining gall. Of this mixture, 5.50% in 20 ml of hydrofluoride and polyurethane are added to the reaction derivatives in Example 2 to give a liquid polyaer an internal vacuoate of 1.12. vmí ”QUALITY 1; 12 '2201871-6 Bxenggl ¿A 1 kg sample of poly (benaophenone ether) down to the internal capacity 1,43 atrlngl was sprayed at 410 - 420 ° C using a 3/4 "Brabender type spray gun. A twisted 0.8 mn nickel-plated copper wire natadea was passed through the duct, and the polymer altar was drawn down on the wire to form a thin and cohesive insulating layer, this insulating layer having a tensile elongation of 125%. 1335 kp / cnz The insulated wire was exposed to various elevated temperatures in air, and the time required for the elongation at break to reach 0%.

The results obtained are shown in the following table: V Temperature Time for S0 $ elongation o'h C 360 19 340 37 320 89 300 187 280 1 648 At 2 $ 0 ° C the insulation layer has a tensile strength of 600 kp / clz - and an elongation at break of 150 $. The example illustrates the malleability, atomic elongation at break and the good high temperature properties (eg oxidation resistance) of a polyner according to the invention.

Example 5 A sample of poly (beneophenone ether), which was precipitated in a PTFE reactor and had an internal coefficient of 1.55, gave a colorless plate during pre-preparation and did not leave any lethal contaminant on subluxation by fluoreacene epectronetry. This material formed apricots when exposed to acetone during drawing. Genoa 15 hours of extraction of this polynorium down acetone in a Soxhlet apparatus obtained: a downy white extract (4 Z) with an internal vacuoity of 0.69, while the extracted polymer now showed an internal vacuoity of 1.62. One of the extracted polymer preformed plate rested no apricot formation during tensile bonding in acetone.

Test drug in an Inmtron device and aeeton aprayadea note atavarna nrr atrlekgrlnmen uppnlttm. The effect of this treatment on the traction fracture grnna and fracture elongation viaaa below: _ _ 7201871-6 14 Egenekap Polyneren not Polyneren eëgraherad. extragggad Stretch limit, bp / cnz 590 1 360 Tensile strength limit, bp / cn2 675 870 Bridge tearing,% in zo 85 Example 6 This example illustrates the preferred work-up by spray drying. A 25-percent. solution of poly (benzophenone ether) in hydrogen fluoride was diluted with liquid sulfur dioxide to a solids content of 1.3 5.

The viscosity of the solution was reduced from 1900 cP to 2 cP. The solution, neon contained in a poly (chlorotrifluoroethylene) -coated container, was then fed to a laboratory spray dryer (Koch model 10D, 1 m diameter). Air 'with an overpressure of 0.35 - 1.0 kp / cnz in the nozzle provided the driving force required to overcome friction losses in lines and valves. All construction materials had been selected for maximum corrosion resistance and included fluoroplastics, Hastelloy C and type 304 stainless steel.

The spray dryer consists of a hot gas cylinder with a perforated plate through which the hot gases (in this case air) pass before contact with the liquid spray, an insulated cylindrical drying jug with a conical bottom, and a cyclone separator to separate the solid polymer powder from the hot gases. The HF / SO2 / polyner solution is atomized in a Lurgi two-component nozzle with ambient temperature air, to which a volume stream of about 0.3 Nn3 / min and an overpressure of 1.4 - 2.8 kp / cs is added to the nozzle.

The nozzle is located below the perforated plate in the cylindrical cooler on the center line of the cylinder.

The spray dryer, cyclone separator and associated pipe system are constructed of stainless steel 304 down all flange joints sealed with a sealing element consisting of Siloxane plastic. Braided protective gaskets made of PTFE are inserted between the inner surfaces of the dryer and the sealant. "The exhaust gases are cooled in a post-cooling tower constructed of stainless steel 304 by being passed through a plurality of cold water showers. are constructed by Hastelloy C. "The polymer solution is fed to the twin component piece down a volume 65 of 65 l / h and a temperature of -6 ° C to ensure that no one enters the solution prior to release of the solution. The warning air used as a drying medium is sprayed into the dryer at 220 ° C down to a volume of 12.6 13 / min and is removed at a temperature of 16000. The heat losses due to the mixing of the hot and cold air strands and the genonization are similar. for 20 6 30 ° of the specified temperature drop. The rest of the protective energy is needed for the extension of the solvent. The warp air enters the dryer with a pressure of 75 nn v.p. and in the cyclone separator with a pressure of 50 now v.p.

The polymer is collected at the bottom of the cyclone separator in the form of a powder. This virus at 150 ° C during the overnight vacuum in an oven to remove the last traces of volatiles before the extrusion of the polymer. After drying, the polymer has a breaking elongation of over $ 100.

The fluorine content of the spray-dried polymer is determined by first melting the polymer into sodium peroxide at elevated temperature in a closed nickel bean (Hilos Hudlicky, Chemistry of Organic Fluorine Columns, Macmillan Co., New York, 1962, p. 322) and The eluent then orders spectrophotonetrically with a zirconium cyanine pigment (zirconiul 'Erioohrone Cyanine R) according to a method given by Stephen Megregian (Anal. Chen., 26 (1954) 1161. The dried polymer on the indicated surface did not contain down to about S0 - 100). ppm fluorine.

Example 2 A polynomer down the internal viscosity of 0.84 was spun at 40596 from a ß5; 3šmolve sprayer equipped with a I 0.5 Is spinneret and a gear driven piston. The salted polymer was pressed through the spinneret and cooled by air at the passage from the spinneret over guide rollers to a surface driven reel at a distance from the spinneret. The fibers were then oriented at 300 ° C and heat treated at 250 ° C below they were kept suspended unloaded for 1 n lengths in a hot air oven sprinkled. The elongation at break of a 123 den. fiber was $ 16. The initial nodule was 85 gld, and the force factor 22.

Example 8 In a Brabender type extruder, in which the ratio of the length of the syringe barrel to the diassets was 24tl, the use of a screw having a compression ratio of 3: 1 was sprayed through a 50 x 0.63 In slot nozzle with a polynomial the internal viscosity 1.0 at cylinder temperatures of 375 - 40 ° C over to a take-off roll, son was kept at 120 - 170 ° C. Films with thicknesses ranging from 0.5 to 0.025 L were prepared by varying the speed of the take-up roll.

The deposited film had low water absorption, good tear resistance and preceded the soot path to continued tearing.

The polymers of the invention may contain monomers which may impart advantageous properties to the polymers, e.g. greater strength and crystallinity or higher melting point. Thus, for example, in the polyneration ion, about 5 to 50% by weight of aidanic monomers of 3- or 4- (1'-naphthoxy) -benaoyl fluoride, 3- or 4- (2'-naphthoxy) -benaoyl fluoride may be used. , 3- or 4- (4I-biphenyloxy) -benaoyl fluoride and 3- or 4- (2'-biphenyloxy) -benaoyl fluoride. For example, in the case where a high contact point and solvent resistance are not particularly critical, m-phenoxybenzoyl fluoride can be copolymerized with the paraiaomer.

Of course, other Friedel-Craft catalysts can be used in BBBs, e.g. AIFS, PF5, etc., but boron trifluoride is preferred because of the ease with which it can deflate, relative toxicity, and the like.

These and other variations of the preferred embodiments described above will be apparent to those skilled in the art from the foregoing detailed description. In any case, as a whole, the invention has made it possible for the company to produce polymers that are relatively high-temperature, processable in the molten state, and with an elongation which is sufficient for use in wire and cable insulation.

Claims (13)

7201871 -6 PATENT REQUIREMENTS Polymeric product containing one or more polymers having the recurring unit {__ \ c characterized by the fact that the polymer or polymers have an intrinsic viscosity of about 0.8 - 1.65 dl / g (measured on a solution of 0.1 g polymer in 100 ml of solution of concentrated H2SO¿ at 25 ° C), has an elongation at break at room temperature of at least about 50% and is terminated with residues of a terminating agent, the reactivity of which towards acetylation compared to benzene is greater than about 150, which polyketone can be processed into shaped products in the molten state. Polymer product according to claim 1, characterized in that the intrinsic viscosity is 1.0 - 1.55. Polymer product according to claim 1, characterized in that the intrinsic viscosity is 1.2 - 1, h. 4. A polymeric product according to claim 1, characterized in that the agent is aromatic. in Polymer product according to claim 4, characterized in that the agent is free of aliphatic groups and unsubstituted in the ring. Polymer product according to claim 4, characterized in that the agent is biphenyl, diphenyl ether, h-phenoxybenzophenone or 4,4'-diphenoxybenzophenone. ü A process for preparing a polymeric product containing one or more polymers with the recurring unit / \ C wherein the polymer or polymers have an intrinsic viscosity of about 0.8 - 1.65 dl / g (measured on a solution of 0.1 g of polymer in 100 ml solution of concentrated H2SO¿ at 25 ° C), has an elongation at break at room temperature of at least about 50% and is terminated with residues of a terminating agent, the reactivity of which towards acetylation compared to benzene is greater than about 150, according to claim characterized in that one or more monomers of the formula (ífš-O-Qco x _ ~ v2o1s71-s u 18 where X represents a hydrogen-leaving group) are polymerized under Friedel-Crafts acylation conditions to form a polymer containing the above-mentioned recurring unit, the polymerization being carried out in the presence of an aromatic terminating agent, the reactivity of which against acylation compared to benzene is greater than about 150. Process according to Claim 7, characterized in that the polymerization is carried out in a non-metallic environment. 9. A process according to claim 7 or 8, characterized in that the Friedel-Crafts catalyst is boron trifluoride. 10. 'l0. Process according to any one of claims 7 to 9, characterized in that the terminating agent is free of aliphatic groups. 11. ll. Process according to claim 10, characterized in that the agent is biphenyl or diphenyl ether. Process according to one of Claims 7 to 11, characterized in that the polymer is recovered by spray-drying the reaction solution. " 13. » Process according to Claim 7, characterized in that - p-phenoxybenzoyl chloride is polymerized in the presence of a catalytic amount of boron trifluoride and a non-aliphatic aromatic terminating agent in an amount sufficient to give a polymer with at least about 50% elongation at break. and having an average intrinsic viscosity in the range of about 1,1 - 1,65. f _ PRESENTED PUBLICATIONS: United Kingdom 1 D86 021 (C089 33/00) US 3,441 5381260-49)