BE639634A - - Google Patents

Description

       

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  Production of polysulfones.



   The present invention relates to the production of polysulfones as well as novel polymeric materials containing sulfone groups in the polymer chain.



   The present invention relates to a process for the production of polysulfones in which a first compound containing two sulfonyl halide groups bonded to an aromatic system and at least one second compound containing at least two bonded hydrogen atoms are carefully melted. to an aromatic system in the presence of 0.05 to 5% by weight of the compounds of an iron salt soluble in the polymerizable mixture or of antimony pentachloride.



   Alternatively, at least one simple organic compound, containing a sulfonyl halide group and a hydrogen atom both bonded to an aromatic system may replace the combination.

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 of the first compound and of the second compound above, Monomers.



   The first compound must have two sulfonyl halide (-SO2X) groups each bonded to an aromatic ring. They can be linked to the same nucleus or to different nuclei. The nucleus can be derived from benzene or from a polycyclic aromatic hydrocarbon. By polycyclic aromatic hydrocarbon is meant a hydrocarbon containing two or more condensed rings, at least one of which is aromatic. By way of examples, there may be mentioned indene, naphthalene, anthracene, phenanthrene and chrysene.



   However, it is preferred not to use disulfonyl halides which are derived from compounds such as anthracene, phenanthrene or chryaene, which contain three or more condensed aromatic rings as this can result in crosslinking of the polymers. Although this tendency can be reduced by deactivating all jump-two rings by substitution of the aromatic hydrogen atoms, for example, with nitro, carboxylate, aldehyde, ketone, nitrile, sulfone, sulfate or sulfonate groups, it is used. - re-use polycyclic aromatic hydrocarbons containing no more than two aromatic rings such as naphthalene, indene and fluorine.

   Further, it is preferred to use disulforyl halides in which each sulfonyl halide group is bonded to an optionally substituted benzene ring.



   These compounds fall into three categories represented by the following structures
 EMI2.1
 or pure substituted derivatives of those compounds in which one or more aromatic hydrogen atoms are replaced by other atoms or by monovalent groups.



   In III, Y represents any suitable bivalent bridge. For example, Y can be:

 <Desc / Clms Page number 3>

 
 EMI3.1
 -0 $ 8 # -sa-, -S02-, .co, -MONU-0 .co.O-, Q.CO.0-, a bivalent hydrocarbon radical a bivalent ether or th10éthlr radical or the residue of a diol . By residue of a diol is meant the bivalent structure obtained by removing the two hydrogen atoms
 EMI3.2
 hydroxylic compounds of an organic compound containing two hydroxyl groups.



  The first compounds specified in the group 1 are the ben * alsulfonyl halides and their substitution derivatives in which one or more of the four hydrogen atoms bonded to the
 EMI3.3
 benzene ring can, if desired, be tpl.c6. by other substitutes. Examples are the 13- and., 4-benx? Ned.su..fonyl halides. The 1,3- derivatives are pr'pr6r4. because of their ease of preparation.

   Suitable subatlutants for the benzene ring are, for example, mono hydrocarbon groups. valents, ether and thioether groups and their substituted halogenated derivatives, hydroxy groups, thiol groups, carboxyl groups, amine and substituted amino groups, nitro and nitroso groups, aldehyde groups, ketone groups,
 EMI3.4
 nitrile groups, sulfone groups, aultonatt groups, sulfate groups, and halogen atoms. It is preferred that the optional substituents be in the meta position with respect to the hole.
 EMI3.5
 pe -502X because the substitution of one ortho ttnd positions cause steric hindrance during poly # cSr1, .t.1on.



  Suustitution on the b8naén1qUt nucleus affects the aotivx-
 EMI3.6
 The nature of the xultonyl halide in the polymer and the nature and position of the substituent are therefore important.



  The effect of such a substitution can be demonstrated by a simple test. It was generally observed that the presence
 EMI3.7
 groups known to activate an elrtxaphilr substitution in the mett position adversely affect the polymerization; and therefore cannot be used compounds bearing, for example, nitl'ot curboxylate, aldehyde, odtone, nitrile, sulfone, sulfate or sulfpnrrto groups. Substituents that contain hydroeene atoms (Active (pilar exeapie amine, mono-amine groups)

 <Desc / Clms Page number 4>

 substituted, thiol and hydroxy) tend to react with the polymerization catalysts and it is also preferred that they be absent.

   Substituting them! preferred are halogen atoms, as well as hydrocarbon groups, ether and thioether groups
 EMI4.1
 and halogen derivatives. Substituted benzened1ltOnyl and benzenedisulfonyl chlorides are, for example, benzene-1,3-disulfonyl chloride, talubn2kdlsuJ.fonyJ.s chloride, toluene-3,5-disulfonyl chloride, ootylbenxene3 disulfonyl chloride. , chlorabenxetx-R'4-dil.tonyl chloride, anisole-3,5-disulfonyl chloride and bensene-1,4-disulfonyl chloride.



   It has generally been observed that when the first
 EMI4.2
 My specified compound has both sulfone halide groups on the same benzene ring, polymerization is too slow and! it is therefore preferred to use the compounds of structure II or III.



  Among the compounds of structure II or III, the derivatives are preferred.
 EMI4.3
 of the 4,4'-disulfonyl chloride type which are the most accessible.



  It is also possible to use the substituted derivatives of these compounds in which the hydrogen atoms of the aromatic rings and / or the hydrogen atoms linked to carbon atoms of the optional bridge are replaced by other atoms or monovalent groups.



  In the case where the substitution relates to the aromatic rings, the activation rules described for the substitution of the compounds of structure I also apply * The preferred substituents are therefore halogen atoms, hydrocarbon groups, ether groups and thiodthor and their halogen derivatives.



   In general, it is preferred that there are no bulky subatituents in the ortho position to the sulfonyl halide groups as they tend to cause steric hindrance during polymerization. It is further preferred that in the aromatic rings only the hydrogen atoms ortho to the bridge are replaced by other atoms or other groups,
In compounds of structure III, it is preferred that the bridges are not those which tend to deactivate the rings.

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 aromatic, such as sulfone or ketone groups, and which therefore
 EMI5.1
 inhibit polymerization or unstable groups in the reaction candidates (for example sultoxydet carbonatez carboxylftte groups,

   citrbaiante aaido or aliphatic hydrocarbons biva. slow containing aliphatic carbon atoms in the chain between the aromatic rings or residues of a11ptu.t.lque diol). In addition, when the pontontiont an aroaat nucleus, 1 that, it is proffered that this is deactivated so that it cannot participate in the polymerization and thus rùyor18or crosslinking. It was also preferred that the bridges be such that they there are no more than four atoms in the chain between neighboring aromatic rings, because with longer bridges the products obtained tend to have
 EMI5.2
 raJ pointa: 1Ol11ueuum t too low.



   Preferred bridges are oxygen atoms, sulfur atoms and structural groups:
 EMI5.3
 
 EMI5.4
 where K and I 'are selected from the class consisting of oxygen and sulfur atoms and L is -CO- or -80, Fl, The first compounds specified may have a third sulfonyl halide group, if it is desired to obtain a crosslinked product.



   The second compound of the process using two components can be any aromatic compound containing at least two atoms.
 EMI5.5
 of hydrogen bonded to the aromatic system. The aromatic compound may be a polycyclic aromatic hydrocarbon such as indone, anth. cene, ph6nantrene or chrysene (but is preferably a hydro carbide containing no more than two aromatic rings, such as naphthalene, illudene or fluorene) or a compound of structure 1, II or II! above in which the sulfonyl halide groups are replaced by hydrogen atoms.

   In the case where the aromatic compound comprises only one benzene ring # as in the

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 structure I, it can carry up to four constituents and in the case where it has structure II or III, each bensene nucleus can contain up to five substituents (including the bridge) thus retaining in each das at least two hydrogen atoms linked to aromatic nuclei.



   For substituted aromatics, the preferred types of substituents and preferred positions of substitution on the aromatic rings are those described above for the disulfonyl halides.



   It is generally observed that if benzene or a substituted benzene is chosen as the second compound of the two-component process, the reaction is very slow and it is therefore preferred to use compounds of structure II or III which do not bear a halogen group. - sulfonyl nide.



   The second preferred compounds are therefore those which have structure II or III in which Y is an oxygen atom, a sulfur atom or a group having the structure:
 EMI6.1
 defined above, or substituted derivatives of structures II and III bearing halogen atoms, monovalent hydrocarbon groups, ether or thioether groups or their corresponding halogenated substituted derivatives, but preferably halogen atoms, groups alkyl of 1 to four carbon atoms or alkoxy groups of one to four carbon atoms, on one or more of the positions of the aromatic rings ortho to the pons.



   In general when the first and second compounds of the polymerization have the structure of type II, the products tend to be inflexible and brittle and it is therefore preferred that at least one of the compounds has the structure III.



   In a preferred embodiment of the production

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 EMI7.1
 of polysultbnes according to the invention by a proedd4 with soft con.t1tuarù 'the first compound is chosen from those of etruoturt t
 EMI7.2
 
 EMI7.3
 
 EMI7.4
 and the second compound among those of .truoture 8.
 EMI7.5
 
 EMI7.6
 where Z and Z # are chosen from the class formed by 11 & 1.on.

   direct, the oxybene atoms, the atoms of the Other and the grouped
 EMI7.7
 do structure
 EMI7.8
 4
 EMI7.9
 
 EMI7.10
 where K and K * are each selected from the class closed by oxygen and sulfur atoms and L is -80x- or -C0- | and at least one of groups 2 and Z 'is not a direct bond and IR, 1, R3 ot R
 EMI7.11
 are each chosen from the class formed by hydrogen atoms,
 EMI7.12
 d3llialogen atoms, alkyl groups of 1 to 4 carbon atoms
 EMI7.13
 ne and alkoxy groups of 1 to 4 carbon atoms.
 EMI7.14
 



  Examples of these compounds are diphenyl, diphenyl ether, diphdnyl sulfide, di (O-Chlorophenyl) sulfide, ttaar di (: -6thuxyphûaylique), .pnoyta.ub $ leduler dl -3,5-dictilorophZnyllluet di-o-tolyl ether and 4,4'-diphnvxrdiphenylsall'anc ot their derivatives 4,4'-duu, onylre,
 EMI7.15
 We can use mixtures of the first and second
 EMI7.16
 composa SPéc1rt4o in the process, 6dd of the invention to form mixed pol) nnére3. The choice of composas porinet to modify conisidd rabletaent the physical properties of the polymer products. In senna

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 RAL, it is preferred to use equimolecular amounts of the first compound and the second compound. However, when it is desired to limit the molecular weight, one can use one of the compounds in excess.



  Alternatively, the molecular weight can be changed by adding a mono-functional compound to the polymerization mixture. By mono-functional compound is meant a compound which has only one atom or active group under the reaction conditions. An example is a 3,5- disubstituted benzenesulfonyl halide such as 3,5-dichlorobenzenesulfonyl chloride.



   In another embodiment of the invention, the disulfonyl halide (s) used in the polymerization may be replaced in part by one or more compounds containing two carbonyl halide groups bonded to an aromatic ring. These compounds can have the structure I, II or III where the groups CO. X replace SO2.X groups. The preference criteria for these carbonyl halides are in general the same as for the disulfonyl halides and the products obtained from these polymerization mixtures are mixed polymers containing -CO- and -SO2- groups in the compounds. polymer chains. Products with very varied physical properties can be obtained by acting on the nature and the concentration of the compounds participating in the polymerization.

   However, products which contain groups which are derived from dioarbonyl halides generally tend to be crystalline.



   In the modified process of the invention according to which the combination of the first and the second compound is replaced by a single compound as described above, it is possible to use any aromatic compound bearing on a single nucleus or on different nuclei at the same time a an aromatic sulfonyl halide group and an aromatic hydrogen atom. Examples are monosulfonyl halides derived from benzene and polycyclic aromatic hydrocarbons (preferably containing no more than two aromatic rings) and compounds of structures II and III above, but bearing only one halide group. from sul-

 <Desc / Clms Page number 9>

 
 EMI9.1
 fonyle.

   The rules for the selection of these compounds are at the same time that those of the first and second compounds of the process have two conttl- tants, and it is preferable for the compounds of structure 1 to be selected.
 EMI9.2
 
 EMI9.3
 where Z, h, 112P h3 and "4 have the meanings given to them above.



  Clauses of these aonosulfonyl halides can be used, if desired * to give mixed polymers,
 EMI9.4
 and the aodiric process is therefore particularly suitable because of its flexibility. Aromatic taonooarbonyl hidides of equivalent structure can be copolymerized also with the culfonyl halides to give aixteo polymers.

   If desired, the limitation of the molecular weight of the products obtained by this modified process can be achieved by adding to the mixture of
 EMI9.5
 Polymerization of a mono-functional compound, as defined pre-deaKcentt It will be appreciated that an equ3max mixture of the pruter and second specified compounds may come into contact with one or more of the aonosulfonyl halides specified to give highly polyjterized products by the process of the invention * Any deviation from the equiaoleeuitires proportions in the mixtures of the first and second compounds will tend to reduce the molecular weight.

     
The polymerization can be carried out by heating the compound (s) and the catalyst, in the presence or absence of an inert Mirent. Suitable solvents are highly polar compounds
 EMI9.6
 co = e 1 & cyclic tetraaethylenesulfone, iiitrondume and nitrobenzene. However, the presence of solvents generally slows down the reaction and the products obtained usually have a heavy weight.
 EMI9.7
 low molecular weight because the low molecular weight polymers

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 wax are soluble in solvents.

     In addition, the use of a solvent is economically unattractive and it is generally preferred to do without.



   In the two-component process, it is preferred that the disulfonyl halides and the second components are all in approximately equimolecular proportion. However, the proportions may deviate from equimolecular proportions when it is desired to reduce the molecular weight of the product. In the modified two or more component process, these may be added in any desired proportions *.



   The polymerizable compound or compounds are advantageously heated to melt and mixed thoroughly before incorporating the catalyst into the melt. During the polymerization the temperature is increased so as to maintain the constituents in the molten state and when the maximum required temperature is reached it is maintained for an additional period generally of the order of 2 to 3 hours. , to complete the polymerization.



  During the polymerization gaseous hydrochloric acid is evolved, and must be removed, for example by carrying out the reaction in vacuo. The reaction is preferably carried out in the presence of an inert gas, such as nitrogen, to avoid the presence of oxygen on the molten mixture. When it is desired to obtain a high molecular weight polymer, in a reasonable time, temperatures of 200 ° C. and above are generally required.



   The catalysts used for the polymerization are iron salts soluble in the polymerizable mixture or antimony pentachloride; the salts can be ferrous salts or ferric salts. As the molecular weights of the polymers formed by this process generally increase with the polymerization temperature, it is preferred to use catalysts which do not dissociate into inert products, even at high temperatures between 200 and 250 * C. Antimony pentachloride tends to dissociate at around 170 C and is therefore not suitable for obtaining products

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 high molecular weight,
Examples of suitable ter salts are fluorine
 EMI11.1
 ferric ride, ferric chloride, ferrous broaide, ferrous iodide,

   ferric orthophsphate and ferrous and ferric aoetoacetonates. In general, iron halides are preferred to be used because of their valuable catalytic activity and ferric chloride is particularly preferred because of its solubility in many solvents and its ease of preparation in very pure form, and above all because it high molecular weight polymers always give suitable conditions.



   The catalysts are used in quantities included
 EMI11.2
 between 0.5 and 5, of the weight of the constituents polyaerit & blos. Amounts below a. 05 generally give only very slow polymerization. It is preferred not to use more than 1% by weight of catalyst because the residues thereof are difficult to separate from the polymer.

   Amounts between 0.1 and 0.854 are preferred *
 EMI11.3
 As already pointed out, polymers of high aolocular weight (which are generally those which have the most interesting physical properties) are obtained in a reasonable time by
 EMI11.4
 performing the polyzu "rlsatlon at temperatures el Vdeo # generally of the order of 200 C or more Indeed an increase in weight,

       molecular is accompanied by an increase in the softening point
 EMI11.5
 ment of the polymer and when the molecular weight of the polymer fora 4 is such that its racaal.lsaanant point reaches or exceeds the polymerization temperature * the reaction mass tends to solidify and the polymerization becomes very slow or s' stopped. Any.
 EMI11.6
 folop it has been found that polymers have an undesirable tendency to curl if subjected to too high temperatures, in particular.
 EMI11.7
 generally close to t50G during polymerization.

   On the other hand, ; it is only when the polymerization temperature is maintained at
 EMI11.8
 about 5t1G or more than products having good physical strength are obtained. Cross-linked polymers are generally
 EMI11.9
 insoluble in usual solvents and cannot be handled 8tr,

 <Desc / Clms Page number 12>

 They are therefore of little value for molding, spinning and solvent casting.



   A subject of the present invention is therefore also an improved process for obtaining polymers of high molecular weight according to which the polymerizable material is subjected, in the presence of the catalyst, to a temperature higher than its melting point but lower than that resulting in a temperature. appreciable crosslinking of the polymerized product until the mixture becomes viscous or solid; this mixture is cooled and ground, and the ground product is reheated to a temperature inside that at which substantial crosslinking would take place to complete the polymerization.



   In the preferred method, the polymerizable material is introduced into the polymerization vessel and heated until melting. When two or more compounds are used, they are thoroughly mixed in the molten state. The polymerization catalyst is then dissolved in the molten mixture. In general, a short induction period is observed, then a rapid evolution of halogenated hydracid (usually hydrochloric acid gas) shows the onset of polymerization.



   Since some of the polymerization reagents can react with water, it is preferred, when high molecular weight products are desired, to remove moisture completely from the reaction substance during polymerization and, in the improved process, during grinding. . It is also preferred to carry out the reaction in the absence of air, for example, by venting the reaction vessel or purging it with an inert gas, such as nitrogen, or by using both of these methods.



   The degree of progress of the polymerization can be measured by the evolution of halogenated hydracid.



   After the addition of the catalyst, the sheared mixture is kept at an elevated temperature until it becomes a very viscous or solid mass. It has generally been observed that the polymer product crosslinks if the polymerization mixture is subjected to temperatures above about 250 ° C. and it is preferred.

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 therefore do not work above this temperature. To avoid crosslinking, it is preferred to carry out the first stage of polymerization.
 EMI13.1
 tion at 20t'C or below, until the product becomes viscous or solid.



  The rapid increase in viscosity and 4yctu.ll..nnt solidification of the molten mixture shows that the polymers have reached a molecular weight which gives them a softening point above the temperature of the polymerization mixture. solidification depends on the temperature of the molten mixture: an increase in temperature usually results in a reduction in time. It is therefore preferred to use a temperature
 EMI13.2
 as high as possible which does not result in riUCNlaU01'h Temperatures from isd to 200 * C are usually 00l \ ... b1 ...



   The molten mixture generally forms in the reaction vessel a viscous or expanded solid mass which is then cooled and ground to a fine powder. The heather is produced * in
 EMI13.3
 under anhydrous conditions in order to avoid catalyst traction. Any suitable method of grinding may be used The fine powder is then reheated and maintained at a high temperature, below
 EMI13.4
 However, at the crosslink temperature, until the end of polymerization.

   It is preferred that this heating be carried out under reduced pressure in order to facilitate the removal of the hydrogen gas aid. Temperatures of 150 ° C to 250 ° C are suitable. The time required for the second heating depends, equal in t, on the t¯pÓra tuz1. ' high temperatures corresponding to short times. Times of 15 minutes to a few hours are generally suitable, depending on the molecular weight desired and the scale at which it is desired. The end of the reaction is indicated in gM4ftl by the end of evolution of the gaseous halogenated acid *
After polymerization .. it is preferable to separate from the product the catalyst residues, the presence of which may cause
 EMI13.5
 alteration of 1, n color ot sometimes .'-: te a degradation. Any suitable method is suitable.

   For example, pol) 'llith can be ground into a powder and treated with hydrochloric acid in an alcohol,

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 preferably methanol, at reflux. However, this process is often impractical and only separates small amounts of the catalyst. It is therefore preferred to use the process described in English patent application n * 38.974 / 63, which follows that the polymer is dissolved in a suitable solvent such as dimethylformanide or nitrobenzene and treated in solution with a complexing agent, preferably a chelating agent. , to complex the catalyst. The complex is then separated from the polymer.

   The treated polymer can be reprecipitated by pouring the filtered solution into a suitable non-solvent for the polymer, such as an alcohol, preferably methanol; or acetone, then it is carefully dried, preferably at high temperature and vacuum,
The products often tend to set "during high temperature treatments, especially in the molten state. This" setting ", which can be small, is estimated to be evidenced by an increase in the viscosity of the melt, is caused by a decomposition of carbonyl or sulfonyl halide end groups which creates active sites on the polymer chain.

   These active sites result in a crosslinking reaction which can ultimately reduce the polymer to an insoluble and infusible mass, unusable in conventional processes of processing plastics, such as injection or compression molding or extrusion. The "setting" reaction can be substantially reduced or eliminated entirely by the process described in UK Patent Application No. 38,973 / 63, according to which the polymers are reacted in solution, at a temperature below that at which the "set" would manifest itself with an organic compound containing per molecule one or two groups capable of reacting with the sulfonyl or carbonyl halide groups of the polymer to give products which are stable at the temperatures at which the polymer is melted.

   Suitable compounds are aromatic amines, particularly aniline, and the process can advantageously be carried out before, during or after the separation of the catalysts from the polymer. In this case, any excess of the compound can be separated from the

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 polymer at the same time as the complexed catalyst *.
 EMI15.1
 11.18 'DCI1Yl # era8.



  The products obtained are polymers which contain
 EMI15.2
 repeating units in which a sulfone group is bonded to two aromatic residues. Noncrosslinked products are thermoplastic, generally high softening point, and can be used in any suitable plastics process.

   High molecular weight noncrosslinked polymers
 EMI15.3
 These are tenacious solids which are practically resistant to many chemical agents, both acidic and alkaline. They can be melt spun into fibers and filaments or cast into films from solutions in suitable solvents. They can-
 EMI15.4
 can be mixed with other suitable constituents of pigments, light and heat stabilizers, plasticizers, lubricants, mold release agents and fillers and they can be mixed with other polymers, if desired.
 EMI15.5
 



  The process of the invention aims to produce a new group of polyeulfones which have high softening points and remarkable stability at high temperatures even above. laughing at their points of rolll'8ent. The amorphous polymers of this group are soluble in many organic solvents, tenacious, often transparent and stable for a long time in the molten state. They therefore lend themselves particularly well to shaping by products.
 EMI15.6
 Usual cedes retorts the mold by injection and by coOolpro.tJ1on, 'and extrusion.



   The present invention also relates to novel polymeric materials for drilling repeating structural units.
 EMI15.7
 -Ar..S02- where Ar is a divalent aromatic residue which derives from bonzëne, from a polycyclic hydrocarbon, from diphcnyl, from a compound of structure:

   

 <Desc / Clms Page number 16>

 
 EMI16.1
 where P represents -0-, -8-, -SO-, a divalent hydrocarbon radical, a substituted bivalent hydrocarbon radical, the remainder of a diol containing only carbon atoms or groups of structure -COC- and -C -8-C .. in the chain between the two hydroxy groups, or substituted derivatives of those aromatic residues in which one or more of the aromatic hydrogen atoms are replaced by groups or other monovalent atoms, and Ar can vary from one unit to another in the polymer chain, In the case where the remainder is derived from an aromatic polycyclic hydrocarbon, it is preferred that it be that of a hydrocarbon containing no more than two aromatic rings, because the products are thus less likely to crosslink.



   When these polymers are obtained by the two-component process described above, for example by using a disulfonyl halide of structure: X.SO2-Ar-SO2.X and a second compound of structure: H-Ar'-H (where Ar 'has the meaning given to Ar), they have repeating structural units: -Ar-SO2-Ar'-SO2- but when they are obtained by the modified process using one or more compounds each carrying a only one sulfonyl halide group bonded to an aromatic system and one single aromatic hydrogen atom, they comprising repeating units of structure 1 -Ar-SO2- distributed statistically, where Ar can vary from one unit to another in the chain .



   It will be appreciated that in the first mentioned process, two or more disulfonyl halides of general structure t X.SO2-Ar-SO2.X can react with one or more aromatic compounds of general structure H-Ar'-H.



   A subject of the present invention is also polymers comprising repeating units of structure t -Ar-SO2- as defined above, and units of structure: -Ar-CO-

 <Desc / Clms Page number 17>

 
 EMI17.1
 oh Ar can take the above meanings higher
Polymers which contain $ -Ar-CO structure units tend to have an oristalline character, even when Ar
 EMI17.2
 represents two nuclei ben & (1qu'J united by a bridge.



  Owing to their easy preparation and their advantageous physical properties, the preferred polymers of the invention are those in which Ar is a residue derived from bencene, diphenyl, compounds of the structure:
 EMI17.3
 or derivatives of those residues in which one or more aromatic hydrogen atoms are replaced by other atoms or monovalent groups.

   Among these polymers, more preferred are those in which at least part of the Ar residues are derived from compounds of structure IV or from derivatives of these compounds in which one or more aromatic hydrogen atoms are replaced by other atoms or monovalent groups, park * only polymers
 EMI17.4
 are particularly well suited for molding into tough, high-softening, tri-parent articles. Preferred when substituted drifts of the residues
 EMI17.5
 are present in the polymer chain whether the aubatiimenta are halogen atoms, lower hydrocarbon groups, ether or th10ether groups or halofenated derivatives of CI 'croup.

   because the polymers are then inert * with respect to many chemical agents * It is particularly preferred that the optional substituents are halogen atoms, alkyl groups having
 EMI17.6
 from 1 to 4 carbon atoms or alkoxy groups having 1 14 atoll. of carbon. Further preferred are polymers in which the aromatic hydrogen atoms optionally replaced are only those bonded to meta carbon atoms to the bridges.

 <Desc / Clms Page number 18>

   -SO2- because of their ease of preparation.

   In general we lent. re polymers in which no aromatic hydrogen atom is replaced by other atoms or groups., due to their remarkable inertness towards acidic or alkaline chemical agents, even at very high temperatures, Polymers with aromatic residues of structure IV in which P is an oxygen or sulfur atom, or a residue of a diol containing up to 4 carbon atoms or a divalent aliphatic hydrocarbon radical containing 1 to 4 carbon atoms in the chain between the aromatic rings and not more than ten carbon atoms in the tetal,

   are formed from easily accessible monomers * Derivatives of these monomers in which one or more aromatic hydrogen atoms in the ortho position to the P bridge have been replaced by halogen atoms or alkyl or alkoxy groups of 1 to 4 carbon atoms, are also easily accessible. accessible. # Preferred polymers according to the invention, which are generally thermally stable lA. very high temperatures, even above their melting points, include repeating units of structures t
 EMI18.1
 where P is an oxygen atom or a sulfur atom, and R1, R2, R3 and R4 are selected from the group consisting of halogen atoms, alkyl groups having 1 to 4 carbon atoms and alkoxy groups of ! 1 to 4 carbon atoms.

   



   Particular examples of these polymers are those which are forced by a combination of structural units:
 EMI18.2
 

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    and structural units:
 EMI19.1
 
It is generally observed that an increase in the number of units of structure VI corresponds to an increase in the softening point of the preferred copolymers, but makes them more and more brittle. Those of the preferred polymers in which these units represent more than 80% of the total number of units tending to be crystalline and insoluble, and which can only be worked with difficulty by the usual processes for easy use of plastics.

   On the other hand, polymers that contain 5% monk
 EMI19.2
 of these units have a low rr.co.liaucrt point. This is why we are looking in particular for those of the preferred polymers in which these units represent $ to 80% of the total units.
 EMI19.3
 Preferred polymers which contain about 0% of this unit exhibit an excellent combination of tensile and softening point properties.



  The polymers of the present invention have
 EMI19.4
 Remarkably high softening., frequently on the order of 300 ° C. or more, are thermoplastic and, after treatment to avoid "prie", are long stable in the molten state. Amorphous polymers form particularly well by virtue of their softening properties without undergoing degradation, to give objects which are generally tough, transparent and inert to many chemical agents, both acidic and alkaline.

     '
 EMI19.5
 They can be spun into fibers and filaments which can be used in applications where resistance to
 EMI19.6
 chemicals and high temperatures are desirable, for example in the manufacture of your own protective products, and they can be extruded into tough, transparent films which-regulate-

 <Desc / Clms Page number 20>

 flexural strength and are suitable for packaging or electrical applications, where their high softening point is particularly advantageous.

   They can be shaped by any suitable method to give tough, transparent and tough molded articles which have good thermal degradation stability at temperatures up to 300 C. The manufactured products are suitable, for example, as electrical insulators. for example in transformers, circuit breakers and capacitors.



   Many of the products are soluble in polar organic solvents such as nitrobenzene and dimethylformamide.



  Fibers and films can be formed from the solutions and coatings can be deposited as well, for example on wire to form a good electrical insulator. The coated products can be used under conditions in which high temperatures may be encountered, for example in electrical transformers and high voltage circuit breakers.



  The products of the invention whose molecular weights correspond to reduced viscosities of 0.6 or more (measured on a solution of 1 g of polymer in 100 cm3 of dimethylformamide at 25 ° C.) have a combination of physical properties. , such as tensile strength, modulus and softening point, which make them particularly suitable for molding. For applications which require their mechanical strength, polymers whose reduced viscosities are at least 1.0 are preferred.



   Polymers have good adhesion to surfaces such as glass and metals and adhere particularly well to glass. They can therefore be used as high temperature thermoplastic adhesives for metals (eg stainless steel), pure example for the manufacture of household items such as ovens, irons, etc.



   The polymers can be mixed with other suitable constituents such as dyes, pigments, sta-

 <Desc / Clms Page number 21>

 
 EMI21.1
 b111, ant. by heat and light * plasticizers, release agents .. lubricants and fillers and threads can be mixed, if desired, with other polymers *
The invention is illustrated by the following examples in which the parts are by weight,
 EMI21.2
 tpaafpus.iv 734 <8 parts (2 moles) of aliphnylether chloride, 4'-diauïTonyla with 308.52 parts (2 moles) of diphenyl are melted in 0 ° C. under a slow stream of nitrogen in a heated vessel. and, after stirring for 30 minutes.

   we add 4 parts
 EMI21.3
 of ferric chloride freshly sublimated to the sheared mixture. The CItAIT] sor dissolves rapidly on stirring with a sharp evolution of acid.
 EMI21.4
 hydrochloric acid gas. The reaction temperature is increased rapidly, but the mixture solidified at a bath temperature of about 180 C. The reaction temperature is then raised to 280 ° C, at which point the mixture solidifies. mixture is still solid. Total reaction time is 40 minutes.



   The mixture is cooled and the product is then ground
 EMI21.5
 and stirred with 1S!> 0 parts of boiling isopropanol. The insoluble product is filtered off and the process is repeated two fathoms. After drying, 880 parts of a polymer having a reduced viscosity are obtained.
 EMI21.6
 measured on a 1% solution in d1Jaeth) 'lfonau1dl, 25 * Ce of 0.15 * The polymer is amorphous as shown by x-ray examination and can be cast into transparent films from a
 EMI21.7
 solution in dlmethylformamide * f.Xr1otPLb.



  530.64 parts (about 1.3 moles) of 4-diphenyl ether chloride # 40-dimafonylp 137.76 parts ($ 0.1 mole) are melted at 90 ° C under a slow dlatote stream in a heated vessel. Benzen6-1,3-dlsulfonyl chloride and 307.56 parts (approx. 2 moles) of diphenyl * After stirring for 30 minutes, 6.5 parts of ferric chloride are added and a sharp acid is released
 EMI21.8
 hydrochloric acid gas begins. The reaction temperature is raised over 20 minutes to 280 ° C. It is then slowly raised to 300 ° C.

 <Desc / Clms Page number 22>

 and kept at this value for 40 minutes)) '. The total reaction time is 95 minutes.



   The product is treated as in Example 1 to give
870 parts of a tough, clear polymer having a reduced viscosity of 0.30. The polymer is amorphous as shown by x-ray examination and can be cast into stubborn films from its solutions.



   EXAMPLE 3. -
It is dissolved in 5650 parts of anhydrous nitromethane at
95 C, under a slow stream of nitrogen, 551.94 parts (1.5 mole) of diphenylether-4,4'-disulfonyl chloride, 137.64 parts (0.5 mole) of benzene-1 chloride, 3-disulfonyl and 308.27 parts (about 2 moles) of diphenyl and the mixture is stirred. After 10 minutes 15 parts of ferric chloride are added and a slow evolution of hydrochloric acid gas begins. The stirred mixture is heated at reflux for 6 hours, during which time the polymer precipitates from solution as a fine powder.



   The powder is filtered and treated as in Example 1 to give 260 parts of a polymer having a reduced viscosity of 0.041.



     EXAMPLE 4.-
729.10 parts (about 2 moles) of diphenylether-4,4'-disulfonyl chloride and 315.8 parts (about 2 moles) of diphenyl are dissolved in 7567 parts of cyclic tetramethylenesulfone at 105 ° C. and the mixture is stirred under a slow stream of nitrogen. After
10 minutes of stirring, 8 parts of ferric chloride are added as a solution in 630 parts of cyclic tetramethylene sulfone. Slow evolution of hydrochloric acid gas begins, and the reaction temperature is raised to 210 ° C. over 4 hours and maintained at this value for a further 3 hours.



   The mixture is then cooled and poured into an excess of stirred isopropanol and the insoluble product is filtered and treated, as in Example 1, to give 520 parts of a polymer having a viscosity.

 <Desc / Clms Page number 23>

 sity reduced by 0.07.



   The results of this example and of example 3 show. that only low molecular weight products can be obtained by solution polymerization.
 EMI23.1
 



  XE ... "WL1 !; 5. Melt and stir at 100OC. Or a slow stream of nitrogen 367.24 parts (1 mole) of 4-diphMylether disulfonyl chloride, 275. 17 parts (1 mole) of benx.rno. ,, 3. Disulfonyl chloride and 308.40 parts (2 moles) of diphenyl. After 10 minutes, 2 parts of ferric chloride are added. A violent evolution of acid is observed. hydrochloric acid gas. In 1 hour, the reaction temperature is raised to 320 ° C, temperature at which the product is a very viscous liquid. The mixture is maintained.
 EMI23.2
 for an additional 45 minutes at 320.0 oc under a vacuum of 0.7 mm Hg, then cooled.



   The product is ground into a fine powder, dissolved in a
 EMI23.3
 hot mixture of 9530 parts of methylformaznide and 1 par. Keep acetyloketone and filtered through an excess of stirred ethunol to precipitate the polymer. 520 parts of polymer insoluble in cold solvents are obtained.

   Relatively low yield
 EMI23.4
 of this example and of Examples 6 to 12 had due to a certain degree of cross-linking which occurs at the high polyrxing temperatures, giving some insoluble polymer which is separated during filtration.
 EMI23.5
 m.LË- All a slow stream of axotum, 367.24 parts (1 mole) of diphonylether''4t4 '' "disulfonyl chloride, 154.20 parts (1 mole) are melted. of benzene-1,3-disulfonyl chloride and 340.40 parts (2 moles) of diphenylethers. 2 parts of ferric chloride are added and the mixture is stirred to dissolve the aatx.

   A brisk release of gaseous hydrochloric acid occurs. Polymerization and treatment of the polymer are carried out as in Example 5 and the yield is 620 parts of a polymer insoluble in cold solvents.

 <Desc / Clms Page number 24>

 
 EMI24.1
 



  LE 7 ..- Melt and stir at 100OC under a slow stream of nitrogen 769.16 parts (2 moles) of diphenylether-4,4'-disulfonyl chloride and 356.72 parts (2 moles) of dipheryl. , the7c, After 10 minutes, 1.7 parts of ferric chloride are added and a violent evolution of hydrochloric acid gas occurs.

   Polymerization and processing of the polymer is carried out as in Example 5, and the yield is 820 parts of a polymer having a viscosity.
 EMI24.2
 reduced size of 0.61 and a softening point of about 320 * C * EXAMPLE 8 -
The process of Example 7 is repeated and the product is
 EMI24.3
 crushed to a fine powder, dissolved in a hot mixture of dimethyltormamide and acetylacetone and filtered through excess acetone, stirred to precipitate the polymer, A polymer product is obtained having a reduced viscosity of 0.76 and a point softening
 EMI24.4
 about 320OCs m'M .... 9., ...



  735 parts (2 moles) of 4,4'-diBulfonyl diphenylether chloride and 340 parts (2 moles) of di-phenylether are melted at 110 ° C. and the molten mixture is stirred for 10 minutes under
 EMI24.5
 a slow stream of nitrogen. Then 3.3 parts of ferric acôtoacetonate are added to the mixture and the temperature is raised over 4 hours 15 minutes to 290 ° C. The mixture is then subjected to a vacuum of
 EMI24.6
 0.3 Il \ J1 of mercury and the temperature is raised to 320 C in 25 minutes and maintained at this value for a further 20 minutes * The molten mixture is then cooled and the solid obtained is ground into powder and stirred and heated to reflux with 7850 parts of isopropyl alcohol and 488 parts of acetylacetone. The polymer is then filtered,

   washed and dried to give 580 parts of a product having a deduced viscosity of 0.28. The polymer is soluble in nit
 EMI24.7
 benzene and d1ftEÍthyltorulLU41de and can be cast in transparent films from its solutions.
 EMI24.8
 SIMPLE .J.C4 ..- The process of Example 9 is repeated using 10

 <Desc / Clms Page number 25>

 parts of antimony pentachloride as a catalyst. The temperature
 EMI25.1
 The polymerization process is finally brought to 30 ° C. for 10 minutes, and the product is a polymer having a reduced viscosity of 0.21.
 EMI25.2
 



  .1J .. "The process of Example 10 is repeated, but the temperature
 EMI25.3
 melting temperature of the mixture to .Ao: 4ent. where the catalyst is added is 130 C and 48 parts of antirAo1n pentachloride are used.



  The polymerization temperature is maintained at 130 ° C for an additional 34 minutes, then raised to 310 ° C over 2 hours. The melan-
 EMI25.4
 The molten ge is then subjected to a vacuum of 0.3 sua of mercury for 10 minutes at 310 ° C before being cooled. The solid product is ground into powder and dissolved in 9530 parts of dibt, hxJ.i'prcaida, then the solution is filtered * in an excess of methanol to precipitate the polebre, The precipitate is washed and dried at 80 C for 3 hours under vacuum to give 520 parts of a polyaur having a reduced viscosity of
 EMI25.5
 it3xe W.4t (12 We melt at 1t, 4C, 367.24 parts (1 stole) of diphenyl chloride ther-4,4 '-di sul tonyl 1 and 402.42 parts (1 mole) of 4,

  4′¯diphenoxydiphenylsulfont and the mixture was stirred under a slow stream of nitrogen for 10 minutes, then 8 parts of ferric chloride 00111.1 was added catalyst. The temperature is brought to 310 ° C in 2 hours, then a sample (sample 1) is taken. The remainder of the adlange is subjected to a vacuum of t.3 SKa of mercury for an additional 45 minutes rice 310 ° C before being cooled to give sample II *
Both samples are treated as described in Example 11, and Sample I gives a polymer having a viscous viscosity.
 EMI25.6
 reduced rate of 0.37, while sample II coated a polymer with a reduced viscosity of 0.47.

 <Desc / Clms Page number 26>

 
 EMI26.1
 



  Exme L izt m {1: l Are melted at 140 C, 619.30 parts (2 moles) of chlorobenzene-2,4-disulfonyl chloride, 1 g 5.4 parts (1.2 mole) of diphenyl and 139.40 parts (0.8 mole) of diphenyl ether and the mixture is stirred under a slow stream of nitrogen for 10 minutes before adding 4.1 parts of ferric chloride as a catalyst,
 EMI26.2
 take out the form of a 4, l solution; in tetrahydrofuran. The polymerization temperature is brought to 190 ° C. in 2 hours 15 minutes and to 230 ° C. 20 minutes later, the product still being melted.



  The molten mixture is cooled and the product is ground to a powder, suspended in a mixture of isopropyl alcohol and acetylacetone, then reprecipitated and dried to give a black polymer.
 EMI26.3
 PLE 14 ..- 2.7 parts of diphenyl chloride are melted
 EMI26.4
 anhydrous 4-ether sulfonyl (melting point 44 ° C) in a closed container fitted with a nitrogen inlet and outlet device, in a dry nitrogen atmosphere, then 0.09 part of ferric chloride is added anhydrous which dissolves in the molten monomer. Moisture is strictly excluded from the reaction vessel. The evolution of gaseous hydrochloric acid begins almost immediately.

   After
 EMI26.5
 7 minutes, the temperature is raised to 1800C and, at this moment, 72% of the theoretical quantity of gaseous hydrochloric acid has evolved. The reaction mixture, which forms a very viscous foam,
 EMI26.6
 partially solid, is cooled to a solid and ground in a dry nitrogen atmosphere then the polymerization is restarted by heating the powder to 110 ° C, The temperature is brought to 18t3 C for 10 minutes further then reduced again, and the product is ground again. The reaction is continued by heating the initial powder.
 EMI26.7
 ment at 1500C all high vacuum then at 240 * C in 15 minutes. The mass is maintained at this temperature for 20 minutes before being cooled, dissolved in 30 parts of dimandthylformamide and filtered.



  The polymer is precipitated by pouring the solution into a stirred mixture of 240 parts of acetone and 30 parts of concentrated hydrochloric acid. The precipitated polymer is filtered off, washed with

 <Desc / Clms Page number 27>

 methanol and dried overnight at 60 ° C under vacuum to give
 EMI27.1
 1 $ 8 part of poly (p-sultonyld1phenylether) having reduced viscosity, measured on a z solution in d1l1etJ111torll & lllde.



  $ 259c of 1.2.



  Samples of this polymer are molded by compress-
 EMI27.2
 At 310 ° C at a pressure of 3150 1sg / a: a in tough, transparent, good quality films which can be folded often without breaking.



   The dynamic mechanical moduli of the polymer are measured at various temperatures by the 100 cycle cantilever vibration method. The modulus decreases slightly by 3.8 x 1010 dy-
 EMI27.3
 neom2 & -1500C at 1.9 x 1010 dynes / cm2 at + 220 * C, EXhMPLK 1S. 2.8 parts of 800C dlphenylether-4-sulfonyl chloride are melted in a dry nitrogen atmosphere and 0.085 part of ferric chloride is added. Moisture is carefully excluded from the reaction vessel.

   After 10 minutes, the temperature
 EMI27.4
 is brought to 2O0 C and, at this moment, 68, of the theoretical quantity of gaseous hydrochloric acid have evolved * The mixture, which is in the form of a viscous foam is solidified by re
 EMI27.5
 rroid1SBe.J100t and ground in a nitrogen atmosphere then the polymerization is taken up by heating the powder to 100 ° C. under an absolute pressure of 0.1 mm of mercury.

   The temperature is brought quickly to 220 "C and maintained at this value for 2 hours, then brought to 240 * C in another 90 minutes, after which the mass is cooled,
 EMI27.6
 dissolved in 30 parts of dlÓth) 'lro1'lll ... ld. hot and filtered, and the polymer is precipitated by pouring the solution into stirred chloroform The precipitate is filtered, washed with methanol and dried for 1 hour at 200 C under high vacuum to give 1.8 parts of a polymer having a reduced viscosity of 1.35, measured on a solution
 EMI27.7
 tion to 1 in the d1U1Ót.h, ylto1 "! I16J:

  11of it 25 * This
Clear films are cast from a 10% solution of the polymer in nitrobenzene and are found to be
 EMI27.8
 are tenacious up to 60 C. {.

 <Desc / Clms Page number 28>

 
 EMI28.1
 



  EXF-PLF 16.- 3.5 parts of dlphenylether-4-aulfonyl chloride are sheared at 80 ° C in a dry nitrogen atmosphere, and 0.09 part of ferric chloride is added to the molten product. moisture is carefully excluded from the reaction vessel. After 10 minutes, the temperature
 EMI28.2
 rature is brought to 180 "C and at this point the reaction reaches a progress of 78%, calculated on the basis of the evolution of hydrochloric acid gas. The viscous foamed mass is solidified.
 EMI28.3
 by cooling, crushed and reheated 1500C under high vacuum. The temperature is brought to 2b0 C in 10 minutes and maintained between 240 ° C and 2500C for another 30 minutes, before cooling the mass.

   The cold polymer is dissolved in 40 parts of dimethylfor-
 EMI28.4
 Ntuaid, precipitated by pouring the solution into 300 parts of 5N hydrochloric acid well stirred, filtered, washed with methanol and dried overnight at 60 C under vacuum to give 2.8 parts of a polymer having a reduced viscosity of 0.99, measured on a
 EMI28.5
 1% solution in dimôthYlrormamide at 25 C.



  The viscosity of the polymer melt under constant shear of 8.2 x 1Q dynea / cm2 is 2.3 x 10 3 poises at 35O C.



  TEMPLE \ '1 .., -
 EMI28.6
 According to the process of Example 3, 2.9 parts of diphenylether-4-sulfonyl chloride are polymerized in the presence of 0.07 part of ferric chloride as catalyst. The temperature is raised to 170 C in 9 minutes and, at this time, the degree of progress of the polymerization is 67, calculated on the basis of the quantity of gaseous hydrochloric acid released.
 EMI28.7
 queuse obtained is solidified by cooling, crushed and reheated to 1500C. After 12 minutes at this temperature, the mass was cooled and ground again and then slowly warmed to 250 ° C under high vacuum over 30 minutes.

   The mass is held at 250 ° C for an additional 10 minutes, cooled and then treated by the process described in Example 3 to give 2.3 parts of a polymer having a reduced viscosity of 0.78. measured on a 1% solution in dimethylformamide at 25 C.

 <Desc / Clms Page number 29>

 
 EMI29.1
 



  33.3 parts of dlphenyldther-4-sulfonyl chloride are mixed with 1 part of freshly boiled ferric chloride, then the mixture is heated to 200 ° C over 15 minutes and maintained at 200 ° C for 2 hours while passed. a slow stream of dry nitrogen over the reaction mixture. During this period, 96% of the theoretical amount of hydrochloric acid gas was evolved. The product, which appears in the form of a brown foam, is ground and then heated at 230-234 ° C for 5 hours at an absolute pressure of 0.9 mm of mercury. The brown polymer obtained is
 EMI29.2
 dissolved in 300 parts of diaethylfor.a <Anhydrous Mide and 1 part d of aniline and stirred for 1 minute.

   Add 4 parts resol 8-hydroxy qulnol'lntt-5-wltonlque and stirring is continued for 30 minutes. The solution is then percolated through a column 26.7 cm long and diameter. of 3,, ground ai lined with Spence type H alumina from 149 to 74 nuerons. The intense dark green iron complex is adsorbed on the first $ centi-
 EMI29.3
 meters from the column. After the solution drops through the column, the adsorbed polymer is eluted with an additional 150 parts d1Jaethyltomu.tdlMl. The polyera is precipitated from its nearly colorless solution by pouring it into 200 parts of a well stirred 5% aqueous hydrochloric acid solution.

   The white precipitate is filtered off, washed twice with 500 par-
 EMI29.4
 parts of distilled water and once with 250 parts of .4Itn4U \ ol and finally dried at 120 ° C under vacuum for 16 hours, to give 25.6 parts of polymer. Analysis shows that the pollUltone contains less than 20 parts per million irons The polymer can be
 EMI29.5
 held at 320 ° C for several minutes without appreciable increase in viscosity and transparent films of a very yellow
 EMI29.6
 plaice can be molded from the product at, tfC. e, .rhP1 19.

   w 35 parts of diphenylether-4-sulfonyl chloride are polymerized by the method described in Example 18 using

 <Desc / Clms Page number 30>

 1.62 part of ferric chloride as a catalyst. The gross product
 EMI30.1
 is dissolved in 300 parts of dlmdthyltormamide at room temperature and the solution is divided into four equal parts which are each stirred with 1 part of aniline for 15 minutes. To three of the four parts is added the singing agent indicated in .le
 EMI30.2
 table below and the four solutions are p.roole8 through an alumina column, as described in Example 18,

   then the polymer is precipitated and isolated by the procedure of Example 18. The results are shown below.
 EMI30.3
 
<tb>



  Quantity <SEP> Concentration
<tb>
<tb> Solution <SEP> Chelating agent <SEP> <SEP> added <SEP> added <SEP> in <SEP> iron <SEP> in <SEP> on
<tb>
<tb> (in <SEP> parts <SEP> polymer <SEP> (ppm)
<tb>
<tb> in <SEP> weight)
<tb>
<tb>
<tb>
<tb> A <SEP> None <SEP> - <SEP> 70
<tb>
 
 EMI30.4
 B 8-hydraxyquinoline acid 2,8 20 -5-aulfonic C dimethylglyc> xime 0.7 30 D ethylenediemine-acid 1.6 30
 EMI30.5
 
<tb> tee <SEP> plotted <SEP> tick
<tb>
 
In each case, the polymer obtained has a reduced viscosity of 0.72. Each of the four samples can be held for a long time (up to 20 minutes and more) in the molten state without detectable increase in its viscosity.



    PEOPLE 20.
Melt at 130 ° C in a nitrogen atmosphere, 7.73 per
 EMI30.6
 1 parts of diphenylether-4-sulfonyl chloride and 13.09 parts of diphenyl-4-sulfonyl chloride. 0.39 part of ferric chloride is added to the molten mixture and the temperature is raised to 180 ° C in 26 minutes during which 80% of the theoretical amount of gaseous hydrochloric acid are released * The expanded mass is cooled and ground and the powder is heated to 140 ° C. under vacuum, then heated to 210 ° C. over 25 minutes * The mass is cooled and ground again then reheated a second time at 120 ° C. under vacuum.

   The temperature
 EMI30.7
 The temperature is brought to 240 ° C in 12 minutes and held at 240-2 $ 0 ° C for 130 minutes. The musse is then cooled and dissolved in

 <Desc / Clms Page number 31>

 
 EMI31.1
 220 parts of dimethylforaamide plus 2.0 parts of the line and 1.8 parts of 8-hydroxy-quinoline-5-sulfonlque acid. The mixture is stirred for 20 minutes and then percolated through a co-
 EMI31.2
 alumina column, coame described in text 18.

   The polymer is precipitated by pouring the solution obtained into hydrochloric acid.
 EMI31.3
 than diluted, then washed twice with hot taethanol and dried for 18 hours at 100 ° C under vacuum to give 16.7 parts of a copolymer having a reduced viscosity of 0.91 and a very soft softening point. high, above 300 C, and containing only 20 parts per million of iron.



   An almost transparent and colorless film is cast
 EMI31.4
 from a solution of this polymer in nitrobenzene at 90C, E¯ H'tF'L 21.-
A series of polysulfones are prepared by applying the method described in Example 20, but using quantifications.
 EMI31.5
 Diphenylether-4-sulfonyl chloride and dlphenyl-4-sulfonyl chloride variables. Certain properties of the products obtained are described below.
 EMI31.6
 



  5i & K? Ïïï !! r Modulo (2) Point dt dlphny16thcr- dyne. 9 / ca2 r0111 ...- s111fonu in 10 ment copolymer (by (1),. U ........... # # . # ,.! ##,., "" '* "' analysis Ih) Force -150 C + 200.C 100 a. se 3.8 x 1010 1.9 x 1010 approximately 240 * C 84 a. se * 6 x 1010 1.6 x 1010 2G 74 a.8z, 9 x 1010 2.0 x 1010> 250 * C 43. 8. 2el x 1010 103 x 1010) 2'0.0 23 aa no J:

  1t1wrd> 250 "C Ox c. 1. li x 1010 1.2 x 1010) 2M'C ¯jjuiiLn.ui ii-i -i.-rri-i.ua ami urt they wmii mu # n \ m iwmw itt jh j - -> ,. aitwf.mj L. rr - (1)
 EMI31.7
 a * amorphous c * crystalline s = soluble i = insoluble (2)
 EMI31.8
 measured by the ioabd, of vibration on uortuiJ'x described by hob1nl'on dbns J.

   f1ci.Instrwuents, page 2, 1955 'x This polymer.' does not 8'xpnn6e during polymerization

 <Desc / Clms Page number 32>

 
All amorphous copolymers can be cast in solution to give tough films, but these become more and more brittle with the decrease in the number of diphenyl ether sulfone groups in the polymer.
 EMI32.1
 EXAMPLE 22 295 parts of diphenyl-4-sulphonyl chloride (mp 73 ° C) are melted at 120 ° C. in a dry nitrogen atmosphere and 5.4 parts of rerrl chloride are added to the molten mixture. - 'that freshly sublimated. The temperature is raised to 180 C in 12
 EMI32.2
 minutes at the end of which the quantity of gaseous hydrochloride acid # ique represents 74% of the theoretical quantity.

   The product is cooled, ground to powder and heated under high vacuum to a temperature of 140 C to 230 C in 14 minutes. The mixture of
 EMI32.3
 The reaction is finally maintained at 230-240 ° C for 105 minutes then cooled and dissolved in about 5000 parts of dimethylforaamide. This solution is treated with 51 parts of aniline and then with 35 parts of g-hydr, aay quinoline-5-sulfonic acid. The mixture is stirred and then percolated through an alumina column, as described in Example 18.

   The polymer is precipitated in chlor acid. diluted water, washed with hot methanol and dried at 100 C under vacuum to give 210 parts of a product having reduced viscosity (measured on a solution of 1 g of polymer in 100 cm3 of
 EMI32.4
 dimethylfornuunide at 5U C) of 0.56 # X-ray examination shows that the polymer is amorphous.

   
 EMI32.5
 EXMHLK 23.-
In a series of tests, 267 parts of di-phenylether-4-sulfonyl chloride are heated with a catalyst (shown
 EMI32.6
 in the table below) at 150 C for 40 minutes to give an expanded mass which is cooled, crushed and reheated under high vacuum (about 0.2 mm Hg, absolute pressure) at 230 C over 15 minutes * The mixture of reaction is finally maintained at 230 C for 1 hour, then cooled, dissolved in about 3000 parts
 EMI32.7
 of dindttiy7.i'ozuutidc and treated, as described in Example 22, by

 <Desc / Clms Page number 33>

 
 EMI33.1
 30.6 parts of aniline and 22 parts of 8-hydroX1quino16int-5-culfonic acid.

   In each case, the polymer obtained has a reduced viscosity (measured on a solution of 1 g of polymbre in 100 cc of d1sethylfor.Aulde Ù. 25 "C) of 0.1 fA 0.2.
 EMI33.2
 Test Ctlr.1Y $ wr Quantity used
 EMI33.3
 
<tb> read <SEP> (in
<tb>
<tb> part)
<tb>
 
 EMI33.4
 Toric tuloptiotiphthate 60-i
 EMI33.5
 
<tb> B <SEP> ferric <SEP> fluoride <SEP> 3,4
<tb>
 
 EMI33.6
 C Ferrous joint 605
 EMI33.7
 
<tb> D <SEP> Iodide <SEP> ferrtux <SEP> 9.3
<tb>
 
 EMI33.8
 :; QltPMJt 2 ..



  15.1 parts of 4 "phenoxy <'benzoyic chloride (bp 146 ° C at 0.4 mm Hg) and 27.1 parts of 4-diphenylether-rulronyl chloride (point melting point 44 ° C) at 130 ° C in a slow stream of dry zate. 1.4 parts of freshly sublimated ferric chloride are dissolved in the sheared mixture, the temperature is brought to 220 C in 75 minutes, and observed. while
 EMI33.9
 '9 of the theoretical amount of hydrochloric acid <hjfeux are released. The mixture is cooled to give a hardy foam which is crushed and reheated to 230-240 C in 40 minutes under high vacuum.



  The mixture is again cooled, ground into powder and washed with
 EMI33.10
 diaethylfora cold then with methanol and know t 80 ° C for; t 2 hours under vacuum to give 29 parts of a crystalline polymer L-analysis by infrared spectroeraphy (by comparison with standard mixtures of homopolyacres derived from each of the polymerizable monomers) shows that the product contains 35% by weight of structural units 1 it
 EMI33.11
 The determination of the sulfur in the polymer shows that it contains 36% by weight of these units.

 <Desc / Clms Page number 34>

 
 EMI34.1
 



  BCKMPLE 2- 41.7 parts * of 4-, Pheno-V-benzoyl chloride and 5.3 parts of diph-snylether-1, tsuu7.onyl chloride 170 C are melted and dissolved in molten mixture 2, 5 parts of freshly sublimated ferric chloride. After 2.75 hours at 170 * cl 86% of the theoretical amount of gaseous hydrochloric acid has been released and the mixture is cooled, ground and warmed to 240 C in 90 minutes under high vacuum (0.1 mm absolute pressure ). The product is cooled again, ground to powder, washed with hot acetone and dried overnight at 90 C under vacuum to give 36 parts.
 EMI34.2
 of a polymer partially soluble in nitrobenzene and soluble in 4,4 * -diphcnoxydiphenylsulfone at 200 ° C.



  Analysis by infrared spectrography, by the method described in Example 24, shows that the polymer <t contains 90 by weight of structural units.
 EMI34.3
 The polymer is highly crystalline and its crystal form
 EMI34.4
 line is that of the homopolymer of 4-phenoxyben% oyl chloride.



  '1; I'1'tPN.' 26. -
A series of polymerizations are carried out using the process of Example 25, but using concentrates.
 EMI34.5
 Variable Monomer and Catalyst Tions * The concentrations of each of the monomers and catalyst and the form of the products obtained are shown below.
 EMI34.6
 



  Test 1- Mohomërëg * '\ ± by weight of, Form of Test II Catalyst units in 1polymbre - 1 11 Catalyst 1; . d & nS polymer
 EMI34.7
 
<tb> A <SEP> 37.0 <SEP> 10.7 <SEP> 2.2 <SEP> 78 <SEP> crystalline
<tb>
<tb> B <SEP> 32.4 <SEP> 16.1 <SEP> 2.4 <SEP> 67 <SEP> crystalline
<tb>
<tb> C <SEP> 23.2 <SEP> 26.7 <SEP> 1.8 <SEP> 46 <SEP> crystalline
<tb>
 
 EMI34.8
 x I = 4-phenoxybenzoyl chloride. Il = diphenyl ether-4-sulfonyl chloride


    

Claims (1)

EMI35.1 r k Y. N I I C A ü i 8. .t) -. 0. t <t * <- # K. t! . * t # tW ## mttft 1 ,. A process for the production of polysulfonfsj characterized in that at least one first compound was melted together with two sulfonyl halide groups bound to an aromatic system and / at least one second compound contained at least two hydrogen atoms * 1 EMI35.2 EMI35.3 eëfna linked to an aromatic system, in prt $ '& uico from 00 to 3% of the weight of the compounds of a soluble iron salt. in the polymeric-sand mixture or of antimony pent & chloride 2, frocd according to 1 & claim 1 CêtµtQ % eri * 4 in that the catalyst is an iron halide. 3. A method according to claim 1 or 2 # characterized in that the catalyst is ferric chloride. 4. "A process according to claim 3, cat # ictèrlsd in that the catalyst is used in an amount of between tt.7 and 005% by weight * of the polymeric monomers. 5.- Process followed one or the other must rdiQti, on 1 to 4. characterized in that the molten polyp ri Sabla is heated at a temperature of at% oins 200 ° C. 6.- A process according to one or more of the preceding rwvdioations, characterized in that the polymerlita.- ble mixture is heated in the presence of the catalyst a temedrature higher than its melting point, but lower than that at laqueâ., Se would produce a substantial cross-link, until the m6lns becomes viscous or solid, the mdlilneup is cooled, the cooled aelmige is ground, and the ground product is then reshilled to a temperature below that at which substantial cross-linking occurs. EMI35.4 would * EMI35.5 7. A method according to claim 6, characterized in that the jiaxitua temperature of the first heating is taken between 150 and 200 C, 80. Process according to 1t. claim 6 or '7, oaraçtîlrlod in cc that ln tf% mpdrâture aaxiaua from the second heating is understood <Desc / Clms Page number 36> between 150 and 250 C. 9. A process according to either of the preceding claims, characterized in that the polymer product is treated to separate the residues from the catalyst. 10. A process according to claim 9, characterized in that the polymer product is treated in solution with a complexing agent of the catalyst and then separated from the catalyst complex 'formed. 11. A method according to either of the preceding claims, characterized in that the polymer product is treated in solution with an organic compound containing per molecule one or two groups capable of reacting with the sulfonyl halide or halide groups. carbonyls the polymer to give products which are stable at temperatures above their softening points. 12. A method according to claim 11, characterized in that the organic compound is an aromatic amine. 13. A method according to claim 12, characterized in that the organic compound is aniline. 14.- Process according to either of claims 1 to 13, characterized in that the first compounds are chosen from the class of disulfonyl halides of polycyclic hydrocarbons containing not more than two aromatic rings and of structural compounds. EMI36.1 where X is a halogen atom, and Y is a divalent bridge, or their substituted derivatives in which one or more aromatic hydrogen atoms are replaced by other atoms or monovalent groups. 15.- The method of claim 14, characterized in that the first compounds are chosen from the class of compounds. <Desc / Clms Page number 37> EMI37.1 Xtëa of structures EMI37.2 EMI37.3 o4 Y is a bivalent bridge and h 1t2 'li3 and 84 are each selected from the class formed by the & 4tooAt of h1drocn., the..tom .. cS'haloln., 1 the r..d1c4tux hydrocarbon 5a monovll. 'nt., inonova- lent ether groups, monovalent thiother groups and ddr1,4. halo, 4n "of these radicals. 16, .. flrooÓdt according to the r.vend1e & t.1on 15; o.rAot.4r1., in that the compound pre = lcrs have chosen from the eltate compounds of structure EMI37.4 EMI37.5 Where Z is a direct bond, an oxida atom., A .tcll. ci * sulfur EMI37.6 or a structure group EMI37.7 EMI37.8 where the and lt 'are chosen from & ns 1 & drilling class by the itoat of oxygen and the atoae of sulfur and L is -CO- or "002-' and Hp% # 3 and A4 are each chosen from 016l'8 drilled by the hydrogen atom * the atoms of hclogen, the alKYl groups of 1 & 4 carbon atoms EMI37.9 EMI37.10 and alkoxy groups of 1 to 1 carbon atoms. 17, - Process according to one or the other of the claims <Desc / Clms Page number 38> previous, characterized in that the second compound are chosen from the aromatic class formed by benzene, polycyclic aromatic hydrocarbons not containing more than two aromatic rings, diphenyl, the compound! containing two benzene rings linked by a bridge and their aromatic substituted derivatives which still contain at least two aromatic hydrogen atoms * 18.- The method of claim 17, characterized in that the second compounds are selected from the class consisting of structures EMI38.1 where Y is a divalent bridge and R1, R2, R3 and R4 are each selected from the class formed by hydrogen atom, halogen atoms * r & monoyal hydrocarbon radicals, monovalent ether radicals, thloether radicals monovalent, and the halogenated derivatives of these radicals. 19.- The method of claim 18, characterized in that the second compounds are chosen from the class of compounds of structure EMI38.2 where Z is a direct bond, an oxygen atom, an otter atom, or a structural group EMI38.3 where K and K 'are selected from the class formed by the oxygen atom and the sulfur atom and L is -CO- or -SO2- and R ,, R2, R and R, are each selected from the class formed by the hydrogen atom, <Desc / Clms Page number 39> halogen atoms, alkyl groups of 1 to 4 carbon atoms and alkoxy groups of 1 to 4 carbon atoms ,, 20.- Method according to one or the other of claims 1 to 19, characterized in that the first composites are chosen from the class of structural compounds EMI39.1 and the second compounds are chosen from the class of compounds of structure EMI39.2 where Z and Z 'can be the same or different and are chosen from the class formed for a direct bond * the oxygen atom, sulfur atone and structural groups EMI39.3 where K and K 'are chosen from the dusse formed by the oxygen atom and the sulfur atom and L is. -CO- or -SO2- and R1, R2, R3 and R4 are each selected from the class forced by hydrogen atom, halogen atoms, alryl groups of 1 to 4 atoms. carbon and ulkoxy ridges of 1 to 4 carbon atoms. 21, - A method according to either of the preceding claims, characterized in that the first compost is chosen from the class of structural compounds EMI39.4 where Z is a direct bond, an oxygen atom, an atom do <Desc / Clms Page number 40> sulfur, or a structural group EMI40.1 where K and K 'are selected from the class formed by the oxygen atom and the sulfur atom and L is -CO- or -SO2-. 22.- Process according to either of the preceding claims, characterized in that the second compounds are chosen from the class of compounds of structure EMI40.2 where Z is a direct bond, an oxygen atom, a sulfur atom, or a structural group EMI40.3 where K and K 'are selected from the class formed by the oxygen atom and the sulfur atom and L is -CO- or -SO2-. 23.- proceeds according to claim 21 or 22, characterized in that the first compounds are chosen from the class of compounds of structure EMI40.4 and the second compost are chosen from the class of structural compounds EMI40.5 where 2 and Z 'can be the same or different and are chosen <Desc / Clms Page number 41> EMI41.1 in the class formed by a direct bond, the oxygen atom, t, 10 &to; qe of sulfur and the structural groups EMI41.2 EMI41.3 oH K and K 'are selected from the class formed by oxygen and sulfur atoae and L is -CO * or -: 3t., 246. Proceeds according to one or otter of claims! 1 & 23, characterized in that at least one cocapoad containing two crbonylo tialorenide groups 11; 1.s has an ewt amattic system. EMI41.4 fade with the first and second compounds EMI41.5 25.- Process according to claim 2) characterized in that the diphenyl <5ther-4,4'¯dlaulfonyl chloride is sheared with diphthnyl. 26 .. vroedad according to the resellj.cttion 23, because * cUrl 4 in that the d-iphu'nylether-4,, 40-disullonyl chloride is melted with the diphanylether. 27.- The method of claim 23, in that the diphûnyl4ther-4,4 '- <il8ulfônyi chloride is melted with 4 "4'-diphdnoxydiphonylsulfone 28.- To? Roc4dé according to Revondication 14, characterized in that the chloride of diph <5nyléther-4,4 * -dlifUlfônyl is melted with the diphonyl and the chloride of ben Qne-l, 3-di-ulfonyl. 29.- Process according to claim 14, characterized in that the chloride of diphnyltllar-4,4'-dieultnyla melted with the diphenyl ether and the chloride of barièna-1,3-d3aulcnylr. 30. A process according to claim 14 is produced in that the chioroicnrno-, 4-dis.tonyl chloride is melted with the diphenyl and the diphenylether. EMI41.6 31.- Method according to either of claims 1 to 13, characterized in that the combination of the first compound with the second compound is replaced by at least one compound containing EMI41.7 having a single sulfonyl halide group and a hydro- <Desc / Clms Page number 42> EMI42.1 gene, both attached to an aromatic nucleus # 32.- Process according to claim 31, characterized in that this,% compounds are selected from the aromatic monoeuloa fonyl halides derived from benzene of polyoycu '' aromatic quotas not containing more of two arotatic rings are diphenyllic compounds containing two benzene rings * linked by a bridge and substituted derivatives of these lai.oy: aroatic monosulfonyl nides which still contain at least one aromatic hydrogen atom, 33.- Process according to claim 32, characterized in that these compounds are chosen from the classa of compounds of structures EMI42.2 EMI42.3 where Y is a divalent bridge and li 3% P li3 and H4 are each chosen from the class formed by hydrogen ato40 and halogen atoms, and monovalent hydro-carbon radicals, monovalent dicux ether , monovalent thiodther radicals and the halogenated derivatives of these radicals. 34.- Process according to claim 33, characterized in that these compounds are chosen from the class of structural compounds EMI42.4 where Z is a direct bond, an oxygen atom, a sulfur atom, or a structural group EMI42.5 <Desc / Clms Page number 43> where K and K 'are selected from the class formed by the oxygen atom and the sulfur atom and L is -CO- or -SO2-, and R1, R2, 21, and. R4 are each selected from the class formed by the hydrogen atom and halogen atoms and alkyl groups of 1 to 4 carbon atoms and alkoxy groups of 1 to 4 carbon atoms, 35.- The method of claim 34, characterized in that at least two structural compounds are melted together EMI43.1 where Z is a direct bond, an oxygen atom * a sulfur atom or a structural group EMI43.2 where K and K 'are selected from the tonal class by the oxygen atom and the sulfur atom and L is -CO- or -SO2-, and R1, R2, R3 and R4 are each selected from the forged class by the hydrogen atom and halogen atoms and alkyl groups of 1 to 4 carbon atoms and alkoxy groups of 1 to 4 carbon atoms, at least one of them having the structure or 2 , is a direct bond * and at least one of them has the structure where Z is not a direct bond. 36.- Method according to claim 35, characterized in; what we melt together two structural compounds EMI43.3 where Z is a direct bond, an oxygen atom, a sulfur atom, or a structural group <Desc / Clms Page number 44> EMI44.1 where K and K 'are chosen from the class formed by the oxygen atom and the sulfur atom and Lest -CO- or -SO2-, one of them being a compound where 2 is a direct bond and the other a compound where Z is not a direct bond, 37.- A process according to claim 34, characterized in that the compound is diphenylether-4-sulfonyl chloride. 38.- The method of claim 34, characterized in that the compound is diphenylthioether-4-sulfonyl chloride. 39. - A method according to claim 36, characterized in that the diphenylether-4-sulfonyl chloride is heated with diphenyl-4-sulfonyl chloride, 0 40, - A method according to one or the other of claims 31 to 39, characterized in that at least one compound containing a single sulfonyl halide group and a hydrogen atom both attached to an aromatic ring is fused with at least one compound containing a single carbonyl halide group and a carbonyl atom. hydrogen both attached to an aromatic nucleus. 41.- Process according to claim 40, characterized in that the 4-phenoxybenzoyl chloride is heated with the chloride ';, of diphenylether-4-sulfonyl. 42.- A method according to either of the preceding claims, characterized in that a mixture of at least a first compound containing two sulfonyl halide groups bonded to a system! aromatic and at least one second compound containing at least 2 hydrogen atoms bonded to an aromatic system is fused with at least one compound containing a single sulfonyl halide group and a hydrogen atom both bonded to an aromatic ring. 43.- Process according to claim 42, characterized in that a mixture of at least one compound containing two halo groups. <Desc / Clms Page number 45> Carbonyl cenide bonded to an aromatic system and at least one compound containing at least 2 hydrogen atoms bonded to an aromatic system is also present. 44. A process according to claim 42 or 43, characterized in that at least one compound containing a single carbonyl halide group and a hydrogen atom both bonded to an aromatic ring is also present. 45.- Method according to either of the preceding claims, characterized in that a mono-functional compound is added to the polymerization mixture to act on the molecular weight! ! re products. 46. A method according to claim 1, substantially as described above with reference to Examples 1 to 13. 47. The method of claim 31, substantially as described above with reference to Examples 14 to 17. 48. The method of claim 31, substantially as described above with reference to Examples 18-20. 49. ' A method according to claim 31, substantially as described above with reference to Examples 21 to 23. 50. A method according to claim 6, substantially as described above with reference to Examples 14 to 17. 51. The method of claim 6, substantially as described above with reference to Examples 18 to 20. 52. A method according to claim 6, substantially as described above with reference to Examples 21-26. 53. - A method according to claim 40, in substance as described above with reference to Examples 24 to 26. 54. A polymeric product prepared by the process according to any one of the preceding claims. 55. - Polymeric material formed from repeating units of structure -Ar-SO2- where Ar is a divalent aromatic residue derived from benzene, a polycyclic hydrocarbon, diphenyl, a compound of the structure <Desc / Clms Page number 46> EMI46.1 where P is -O-, -S-, -SO-, a divalent hydrocarbon radical, a substituted bivalent hydrocarbon radical or a residue of a diol containing only carbon atoms or groups of the structure -COC- or - CSC in the chain between hydroxyl groups, or such substituted aromatic compounds in which one or more of the hydrogen atoms attached to the aromatic rings are replaced by other monovalent atoms or by monovalent groups, and Ar can vary from unit to unit of the polymer chain. 56.- Polymeric material formed from repeating units of structure-Ar-SO- where Ar is a divalent aromatic residue derived from benzene, a polycyclic hydrocarbon containing not more than 2 aromatic rings, diphenyl, a compound of structure EMI46.2 where P is -O-, -S-, -SO-, a bivalent hydrocarbon radical or a substituted bivalent hydrocarbon radical, or a residue of a diol containing only carbon atoms or groups of the structure -COC- or - CSC- in the chain between hydroxyl groups, or such substituted aromatic compounds in which one or more of the hydrogen atoms attached to the aromatic rings are replaced by halogen atoms, alkyl groups of 1 to 4 carbon atoms or alkoxy groups of 1 to 4 carbon atoms, and Ar can vary from unit to unit of the polymer chain. 57. A polymeric material according to claim 56, characterized in that at least some of the repeating units are derived from compounds of the structure. <Desc / Clms Page number 47> EMI47.1 EMI47.2 where P is -0 .., -8-j -80- $ a hydrocarbon radical bir4entp un grâdi '! bivalent substituted hydrocarbon cal, or a residue of a diol containing only carbon atoms or structural groups EMI47.3 -C-O..C- or -C-S-C- * in the chain between the hydroxyl groups, or such substituted aromatic compounds in which one or more; hydrogen atoms linked to aromatic rings are replaced EMI47.4 by halogen atoms, alkyl groups of 1 to z, carbon atoms or alkoxy groups of 1 to 4 carbon atoms, 58.- Polymeric material formed from repeating units of ' EMI47.5 structure -Ar-802 - where Ar is a divalent aromatic nucleus of structure EMI47.6 EMI47.7 where P is -o- or -S- and..H1I li2j, i at 114 are selected from the class forced by the hydrogen atom and halogen atoms and alkyl groups of 1 to 4 carbon atoms and alkoxy groups of 1 to 4 carbon atoms, and Ar can vary from unit to unit of the polymer chain. 59. - Polymeric material drilling of repeating units of Structure -Ar-SO- or Ar is a divalent aromatic nucleus of structure <Desc / Clms Page number 48> EMI48.1 where P is -0- or -S-. 60, - Polymer material for.neo of repeating units of structure EMI48.2 and recurring units of structure EMI48.3 where P is -O- or -S- and R1, R2, R3 and R4 are selected from the class formed by the hydrogen atom and 'halogen atoms and alkyl groups of 1 to 4 carbon atoms and alkoxy groups of 1 to 4 carbon atoms ,, 61. - Polymeric material according to claim 60, characterized in that from 5 to 80% of the units of the polymer chain have the structure: EMI48.4 where R1, R2, R3 and R4 are chosen from the class formed by the atom <Desc / Clms Page number 49> hydrogen and halogen atoms and alkyl groups of 1 to 4 carbon atoms and alkoxy groups of 1 to 4 carbon atoms. 62.- Polymeric material according to claim 60 or 61, characterized in that it is formed of unit *! recurrent structure EMI49.1 and recurring unit of structure EMI49.2 63.- Polymeric material, characterized in that it is formed of repeating structural units EMI49.3 64.- Polymeric material, characterized in that it is formed of recurring structural units EMI49.4 65.- Polymeric material, characterized in that it is formed from recurring units of structures EMI49.5 66.- Polymeric material, characterized in what is <Desc / Clms Page number 50> made up of recurring units of structures EMI50.1 67.- Polymeric material, characterized in that it is formed of recurring units of structures EMI50.2 68.- Polymeric material, characterized in that it is formed of repeating units of structure -Ar-SO2- and -Ar-CO-, where Ar is a divalent aromatic residue derived from benzene, of a polycyclic hydrocarbon , diphenyl, a compound of the structure EMI50.3 where P is -O-, -8-, -SO-, a divalent hydrocarbon radical, a substituted bivalent hydrocarbon radical or a residue of a diol containing only carbon atoms or groups of the structure -COC- or - CSC- in the chain between hydroxyl groups, or such substituted aromatic compounds in which 1 or more of the hydrogen atoms bonded to the aromatic rings are replaced by other monovalent atoms or by monovalent groups, and Ar can vary from unit to unit of the polymer chain . 69 ... Polymeric material, characterized in that it is formed of repeating units of structures EMI50.4 <Desc / Clms Page number 51> 70, - Polymeric material according to one or otter of, $ claims 55 to 69, characterized in that it does not contain sulfonyl halide or carbonyl halide groups 71, - polymer dobby according to one or otter of claims 55 to 70, characterized in that it has a reduced viscosity of at least 0.6 measured on a solution of 1 g of polymer EMI51.1 in 100 cm3 of dimethylformamide at 250C, 72.- Polymer hatter according to one or more of claims 55 to 71, characterized in that it has a reduced viscosity of at least 1.0, measured on a solution of 8 of polymer EMI51.2 in 100 cm3 of 25OCt dimethylforiamlde 73. A polymeric material according to claim 55, substantially as described above with reference to Examples 1 to 74. - A polymeric material according to claim 55, in substance as described above with reference to Examples 14 17. 75. A polymeric material according to claim 55, substantially as described above with reference to Examples 18 to 20. 76. A polymeric material according to claim 55, substantially as described above, with reference to Examples 21-26. EMI51.3 77. A polymeric material according to claim 68, substantially as described above with reference to Examples 24-26. 78. A fiber formed from a polymeric material according to any one of claims 55 to 77. 79. A film formed from a polymeric material according to any one of claims 55 to 77. 80. A molded article formed from a polymeric material according to any one of claims 55 to 77.