BE565267A - - Google Patents

Description

       

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   The present invention relates to new shaped articles and especially textile filaments and fibers, and films.



   It is known to react diamines with bibasic acids to form polyamides. These polymers have found wide applications in industry because they can be formed into strong abrasion resistant fibers and films. However, the known polyamides lack several desirable properties. In general, they have relatively low melting points and degrade rapidly on contact with air at temperatures as low as 200 C. A characteristic

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 More important characteristic of these polyamides is that they lose a significant part of their strength at temperatures well below their melting points.

   Many polyamides have little tendency to crystallize, and therefore soften at temperatures considerably below their melting point, and have an undesirable amber color which makes them unsuitable for many purposes. Cold drawn filaments prepared using these polyamides tend to shrink at temperatures considerably below their melting points and degrade rapidly at their melting temperatures.



   The polyamide shaped articles of the present invention are not subject to these undesirable limitations and therefore apply to areas from which polyamides have heretofore been excluded. The new items consist of or contain a polymer having the following repeating structural element:
 EMI2.1
 where Ar1 and Ar2 are divalent aromatic radicals of the same or different composition and where chain extension bonds are attached to non-neighboring carbon atoms in an aromatic ring or ring system. However, these articles generally exhibit the full advantages of their properties only when the polymers have an inherent viscosity of at least 0.6 and preferably greater than 0.8 in concentrated sulfuric acid at 30 C.



  Ar1 and / or Ar2 in the recurring structural element formula may be single ring aromatic radicals or they may contain more than one aromatic ring which may or may not be substituted. Nitrogen atoms, and in general also carbon atoms, can be attached to the radical in the meta position. It is sometimes advantageous that the products have structural elements which, although having the same chemical composition

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 that, have the carbon atoms and / or the nitrogen atoms attached to the aromatic radical in the para position. It is preferable that the articles or, respectively the polymers contained therein, have melting points greater than 300 C.



   The filaments or textile fibers of the present invention possess remarkable new properties in combination with great utility if the polymer molecules are oriented in the direction of the longitudinal axis. The fabrics containing oriented funicular structures have new unsuspected properties. The shaped articles may also be in the form of films which may or may not be oriented. Unoriented films, as a coating on a substrate which may be metal, glass or fabric or other materials, exhibit an unexpectedly high degree of adhesion to their substrate. Self-supporting films are preferably oriented at least in one direction.



   Due to the high melting points of the polymers used in the production of the articles of the present invention, it is desirable or necessary to form these articles from solutions of the polymer, preferably in a solvent containing nitrogen or a sulfoxy group, subsequently removing the solvent.



  The solvent can be the solvent in which the polymer has been prepared from its starting materials. Or, it may be a low molecular weight, high amino nitrogen liquid amine. Often the solvent power of this amine solvent and the properties of the solution can be improved by the addition of hydrochloric acid which converts at least part of the amine to the corresponding hydrochloride. Similar improvements are made by the presence of water in the amine solvent, and in this case the total water content is preferably not more than 10% by weight. Even greater improvements can sometimes be obtained by the simultaneous presence of hydrochloric acid and

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 of water in the amino solvent.



   Certain solvents, such as cyclic polymethylene sulfoxides containing a limited number of methylene groups in the ring, have been shown to be excellent solvents for the preparation of solutions used for shaping articles.



  In many cases, it is desirable or possible to remove the solvent by evaporation, as is the case with dry spinning of filaments and fibers.



   With certain solvents, it is possible to form the articles directly from the solutions of the polymers as obtained in preparing the polymers from the monomeric starting materials, even when the reaction mixture is not. is not a spinnable solution in itself. Sometimes they can be adapted for application to this variant of the process by moderate heating or by neutralizing the acid they contain. Usually excellent results are obtained in this variant of the process when amidated solvents such as those included in formula (E) below and especially dimethylformamide, dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoramide or if desired, mixtures of these solvents have been used without the addition of acid acceptors.



   As has been said, the high molecular weight polyamide's constituting the shape structures of the present invention are characterized by the predominant structural element:
 EMI4.1
 where Ar1 and Ar2 may be the same or different and may be an unsubstituted or substituted divalent aromatic radical. the chain extension links of these divalent aromatic radicals being oriented in meta or para positions with respect to each other and the substituents attached to any of the aromatic rings consisting of one or more or a mixture of lower alkyl,

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 lower alkoxy, halogen, nitro, lower carbalkoxy or other groups which do not form polyamides during polymerization.



   Therefore, the aromatic polyamides of the present invention comprise repeating elements linked by a carbonamide group, i.e., the -CO-NH- radical, nitrogen and the carbonyl group of each radical. of carbonamide yes repeats is attached directly to a carbon atom of the nucleus of an aromatic radical, that is, the nitrogen and the carbonyl group of each carbonamide group yes repeats, replaces a hydrogen of a aromatic nucleus. The term "aromatic ring" denotes a carbocyclic ring having a resonance.

   Examples of aromatic radicals have the following structural formulas:
 EMI5.1
 where R is preferably lower alkyl, lower alkoxy or
 EMI5.2
 a halogen group; n is a number from 0 to 4 inclusive and X is 0 Y preferably one of the groups H t and -O-, where Y is from 11 to Y hydrogen or a lower alkyl group. X can also be lower alkylene or lower alkylene dioxy group although these are less desirable. R may also be a nitro group, lower carbalkoxy or other non-polyamide-forming group.

   All these aromatic radicals are bivalent and oriented in meta or para, that is to say that the unsatisfied bonds of the radicals (the extension bonds of the chains when one considers the radical in the element which is repeats of the structural formula the dupolymer) are oriented in meta or para positions with respect to each other. One or more of the aromatic radicals

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 may contain substituent groups as indicated, and any aromatic ring may contain two or more substituent groups, the same or different. However, high molecular weight polymers are preferred in which the aromatic radicals are unsubstituted or contain only lower allyl groups attached to any of the rings.

   The term "non-polyamide-forming groups" refers to groups which do not form polyamides during the polymerization reaction described.



   High molecular weight aromatic polyamides can be prepared by reacting an aromatic diacid chloride with an aromatic diamine, the acidic groups of the diacid chloride and the amino groups of the diamine being disposed in the meta or para position by compared to each other, at low temperature, less than 100 C.



   The bibasic aromatic acid diacid chloride of interest as a reagent comprises compounds having the formula:
 EMI6.1
 where Ar2 is a divalent aromatic radical, that is, it contains resonant unsaturation, and Hal is a halogen atom from the group consisting of chlorine, bromine and fluorine. The aromatic radical can have a single, multiple or condensed ring structure.



  One or more of the hydrogen atoms of the aromatic ring may be replaced by non-polyamide-forming groups, such as lower alkyl, lower alkoxy, halogen, nitro, sulfonyl, lower carbalkoxy, etc. The terms "lower alkyl, and" lower alkoxy "and" lower carbalkoxy "refer to groups which contain less than 5 carbon atoms.



   Chlorides of diacids which can be used in the preparation of the polyamides contained in the articles of the present invention include isophthaloyl chloride and lower alkyl-isophthaloyl chlorides, such as methyl chlorides.

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 ethyl-, propyl-, etc. isophthaloyl. There may be more than one alkyl group attached to the aromatic ring, as is the case with dimethyl-, trimethyl-, tetramethyl-, diethyl-, triethyl and tetra-ethyl-isophthaloyl chlorides. The total number of carbon atoms in the substituents attached to the aromatic ring should not exceed nine.



   Other isophthaloyl chlorides which can be used include nitro- and lower carbalkoxy-isophthaloyl chlorides. One or more of the latter groups may be attached to the aromatic ring together with one or more alkyl, alkoxy or halogen groups, provided that the total number of carbon atoms in the substituents attached to the aromatic ring does not exceed nine. . Thus, it appears that the aromatic radical of isophthaloyl chloride may contain one or more or any combination of lower alkyl, lower alkoxy, halogen, nitro, phenyl, lower carbalkoxy or other non-polyamide-forming groups.



   In addition to the isophthaloyl chlorides and substituted isophthaloyl chlorides specified above, the corresponding unsubstituted and substituted terephthaloyl chloride can also be used.



   In addition to the single-ringed diacid chlorides specified above, chlorides of multi-ringed diacids, in which the acid chloride groups are arranged in meta or para positions relative to each other, are also of interest for. the. present invention.

   Examples of these compounds are chloride
 EMI7.1
 4,4'-oxidibenzoyl chloride, .4,1E'-sulfonyl dibenzoyl chloride, 4,4'-dibenzoyl chloride, 3,3'-oxydibenzoyl chloride, 3,3'-sulfonyldibenzoyl chloride and 3,3'-dibenzoyl chloride, corresponding bromides and fluorides, and similar compounds in which one or both aromatic rings contain one or more or a combination of lower alkyl, lower alkoxy, halogen, nitro, sulfonyl, lower carbalkoxy.

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   The diamines of interest as reactants for the formation of the polymers of the present invention are compounds having the formula H2N-Ar1-NH2 where Ar2 is a divalent a.romatic radical as defined above, and the NH2 groups are arranged in a po- sitions mta or para in relation to each other. The diamines can contain single or multiple nuclei as well as condensed nuclei. One or more hydrogen atoms of the aromatic ring can be replaced by groups which do not form polyamides, such as lower alkyl, lower alkoxy, halogen, nitro, sulfonyl, lower carbalkoxy, as mentioned above.

   The aromatic nucleus of the diamines may be the same as any of the aromatic radicals mentioned above for the diacid chlorides, and the diamine used in a given case may contain the same aromatic radical or a different aromatic radical from that. diacid chloride was used. The total number of carbon atoms in the substituent groups attached to any aromatic ring should normally not exceed nine.



   Examples of diamines which can be used include metaphenylenediamine and lower alkyl substituted metaphenylenediamine, such as methyl-, ethyl-, propyl-, etc. meta-phenylene diamine. There may be more than one alkyl group attached to the aromatic ring, such as in the case of dimethyl-, trimethyl-, tetramethyl-, diethyl-, triethyl and triisopropyl-metaphenylene diamine.

   The alkyl substituent groups do not need to be the same, since compounds such as 2-methyl-4-ethyl metha-phenylene diamine and 2-methyl-4-ethyl-5-propyl meta-pnenylene diamine can be used. Instead of an alkyl, the aromatic nucleus may be substituted with one or more lower alkoxy groups such as for example methoxy-, ethoxy-, propoxy-, butoxy-, etc. meta-phenylene diamine. A halogen-substituted meta-phenylene diamine, for example chloro, bromo and fluoro meta-phenylene diamine, can be used.

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   In addition to the meta-phenylene diamine and the substituted meta-phenylene dfamines mentioned. above, the corresponding compounds can also be used: unsubstituted and substituted.
 EMI9.1
 of Dc "1-.Tc" Lp, 'EnylNE .'-' Y7! e diamine. us OR more or a combination of substituents may be attached to the aromatic nucleus.



   In addition to the single ring aromatic diamines specified above, multiple ring or condensed aromatic diamines, in which the amino groups are arranged in meta or para positions with respect to each other, are also of interest in the art. present invention. Examples of these compounds are
 EMI9.2
 4, -oxydiphenyldiamine, 4,4'-sulfonyl-diphenyl diamine, 44'-diphenyldiamine, 3, 3'-oxydiphenyldiam.ne, 3, 3'-sulfonyldiphenyldiamine, and 3,3'- diphenyldiamine, and corresponding compounds in which one or both aromatic rings contain one or more or a combination of lower alkyl, lower alkoxy, halogen, nitro, sulfonyl, lower carbalkoxy groups.

   Other reagents suitable for the repair of aromatic polyamides of interest in the present invention are described in the Applicant's patent of the same date entitled "Polymerization process".



   This patent also describes processes for the preparation of fully aromatic polyamides. According to this patent, the diamine and the diacid chloride are reacted in the presence of certain solvents at low temperatures to produce the linear high molecular weight polyamides. The aromatic polyamides forming the articles of the present invention can be derived from two or more aromatic diamines or from two or more aromatic diacid compounds. Further, up to about 10% of the polymer-forming ingredients, which may or may not contain an aromatic nucleus, can be included without seriously harming the extraordinary physical and chemical properties of the articles of the present invention.

   However, it is preferable that the diamine and the

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 The diacid compounds used are wholly aromatic, thus providing a polymer characterized entirely by structural elements of which all nuclei contain aromatic radicals.



   Articles of the present invention can be formed from their solutions. For example, fibers and filaments can be produced by dry and wet spinning processes.



  Films can be produced by casting solutions, and coatings can be applied to a substrate such as wire or fabric.



   As the aromatic polyamides contained in the articles of the present invention are usually not soluble in ordinary solvents, it is necessary to provide solvents capable of dissolving the polymers, and at the same time forming solutions suitable for use. later form. The solubility of the polymer in certain solvents differs depending on the nature of the polymer, or depending on whether the polymer is in the amorphous or crystalline state. In many cases, dimethylacetamide and N-methyl-pyrrolidone, as well as certain amides, are able to dissolve the crystallized polymer and can therefore be used in the preparation of the spinning and forming solutions from the polymer. solid.



   The solvent power of certain polar solvents can be considerably increased so that solutions of concentration, viscosity and stability sufficient for shaping can be obtained, if particular salts are added thereto or if, respectively, the solvents. or solutions contain it.



  These solvents-perfected are; described in the Applicant's patent of the same date entitled Polymer solutions and their preparation Other solvents of interest for the shaping of the articles of the present invention can be found in different classes of chemical compounds such as phosphine oxides.

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   Trimethylenephosphine oxide is an excellent solvent for poly- (meta-phenylene isophthalamide).



   The above amine solvents are preferably liquid at room temperature, and have a molecular weight not exceeding 150 and an amine number (A.V.) as defined. in the following, at least 0.7 and preferably between 0.8 and 1.8. It is often advantageous that the amine solvents or the solutions of polymers in these solvents additionally contain hydrochloric acid and / or water. In general, remarkable increases in the solvent power of the amine, and improved thermal stability of the solution, are obtained by the addition of
3% to 20% by weight of one or both of these addition agents. Depending on the chemical composition of the polymer and / or of the amine, the optimum amount of the additive varies.

   If both addition agents are used simultaneously, the maximum amount may be somewhat higher than for either agent alone. Suitable amines are, for example, methylamine, ethylene diamine, pyrrolidine, triethylene tetramine and tetraethylene tetramine.



   The amine number of an amine depends on the number and nature of the amino radicals present, the presence or absence of nuclei in the structure, the nature of the nucleus and the number of carbon atoms present. . The only amines considered in the present description are stable amines, having melting points below 35 C. The amine group (s) are attached to carbon atoms which, in turn, are attached only to carbon atoms. carbon, nitrogen or hydrogen.



   The amine number is calculated as follows:
1.- Add the points for each of the amino groups present, counting: (a) 2 points for each primary NH2 group; (b) 2 points for each secondary -NH group; (c) 0 points for each tertiary nitrogen-N- (d) only amino groups attached to carbon

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 bone attached itself to carbon, hydrogen or nitrogen, are taken into account.



   2. - To the above sum, add 3 points for, each 5-element saturated nucleus containing only carbon and nitrogen atoms, without adding any points for any other type of nucleus.



   3.- From the sum above, subtract 2 points if there is any atom other than carbon, hydrogen and nitrogen, that is to say sulfur, oxygen, etc. or if there is any unsaturation ...-
4.- Divide the total above by the number one unit greater than the number of carbon atoms contained in the amine molecule:
The indicated concentration range is determined by weight relative to the amine solvent. The effect of this addition is to make the solution more thermally stable, so that subsequent processing stages, such as filament spinning or film casting, can take place within a range of. extended conditions.

   In addition, the presence of the amine salt tends to increase the Affective Amine Index (A.V.) of moderately effective amines. In particular, amines having an amine number in the range of 0.5 to 0.9 without adding agent, see their solvent power increased by the addition of hydrochloric acid and / or water to the, level of amines in the range d @ 0.8 to 1.3 AV, while amines with an AV of 1.0 to 1.8 show the effect of the additive mainly in the form of enhancement thermal stability.



   Amines with an AV less than 0.5 are less effective solvents for aromatic polyamides, but even these benefit from the addition of hydrochloric acid and water and can thus become suitable solvents for shaping. articles of the present invention.



   Another group of solvents useful for shaping following the present invention include polymethylene tallow oxides.

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 cyclic, which are solvents having the general structure
 EMI13.1
 where R1 is an alkaline group containing at least three and not more than five carbon atoms and the total number of carbon atoms does not exceed six. The optimum solvent power and the spinning behavior of the solutions are observed with tetramethylene sulfoxide and cyclic pentamethylene sulfoxide as solvent.



   As stated, the end product of the polymerization for the preparation of the polymers of interest of the present invention is frequently obtained as a solution in the reaction medium, such a solution is directly suitable for subsequent operations. It is thus possible to obtain directly and in a unified system, fibers, filaments and films prepared from fully aromatic polyamides, starting directly from the intermediate products of polymers, without having to go through the stages of production. separation of the polymer and its redissolution for further processing.



   Amide-type solvents mentioned above have all been found to be "solvents for the fully aromatic polyamides of the present invention. The description of the polymerization solvents in Applicants' patent of the same date entitled The Polymerization Process" can also be described. be used to determine good solvents for polymers already formed. The most interesting amide solvents are those which have a solute-solvent mutual action energy Kav of less than -2000 calories per mole, measured on model compounds.



  Since, in the dissolution of an already formed polymer, there is no formation of any acid acceptor salt, it is necessary, for the measurement of Kav in order to determine the solvent power,

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 that the measurements be carried out without any acid acceptor salt being present in the solution. So although the general principles and techniques experimented with used to establish interest; of an organic liquid as the polymerization medium, are similar, the precise experimental conditions and the value of Kav which serve as criteria for a satisfactory result, are different.

   Furthermore, for the determination of a suitable solvent for an already formed polymer, it is not necessary to take into account that the proposed solvent can act with the monomer intermediate forming the polymer, for example with aromatic diamines or aromatic diacid halides, because these substances will not be present in a polymer solution.



   In particular, organic solvents having a Kav of less than -2000 calories per mole exist in the classes of organic amides having the following formula:
 EMI14.1
 laughed.



  [; NL.z-1R4-J ab CE) where Z represents) C = 0, or - P - (N ........ CH 3) Z and Rl 'R and R4 may be CH3 the same or different. R1 and R2 can be cyclic alkyl, alkylene or alkylene, and R4 is alkyl, alkylene, cyclic alkylene or hydrogen.

   The alkylene and cyclic alkylene radicals given in R1, R2 and R4 can be combined, so that, for example, R1, R2 or R1 and R4 together constitute a cyclic alkylene structure, this cyclic structure further containing the radical and where these ring structures must contain a total of at least 5 and not exceeding 6 atoms in the ring, and "a" and "b" are chosen such that they satisfy the residual valences of Z, and " a "is equal to 1 or 2 while" b "is equal to 0 or 1. Preferably, these solvents

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 have a total number of carbon atoms in the radicals R1, R2 and R4 which does not exceed 5, and R1 and R2 are methylene or ethylene radicals.

   While their solvent power is greatest when used to maintain the polymer in solution as it is formed, these amidated solvents can be expected to be of interest to obtain fully aromatic polyamide solutions prepared by the present process. or by other polymerization processes. In general, these amidated solvents dissolve at least 5% by weight of fully aromatic polyamides. When the polymer is exposed to the amidated solvent while it is forming, this solvent allows the formation of stable clear solutions containing at least 15% and sometimes
 EMI15.1
 .... "" "" "" - "----:,:! ;; ',,,,,,, UJ.::;:';:om;I'I:.-=- - ;; - "" :; 'I', = ",.,. Ç-.t" 'lItl up to 30% solids.



   The articles of the present invention are characterized by an exceptionally high melting point. While most of the known polyamide articles melt at temperatures below about 270 ° C, in general the articles of the present invention have melting points which exceed 300 ° C and in many cases exceed 350 ° C. The filaments of the present invention retain their filament shape at temperatures of about 300 C. The articles of the present invention are distinguished from the polyamide articles known in that they are clear as water, have high strength. excellent in corrosive atmospheres, have virtually no flammability, and possess remarkable resistance to degradation by high energy particles and gamma radiation.



  Most of the articles resist melting when put on them at a temperature of 300 ° C. for prolonged periods, while maintaining in a high proportion not yet achieved their physical properties at room temperature. Flash exposure for 20 seconds at temperatures as high as 700 C does not destroy these properties of the fibers. Besides, the new items have high tenacity,

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   good elasticity and long bending life at high tendra bures.



   Articles of the present invention can have a wide variety of physical forms. Among the most important of these forms are fibers and dandruff. The interesting combination of desirable physical and chemical characteristics of these articles is unique. Fibers and films of these polymers not only have excellent physical properties at ambient temperatures, but retain their strength and withstand excellent machining forces at elevated temperatures for extended periods of time. This behavior has industrial utility in a wide range of uses.

   The fibers and filaments can be used as high temperature electrical insulators, protective clothing and curtains, filter media, packing and sealing materials, brake and clutch linings. In the aviation industry, the articles of the invention can be used in parachutes, fuel tanks, tires, ducts, pipes and insulators. In atomic energy applications, outstanding radiation resistance with retention of physical properties as well as thermal stability is important. Ropes for tires and conveyor belts, particularly where such articles are subject to prolonged exposure to high temperatures, are other applications.

   Garment press fabrics for the dry cleaning industry made from these fibers exhibit extreme hydrolytic stability.



   Because they retain their fiber properties at high temperatures, the new fibers of the present invention can be used for high temperature applications along with heat resistant resins and elastomers, such as polytetrafluoroethylene, Fluorinated rubbers and silicone resins. Fabrics made from fibers

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 aromatic polyamide form a base material to which resins can be applied by coating or impregnation; likewise, stranded fibers can be mixed in a network of a resin to obtain a reinforced plastic material.



  Since these fibers melt at temperatures above the melting points of some resins, resins can be melt applied thereto, or be sintered after having been applied as a solid powder, without damaging the fibers. Further, since the fibers retain good tensile properties at high temperatures, resins can be applied to the fabric in a continuous manner, its high strength allowing the fabric to be processed, for example to pass through a sintering furnace without having to. need support items. The products thus obtained can be used at much higher temperatures than is possible with ordinary fibers which decompose or. melt below 300 C.



   The films can be used as interior linings of automobiles and airplanes, as high temperature electrical insulators, eg for slit coatings, temperature use, eg for slit coatings, use in transformers. dry, capacitors, cable sheaths, etc., packaging of items to be exposed in their packaging to high temperature or high energy radiation, corrosion resistant pipes, hot water pipes, ducts, air ventilation hot, aircraft body coatings, radomes for airplanes, embossing or relief printing cylinder linings, tanks and tank coatings, printed circuits, tapes for hot pipe casings,

   laminates in which the films are welded to metal foils, self-supporting mold liners or containers for casting meltable materials melting below 300 C, including metals, and a variety of other similar and related uses.



   Films of the present invention can be stretched or otherwise oriented according to customary methods. Films can be oriented in two axes by stretching

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 or rolling in both directions or by rolling in one direction and stretching in the other direction.



   In the examples below, all parts and percentages represent weights, unless otherwise noted.



  The values of the inherent viscosity are measured in sulfuric acid of, density 1.841 at 15.6 ° C., at 30 ° C. at a concentration of 0.5 g of polymers per 100 cm3 of solution. All of the structures of the present invention are derived from polymers having an inherent viscosity of at least about 0.6 based thereon, and a melting point of at least about 300 ° C.



  EXAMPLE I ..-
5.4 parts of meta-phenylenediamine dihydrochloride is introduced into a reaction apparatus equipped with a high-speed stirrer, and a solution of 12.1 parts of triethylamine in 200 parts of methylene chloride is quickly added thereto. .



  Triethylamine hydrochloride is formed in situ. The mixture is stirred for one minute to dissolve the diamine salt.



  6.1 parts of isophthaloyl chloride in 200 parts of methylene chloride are then added. Polymerization is completed
 EMI18.1
 and precipitates the poly (meta-phenyleneisophthalamide) by adding a volume of hexane equal to the volume of the reaction mass. The product is clear as water, and has an inherent viscosity of 1.71 and a polymer melt temperature of 375 C. It is obtained in a yield of 91%.



   The polymer prepared as described above is dissolved at a concentration of 17% in a mixture of 95 parts of dimethylformamide and 5 parts of lithium chloride. This solution is spun at 128 ° C. through a 5 orifice die, each orifice having a diameter of 0.10 mm, into a column of air maintained at 225 C. The fiber, wound at a rate of 83.7 mm. meters per minute, is then stretched to about 4.5 times its original length, and is scalded in water. The final fiber has a tenacity of 4.9 g per denier, and an elongation at break of 30%.

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   Another sample of the same polymer was dissolved in a mixture of 95% dimethylfomamide and 5% lithium chloride to obtain a 15% polymer solution. This solution is poured into a film. The solvent was distilled in an oven heated to 150 ° C. The resulting film was leached in hot water to remove residual dimethylformamide and salt. Wet film test tapes are hung from frames before vacuum drying them.

   The physical properties of the films at different temperatures are reported in the following table
 EMI19.1
 
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It is also observed that the film has a high dielectric constant, which decreases only in fractions at temperatures as high as 200 C, while insulating materials existing in industry, such as polyethylene or rubber, are completely destroyed or melt at these temperatures.



   To illustrate the non-flammable nature of the polymers, a sample of fiber prepared as described above is subjected to a standard flammability test (AATC test at an angle of 45, American Handbook of synthetic Textiles, 1st Edition, 1952 , Textile Book Publishers Inc. NY) along with cotton fiber as a control. The two fibers are knitted into tubes and exposed to an open flame until they ignite and at that point the flame is removed.

   The test results are given in the following table;

 <Desc / Clms Page number 20>

 
 EMI20.1
 Inflain-reliability of knitted fabrics.
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     As can be seen, the fibers of the present invention are remarkably superior to cotton in terms of flame resistance. In similar tests, the fibers of the present invention were compared to other industrial synthetic fibers, and were found to be more difficult to ignite and, moreover, self-extinguish. A sample of poly (hexamethylene adipamide) yarn fabric will burn to 2/3 of the surface of the fabric, while fabric prepared using fibers of the present invention will carbonize to less than 1/10 of the fabric surface. its surface.



   Another sample of the same polymer is dissolved in a mixture of 80.75 parts of dimethylformamide and 4.25 parts of lithium chloride to give a 15% polymer solution. This solution was cast into a film using a doctor blade allowing a 15 mil clearance. The solvent is distilled in a hot vacuum oven. The resulting film is oriented by hot rolling in a direction perpendicular to the direction of casting, and then hot rolled at an angle of 90 to that direction. This produces a film oriented along two axes. The physical properties of this film are given in the

 <Desc / Clms Page number 21>

 Table below.
 EMI21.1
 
<tb>



  Direction <SEP> of the first <SEP> <SEP> Direction <SEP> of the second <SEP>
<tb> lamination <SEP> ¯¯¯laminagē¯¯¯
<tb>
<tb>, ', adult <SEP> 16308 <SEP> kg / mm <SEP> 12684 <SEP> kg / mm
<tb>
 
 EMI21.2
 Teliaci, tee 543 kg / mm 398 kg / mrn
 EMI21.3
 
<tb> Elongation <SEP> 10% <SEP> 4.5%
<tb>
   EXAMPLE II ..-
Is spinning dry from dimethylformamide of poly (4-
 EMI21.4
 (Nethyl-: eta-p: nényi2ne isophthalamide) clear as water, having an inherent viscosity of 1.64 and a polymer melting temperature of 300 ° C., and the yarn was stretched to three times its original length.

   Samples of this wire, as well as comparative controls, were exposed for various times, (A) to air at 175 ° C. containing 5% water vapor, and (B) to air at 175 ° C. C containing 5% water vapor, and 5% sulfur dioxide. The tenacities of samples A and B are given in the following two Tables.

   - Thread
 EMI21.5
 
<tb> -Exposure <SEP> A <SEP> Tenacity
<tb>
<tb> Duration <SEP> (days) <SEP> retained <SEP> (%)
<tb>
 
 EMI21.6
 Poly (Ta-phenylene isophthalamide) Poly (lilethyl-m-phenylene isophthalamide) Poly (ethylene terephthalate)
 EMI21.7
 Poly (hexwnethylene adipamide)
 EMI21.8
 
<tb> 6 <SEP> 85
<tb>
<tb> 6 <SEP> 45
<tb>
<tb> 6 <SEP> 19
<tb>
<tb> 4 <SEP> too <SEP> low <SEP> for
<tb> the test
<tb>
 Wire
 EMI21.9
 
<tb> Exposure <SEP> A <SEP> Tenacity
<tb>
<tb> Duration <SEP> (days) <SEP> retained <SEP> (%)
<tb>
 
 EMI21.10
 Poly (a-, Yjhenylene isophthalamide) Poly (¯2: cti2yl-i ..- phenylene isophthalamide) Poly (ethylene terehtalate) Poly (hex8.i:

  J. ethylene adipo.! 'Lide)
 EMI21.11
 
<tb> 6 <SEP> 70
<tb>
<tb> 3 <SEP> 49
<tb>
<tb> 1 <SEP> too <SEP> low <SEP> for
<tb> the test
<tb>
<tb> 1 <SEP> too <SEP> low <SEP> for
<tb> the test
<tb>
 EXAMPLE III.-
A polymer having an inherent viscosity of 1.4 and a polymer melting point of 400 C is prepared from
 EMI21.12
 of j, 98 parts of bis (4-Htninophcnyi) mcthane and 3.01 parts of diethylaniliiae in 56.6 parts of cllmethyl tetra "ethylene sulfone,

 <Desc / Clms Page number 22>

 reacted with 2.03 parts of isopytaloyl chloride dissolved in 34 parts of dimethyltetramethylene sulfon.



   The resulting clear, highly viscous solution was wet-spun in a water bath maintained at 20 ° C. using a die with ten orifices each having a diameter of 6 mil. Solid, limpid fibers are obtained with remarkable thermal stability. Likewise, a solution of the same polymer in dimethylformamide is dry spun into a lustrous white yarn having a tenacity of 4.1 g per denier and an elongation of 20%.



  EXAMPLE IV.-
Poly (metaphenylene chloroisophthalamide) is prepared with a high melting temperature of the polymer, from meta-phenylene diamine and chloro-isophthaloyl chloride. The fibers obtained by spinning a solution of the polymer through a spinneret in air at 60 C, are strong and completely non-flammable.



  EXAMPLE V. -
Filaments are prepared from ring-substituted aromatic polyamide having a high molecular weight and a high polymer melting point, the nuclear substituents of which are lower alkyl or alkoxy, as described in Example I by extrusion of a solution of poly (4-methyl meta-phenylene isophthalamide). Likewise, good properties of the finished structures are observed.



    EXAMPLE VI. -
A solution of 6.1 parts of isophthaloyl chloride in 200 parts of methylene chloride is reacted with a solution of 6.33 parts of 4-methoxymetaphenylene diamine monohydrochloride and 12.1 parts of triethylamine in 200 parts of methylene chloride. The resulting polymer has an inherent viscosity of 0.84 and a polymer melting point of greater than 300 ° C. It is dissolved in N-methyl pyrrolidone, and pouring of the solution gives solid, transparent, flexible films.

 <Desc / Clms Page number 23>

 



  EXAMPLE VII. -
A copolymer of meta-phenylene diamine and a mixture of 80 mole percent of isophthaloyl chloride and 20 mole percent of terephthaloyl chloride is prepared by simultaneous addition to a Waring mixer of a solution of 43.9 parts of isophthaloyl chloride, 10.98 parts of terephthaloyl chloride dissolved in 1600 parts of methylene chloride and a solution of 48.87 parts of meta-phenylene diamine hydrochloride, 109.3 parts of triethylamine in 1600 parts of methylene chloride. A polymer is formed having an inherent viscosity of 1.44 and a polymer melting temperature of 370 C.



   36 parts of the polymer thus prepared were dissolved in 114 parts of dimethylformamide and extruded through a five-port die having a diameter of 0.1 mm in a column of cross-flow air, the wall temperature being maintained. at 200 ° C. The wire is collected at a rate of 47.4 meters per minute, and stretched to 2.75 times its original length. It has a tenacity of 3.5 g / denier, an elongation at break of 34% and an initial modulus of 55 g / denier.



   The polymerization is repeated below, varying the proportion of acids so as to obtain a mixture of 70 mole percent of isophthaloyl chloride and 30 mole percent of terephthaloyl chloride. The product has. an inherent viscosity of 1.89.



  A 15 mil thick film was cast from a 15% solution of the polymer in dimethylformamide. The washed and dried structure exhibits excellent physical properties, in particular as given below
Resistance to
 EMI23.1
 
<tb> Temperatures <SEP> traction <SEP> Modulus <SEP> Elongation
<tb>
<tb> kg / cm2) <SEP> kg / cm2
<tb>
<tb>
<tb>
<tb> 20 C <SEP> 1022 <SEP> 44.800 <SEP> 4.05
<tb>
<tb>
<tb>
<tb> 150 C <SEP> 689.5 <SEP> 273 <SEP> 11.8
<tb>
<tb>
<tb>
<tb>
<tb> 200 C <SEP> 567 <SEP> 280 <SEP> 12.3 '
<tb>
 

 <Desc / Clms Page number 24>

 EXAMPLE VIII.-
A solution of 4.06 parts of terephthaloyl chloride in 75 parts of dimethyltetramethylene sulfone is quickly added to a solution of 2.16 parts of meta-phenylene dia:

  groin and 4.04 parts of triethylamine in 75 parts of dimethyltetramethylene sulfone in a Waring mixer. The resulting polymer has an inherent viscosity of 1.04 and a polymer melting temperature of greater than 400 C. It is soluble in concentrated sulfuric acid and in N-methylpyrrolidone containing 5% lithium chloride. Spinning the solution of this polymer provides very high melting point fibers.



    EXAMPLE IX.-
2.554 parts of 4,6-diamine xylene and 3.975 parts of sodium carbonate are dissolved in 100 parts of water. A separate solution of 3.807 parts of isophthaloyl chloride in 136 parts of 3,4-dimethyl tetramethylene sulfone is prepared. The solutions are mixed at room temperature to obtain a solution of a polymer having an inherent viscosity of 0.81. We use the solution directly from the. fiberization of the polymer by dry spinning. The melting point of fibers is greater than. 320 C.



  EXAMPLE X. -
The procedure of Example IX is followed, except that the acidic ingredient circle is used, terephthaloyl chloride instead of isophthaloyl chloride. The proportions of reagents and solvents are the same as described above, and, as before, fibers are spun directly from the solution. Oriented fibers are strong and flexible, lightly colored, and have a melting point of 350 C.



  EXAMPLE XI.-
A solution of 6.1 parts of 2,4-diamine toluene in 200 parts of water is introduced into an apparatus. An equivalent amount of sodium carbonate is added to the diamine solution before the reaction. To the stirred solution is added a solution of 10.2 parts of terephthaloyl chloride in 44.4 parts of tetra-

 <Desc / Clms Page number 25>

   hydrofuran. The polymer is obtained with a yield of 100% of theory; it has an inherent viscosity of 1.37, and a melting temperature above 305 C. Fibers are spun from
 EMI25.1
 of a bzz solution of the polymer in climethylacetamide containing 5% lithium chloride.

   The tenacity of these fibers, after orientation, is 1.4 g / denier with an elongation of 96% at break and an initial modulus of 32.
 EMI25.2
 



  .} C ': 1vIPL1LII ..!. -
A solution of 10.6 parts of 3,3'-dimethylbenzidine in 300 parts of water and 66.6 parts of tetrahydrofuran containing 10.6 parts of sodium carbonate is prepared. This solution is placed in a reaction apparatus and stirred rapidly. A solution of 10.1 parts of isophthaloyl chloride in 222 parts of tetrahydrofuran is added. The dried polymer has an inherent viscosity in sulfuric acid of 1.70 and a melting point of 365 C. It is dissolved in tetramethylene. Tallow oxidizes, and is cast into a film which, after orientation in one direction, is tough and elastic.



  EXAMPLE XIII. -
27.12 parts of 2.2'- are mixed in an apparatus.
 EMI25.3
 di (4-aminophenyl) propane and 25:44 parts of sodium carbonate in 240 parts of water and 266 parts of tetrahydrofuran., This mixture is stirred rapidly while to it is added as quickly as possible 24.36 parts of chloride of isophthaloyl dissolved in 266 parts of tetrahydrofuran. A thick emulsion forms which is stirred for 7 minutes. Then, with rapid stirring, 1200 parts of water are added to re-precipitate the emulsion and precipitate the polymer which is in a fine, easily filterable state. The polymer is washed three times with water and dried overnight at 75 ° C. in a vacuum oven.

   The polymer is obtained with a yield of 95%. The viscosity of the polymer is 1.2 measured in meta-cresol
 EMI25.4
 at a concentration of 0.5j%. Dissolved in a mixture of 90 parts of tetrilihydrofuran and 10 parts of water, this polymer gives a solution having a solids content of about 24%,

 <Desc / Clms Page number 26>

 from which fibers can be spun. The melting point of the polymer is 375 C. Glass fabrics and yarns covered with this polymer have excellent resistance to high temperatures.



  EXAMPLE XIV. -
27.12 parts are mixed in a reaction apparatus.
 EMI26.1
 of 2,2'-di (1 -aminophenyl) propane and 25. parts of sodium carbonate, in 266 parts of tetrahydrofuran and 240 parts of water.



  This mixture is stirred rapidly while 24.36 parts of terephthaloyl chloride in 266 parts of tetrahydrofuran are added as quickly as possible. A thick emulsion is obtained which is stirred for 6 minutes. Additional water is added to precipitate the polymer. The polymer is obtained with a yield of 95% after washing and drying. It has an inherent viscosity, measured in metacresol, of 1.8. The polymer obtained is dissolved in dimethylformamide at a concentration of 14% solids. Yarns can be spun using this solution.



  Yarns of this polymer, drawn to twice their original length in an atmosphere of water vapor at a pressure of 2.5 kg.cm2 have a tenacity of 3.6 g / denier and an elongation at break of 28%. .



  EXAMPLE XV.-
A film of meta-phenylenediamine copolymer with a mixture of 70 mole percent isophthaloyl chloride and 30 mole percent terephthaloyl chloride is prepared as described in Example VII. The film is placed in a multi-channel stretcher and sprayed from above and below with water vapor at 1.4 kg / cm 2. After 30 seconds, the thread is pulled quickly in both directions to produce a two-way stretched film *
After this two-direction orientation operation, the film is tested and the following physical properties are observed.

   Initial modulus measured at 23.3 C in the direction of the greatest stretch, 1.156 kg / cm2 at break and in the direction of the weakest stretch, 9.588 kg / cm2

 <Desc / Clms Page number 27>

   at the breakup. The elongation is measured under the same conditions. reached 24.7% in the direction of the greatest stretch and 26.3% in the direction of the weakest stretch.



   Coating compositions comprising solutions of the above copolymer in dimethylformamide have been applied to fabrics or glass threads. The resulting coatings have excellent high temperature resistance.
 EMI27.1
 



  N.; E! IPT.l; XV'I. -
A fully aromatic polyamide is prepared by reacting meta-phenylene diamine with isophthaloyl chloride using dimethylacetamide as solvent. For best results, dimethylacetamide is distilled before use and kept dry until use.



   25.92 parts of meta.-phenylene diamine are placed in a three-necked round-bottom flask fitted with a stirrer. slats, a nitrogen introduction tube and a drying tube. 226 paties of distilled dimethylacetamide are added. The flask is purged with nitrogen to remove atmospheric oxygen from the reaction mixture. A slurry of dry ice and acetone is placed around the vial to freeze the solution which is thus frozen to a slurry. 48.8 parts of isophthaloyl chloride are then added all at once, and the dry ice bath is replaced by an ice-water bath. Continue stirring for about 20 minutes to 1/2 hour.

   At this time, a very easily changeable mass is obtained. There is in this reaction mixture, an excess of dimethylacetamide hydrochloride relative to the amount soluble in dimethylacetamide, and it follows that a certain amount of this amide salt is dispersed rather than dissolved. About half of the calculated amount of amide salt separates out. The solution contains about 20% polymer, based on dimethylacetamide.



  The inherent viscosity of the polymer obtained in this reaction exceeds 1.8 ..



   If you want a clear solution, heat the mixture

 <Desc / Clms Page number 28>

 above reaction at 60 C or a suitable amount of water is added thereto to obtain a clear viscous liquid. However, because of the reactivity of hydrochloric acid, it is impossible to continue processing this solution in ordinary anti-rust steel devices, because the hydrochloric acid present would attack this metal. However, hydrochloric acid can be separated without producing precipitation of the polymer, by adding an appropriate molar amount of calcium hydroxide. In this case, the polymer solution containing a large amount of calcium chloride is dry spun into fibers by standard techniques.



  If less than the molar amount of calcium hydroxide is used, a partially neutralized solution is obtained, which is wet spun in a coagulation bath, although dry spinning is not possible. The hydrochloric acid can be neutralized by other methods to form a neutralization product which can be more easily separated from the polymer solution, for example by passing through the reaction mass. gaseous ammonia. This results in the immediate separation of ammonium chloride which is insoluble in dimethylacetamide, and the ammonium chloride can be filtered or centrifuged.

   Certain difficulties may be encountered in the filtration of ammonium chloride, if the polymerization has been carried out with high solids contents to obtain a high molecular weight polymer. This is the case because such a solution is very viscous.



  Further, if most of the theoretical amount of the acid halide is used and then the reaction is temporarily stopped, then ammonia gas can be passed through the prepolymer mixture to. 'until the acid is neutralized. Under these circumstances, the precipitated ammonium chloride can be filtered very easily. The filtrate can then be degassed by heating or applying low pressures, if a quantity of ammonia gas greater than the necessary quantity is added.



  The remaining amount of acid chloride is then added to complete the polymerization. This reaction mixture contains

 <Desc / Clms Page number 29>

 a slight residue of hydrochloric acid. Because of this acid, it is not possible to spin the solution to dryness without producing extreme die corrosion, though, as we have already seen. Said, the solution can be easily wet spun. However, the small amount of hydrochloric acid remaining can easily be neutralized, for example by calcium hydroxide, and the completely neutralized solution is then entirely suitable for dry or wet spinning under any conditions, without producing any residue. corrosive action on the die.

   In addition to the use of calcium hydroxide at this stage, other basic materials such as sodium hydroxide, sodium carbonate or other acid acceptors can be used. An important feature of all of these methods of treating the polymerization reaction mass is that the polymer is never separated and never needs to be handled in the dry state. There is therefore no danger of contamination of the polymer, nor any need to redissolve it.



   Other methods of completely removing the acid halide present as a by-product can easily be devised by those skilled in the art. The above process offers the advantage that the acid halide combines with ammonia without the formation of water, as is usual in neutralization reactions.



  In addition, the ammonium chloride produced is insoluble, and separates easily.



   However, other methods are also interesting, and are suitable for the method described above. For example, dimethylsulfite can be used to react with the acid, forming methanol, methyl chloride, and sulfur dioxide, which evolves in the gaseous state. Other suitable materials reacting with the acid halide include inorganic carbonates and hydroxides, mixed inorganic-organic carbonates, epoxides such as epichlorohydrin, propylene oxide, ethylene oxide etc., and organic bases such as amines

 <Desc / Clms Page number 30>

 tertiary and urea.

   As these compounds with acid activity are not used as acid acceptors during the reaction, but are added when it. There is no such thing as a diacid halide which is not uncombined, it is evident that the choice of suitable materials is not limited by mutual action with the acidic polymer-forming ingredient. As a result, a wide variety of substances can be used.



  EXAMPLE XVII.



   The previous experiment is repeated using N-methyl-alpha-pyrrolidone as solvent. A polymerization cycle similar to that of the previous example is therefore applied.



  A solution of 32.4 parts of meta-phenylene diamine in 310 parts of N-methyl-alpha-pyrrolidone is frozen in a three-necked flask, and 61.0 parts of isophthaloyl chloride is added.



  The reaction is continued for about 1 hour, and a solution of spinnable viscosity, containing about 20% solids, is obtained. After decomposition of the amide salt with ammonia and filtration of the ammonium chloride, the solution is wet-spun into solid white fibers. The polymer has an inherent viscosity of 0.95 measured in concentrated sulfuric acid.



   Other examples giving embodiments of amidated solvents are given in the table below. Neutralization as described above is effective in each case. In some of these examples, the polymeric product is isolated for analysis and determination of the yield. In other examples, the polymer is kept in solution. In some examples, the reaction product is a solution of suitable viscosity to be spun into fibers or cast into films. In other cases, it is desirable to dilute or concentrate the solution before submitting it.

 <Desc / Clms Page number 31>

 to subsequent treatments. The concentrations of the reagents can be varied in each case to produce a range of polymer solutions.



   In some examples, the acidic reagent is dissolved in a small amount of inert solvent to simplify addition to the diamine solution. The solvent (benzene, toluene, etc.) has no effect on the reaction or on the product. The solutions obtained in the examples which follow were spun into filaments with high melting points, heat resistant and having good fiber properties.

 <Desc / Clms Page number 32>

 



    TABLE 12.
 EMI32.1
 
<tb>



  EXAMPLE <SEP> DIAMINE <SEP> HALOGENIDE
<tb> OF ACID <SEP> SOLVENT <SEP> DURATION <SEP> OF <SEP> VISCOSITY <SEP> OBSERVATIONS
<tb> INHERENT <SEP> REACTION
<tb> OF <SEP> POLYMER
<tb> XVIII <SEP> 10.8 <SEP> parts <SEP> of <SEP> meta- <SEP> 20.3 <SEP> parts <SEP> of <SEP> chlo- <SEP> 94.3 <SEP > parts <SEP> 20 <SEP> minu- <SEP> 1.53 <SEP> (acid <SEP> The <SEP> solution <SEP> of <SEP> diamine <SEP> is
<tb> phenylene <SEP> diamine <SEP> dis- <SEP> ride <SEP> of <SEP> terephthaloyl <SEP> of <SEP> dimethyl- <SEP> tes <SEP> to <SEP> OOC <SEP> sulfuric ) <SEP> frozen <SEP> in <SEP> of <SEP> the <SEP> ice
<tb> bunkers <SEP> in <SEP> the <SEP> soil- <SEP> solid <SEP> acetamide <SEP> carbonic <SEP> before <SEP> the <SEP> reaction.
<tb> before <SEP> cold. <SEP> The <SEP> polymer <SEP> is <SEP> precipitated
<tb> in <SEP> water.
<tb>



  XIX <SEP> 22.63 <SEP> parts <SEP> of <SEP> 2,2- <SEP> 20.3 <SEP> parts <SEP> of <SEP> chlo- <SEP> 188 <SEP> parts < SEP> 1/3 <SEP> hour <SEP> 1.66 <SEP> (acid <SEP> On <SEP> of <SEP> the <SEP> reaction <SEP> simibis (4-aminophenyl) - <SEP> rure <SEP> of isophthaloyl <SEP> of <SEP> dimethyl- <SEP> sulfuric) <SEP> lar <SEP> to <SEP> Example <SEP> XIV. <SEP> The <SEP> popropane, <SEP> dissolves <SEP> in <SEP> 16 <SEP> parts <SEP> of <SEP> acetamide <SEP> lymer <SEP> precipitates <SEP> by <SEP> the water.
<tb> in <SEP> the cold <SEP> solvent <SEP>. <SEP> toluene.
<tb>



  XX <SEP> 10.8 <SEP> parts <SEP> of <SEP> para- <SEP> 20.3 <SEP> parts <SEP> of <SEP> chlo- <SEP> 97 <SEP> parts <SEP> 30 <SEP> minu- <SEP> 0.63 <SEP> (acid <SEP> On <SEP> only use <SEP> for <SEP> agitation
<tb> phenylene <SEP> diamine <SEP> dis- <SEP> isophthaloyl <SEP> <SEP> of <SEP> N, N, N ', N'- <SEP> tes <SEP> sulfuric) < SEP> to <SEP> the <SEP> main. <SEP> On <SEP> gets <SEP> a <SEP> sosoutes <SEP> in <SEP> the <SEP> solvent <SEP> solid. <SEP> tetramethyl- <SEP> viscous <SEP> lution <SEP> clear.
<tb> cooled <SEP> to <SEP> 5 C. <SEP> urea <SEP> Melting point <SEP> of <SEP> <SEP> greater <SEP> than
<tb> 375 C.
<tb>



  XXI <SEP> 1.04 <SEP> part <SEP> of <SEP> para- <SEP> 1.96 <SEP> part <SEP> of <SEP> chloru-20 <SEP> parts <SEP> 30 <SEP > minu- <SEP> 1.9 <SEP> (acid <SEP> Agitation <SEP> to <SEP> the <SEP> main <SEP>; <SEP> rendephenylenediamine <SEP> dis- <SEP> re <SEP> of <SEP> terephthaloyl <SEP> of hexamethyl <SEP> tes <SEP> sulfuric) <SEP> ment <SEP> of <SEP> 100% <SEP> in <SEP> polymer <SEP> to
<tb> holds <SEP> in <SEP> the solid <SEP> solvent <SEP>. <SEP> phosphoramide <SEP> high <SEP> molecular weight <SEP>.
<tb> cooled <SEP> to <SEP> 20 C.
<tb>



  XXII <SEP> 3,24 <SEP> parts <SEP> of <SEP> meta- <SEP> 6.10 <SEP> parts <SEP> of <SEP> chlo- <SEP> 30 <SEP> parts <SEP> 40 <SEP> minu- <SEP> 0.82 <SEP> (acid <SEP> On <SEP> dissolves <SEP> the <SEP> diamine <SEP> in
<tb> phenylene <SEP> diamine <SEP> dis- <SEP> isophthaloyl <SEP> <SEP> of <SEP> N-acetyl <SEP> tes <SEP> sulfuric) <SEP> the <SEP> solvent <SEP> and <SEP> on <SEP> cools <SEP> the
<tb> bunkers <SEP> in <SEP> the solid <SEP> solvent <SEP>. <SEP> pyrrolidine <SEP> solution <SEP> to <SEP> -1 C <SEP> in <SEP> a <SEP> vial
<tb> to <SEP> 4 <SEP> tubing. <SEP> On <SEP> adds <SEP> on
<tb> <SEP> acid chloride <SEP> within <SEP> 8-10
<tb> minutes. <SEP> The <SEP> temperature <SEP> rises
<tb> finally <SEP> to <SEP> 30 C.

   <SEP> On <SEP> gets
<tb> a <SEP> viscous <SEP> solution <SEP> which <SEP> con-,
<tb> comes <SEP> to <SEP> spinning.
<tb>



  XXIII <SEP> 1 <SEP> 08 <SEP> part <SEP> of <SEP> meta- <SEP> 2.03 <SEP> parts <SEP> of <SEP> chlo- <SEP> 10.2 <SEP> parts <SEP> 20 <SEP> minu- <SEP> 0.72 <SEP> (acid <SEP> On <SEP> freezes <SEP> the <SEP> solution <SEP> of <SEP> diaphenylene <SEP> diamine < SEP> dis- <SEP> isophthaloyl <SEP>. <SEP> of <SEP> N, N-tetra-tes <SEP> sulfuric) <SEP> mine <SEP> in <SEP> the <SEP> ice <SEP> carbonic.
<tb> bunkers <SEP> in <SEP> the <SEP> soil- <SEP> methylene-N ', <SEP> On <SEP> add <SEP> the acid halide <SEP>
<tb> before <SEP> cold. <SEP> N'-dimethyl- <SEP> solid, <SEP> in <SEP> once <SEP>. <SEP> The <SEP> polyurea <SEP> mother <SEP> obtained <SEP> under <SEP> form <SEP> of <SEP> solution, <SEP> is <SEP> precipitated <SEP> by <SEP> the water.
<tb>



    

Claims (1)

CLAIMS --------------------------- 1.- Shaped articles characterized in that they consist of or contain a polymer whose recurring structural element has the formula: EMI33.1 where Ar1 and Ar2 are bivalent aromatic radicals of marls or different compositions and where the chain extension bonds are attached to non-neighboring carbon atoms in an aromatic nucleus or ring system, these polymers having an inherent viscosity of at least 0.6 and preferably greater than 0.8 in concentrated sulfuric acid at 30 C. 2. Shaped articles according to claim 1, characterized in that Ar1 and / or Ar2 is an aromatic radical with a single ring. 3.- Shaped articles according to claim 1 or 2, characterized in that the nitrogen atoms are attached to the aromatic radical in the meta position. 4.- Shaped articles according to claims 1 to 3, characterized in that the atoms are attached to the aromatic radical in the meta position. 5. - Shaped articles according to claim 3 or 4, characterized in that the polymer further contains structural elements of the same chemical composition, in which the carbon atoms and / or nitrogen atoms are attached to the aromatic radical in position para. 6.- Shaped articles according to claims 1 to 5, characterized in that the article or the polymer contained therein melts at a temperature above 300 C. 7. - Shaped articles according to claims 1 to 6, characterized in that they have the form of filaments or fibers in which the polymer molecules are oriented along the longitudinal axis. <Desc / Clms Page number 34> 8.- Fabrics characterized in that they consist of or contain the filaments or fibers according to claim 7. 9. - Shaped articles according to claims 1 to 6, characterized in that they have the shape of a film. 10. Shaped articles according to claim 9, characterized in that the film is in the form of a coating on a substratum, which may for example be metal, glass or fabric. 11. Shaped article according to claim 10, characterized in that the substratum is a metal wire. 12. - Shaped articles according to claim 9, characterized in that the polymer molecules are oriented in at least one direction. 13. A process for producing shaped articles according to claims 1 to 12, characterized in that the articles are shaped from their solutions, preferably in a solvent containing nitrogen or a sulfoxy group, which we separate afterwards. 14.- Process according to claim 13, characterized in that the solvent is a liquid amine with low molecular weight, with a high content of amino nitrogen, 15. A method according to claim 14, characterized in that at least part of the amine exists in the form of hydrochloride. 16. - Process according to claim 14 or 15, characterized in that a minor proportion of water exists in the solvent, and preferably does not exceed 10% by weight. 17. A method according to claim 13, characterized in that the solvent is a cyclic polymethylene sulfoxide. 18. A method according to claim 13, characterized in that the articles are shaped directly from the polymer solution obtained during its preparation from the monomer starting materials. <Desc / Clms Page number 35> 19.- 'Process according to claim 13 or 18, characterized in that the solvent is a solvent of the amide type, preferably having the structural formula (E) given above. 20. - Process according to claim 19, characterized in that the amide solvent is dimethylformamide. dimethyl-a.cetamide, N-methyl pyrrolidone or hexamethylphosphoramide. 21. - Method according to claim 13, characterized in that the filaments or fibers are produced by dry spinning. 22. - Articles of form, in substance as described in the description and the examples cited. 23.- A method of producing new shaped articles, in substance as described in the description and the examples cited.