CA2088115A1 - Aromatic copolyamides, processes for their preparation and structures formed therefrom - Google Patents
Aromatic copolyamides, processes for their preparation and structures formed therefromInfo
- Publication number
- CA2088115A1 CA2088115A1 CA002088115A CA2088115A CA2088115A1 CA 2088115 A1 CA2088115 A1 CA 2088115A1 CA 002088115 A CA002088115 A CA 002088115A CA 2088115 A CA2088115 A CA 2088115A CA 2088115 A1 CA2088115 A1 CA 2088115A1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
Abstract
Abstract Aromatic copolyamides, processes for their preparation and structures formed therefrom Aromatic copolyamides are described which are soluble in organic polyamide solvents and which comprises the recurring structural units of the formula Ia, Ib, Ic and, optionally, Id [ -OC-R1-CO-NH-R2-NH- ] (Ia), (Ib), (Ic), [ -OC-R1-CO-NH-R3-NH- ] (Id) in which R1 and R2 are mainly unsubstituted divalent aromatic radicals, the valency bonds of which are in the para-position or in a comparable coaxial or parallel position with respect to one another, X is a group of the formula -S-, -SO2-, -CO- OR -O-, Y assumes one of the definitions given for X, and R3 is a radical of the formula II, of the formula III, of the formula IV and/or of the formula V
(II), (III),
(II), (III),
Description
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. , HOECHST AKTIENGESELLSCHAFT HOE 92/F 020 R Dr~AC/PP
`;;~ Description '.
Aromatic copolyamides, processes for their preparation and structures formed therefrom The invention relates to novel aromatic copolyamides of the dicarboxylic acid-diamine type, which can be spun from their solutions in organic ~olvents, and also to sh~ped structures produced therefrom, such as fibPrs, films and coatings which have a very high initial modulus (modulus of elasticity), and to processes for their ` 10 preparation.
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- -; As is known, aromatic polyamides (aramids) are raw - materials which have high ~tability to heat and high chemical stability as well as low combustibility. Thus, for example, fibers and films composed of such raw materials have very good mechanical properties, such as high strength and a high initial modulus (modulus of elasticity) and are very suitable for industrial fields of application - for example for reinforcing plastics or ~ as filter materials.
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It is known that filaments or fibers composed of polyara-mides which have high strengths and a high initial ~-~ modulus can be produced if the amide bonds to ~he aromat-ic nuclei are oriented coaxially or virtually parallel to one another, as a result of which rigid, rod-shaped polymer molecules are formed.
A typical polyamide of this type is, for examplel poly(p-phenyleneterephthalamide). Filaments composed of this material are descxibed, for example, in German Patent 22 19 703.
,' This polyamide has a number of advantages, but its .; preparation and its processing are very difficult.
Because of the insolubility in polar organic solvents -: , ~ .
.
.
. , HOECHST AKTIENGESELLSCHAFT HOE 92/F 020 R Dr~AC/PP
`;;~ Description '.
Aromatic copolyamides, processes for their preparation and structures formed therefrom The invention relates to novel aromatic copolyamides of the dicarboxylic acid-diamine type, which can be spun from their solutions in organic ~olvents, and also to sh~ped structures produced therefrom, such as fibPrs, films and coatings which have a very high initial modulus (modulus of elasticity), and to processes for their ` 10 preparation.
~;
- -; As is known, aromatic polyamides (aramids) are raw - materials which have high ~tability to heat and high chemical stability as well as low combustibility. Thus, for example, fibers and films composed of such raw materials have very good mechanical properties, such as high strength and a high initial modulus (modulus of elasticity) and are very suitable for industrial fields of application - for example for reinforcing plastics or ~ as filter materials.
:.~
It is known that filaments or fibers composed of polyara-mides which have high strengths and a high initial ~-~ modulus can be produced if the amide bonds to ~he aromat-ic nuclei are oriented coaxially or virtually parallel to one another, as a result of which rigid, rod-shaped polymer molecules are formed.
A typical polyamide of this type is, for examplel poly(p-phenyleneterephthalamide). Filaments composed of this material are descxibed, for example, in German Patent 22 19 703.
,' This polyamide has a number of advantages, but its .; preparation and its processing are very difficult.
Because of the insolubility in polar organic solvents -: , ~ .
.
.
and specifically also in the presence of inorganic salts, such as calcium chloride or lithium chloride, as solubilizing agents, this polymer will precipitate out of the reaction medium shortly after it has formed. It must be isolated, washed, ~ried and then redissolved in a spinning solvent. The preferred solvent for the prepar-ation of the spinning solutions is concentrated sulfuric acid, which gives rise to particular problems in relation to handling (safety at work, corrosion) and waste disposal.
Attempts have therefore been made to circumvent these difficulties by developing copolyamides which have good solubility in the known amide solvents and which can also readily be spun and the filaments of which, after stretching, are distinguished by high strength values and initial moduli.
Thus, for example, copolyamides obtained from tereph-thalic acid, p-phenylenediamine and 3,4~-diaminophenyl ether, which in amide solvents yield isotropic solutions which can readily be spun, have been described in German Patent 25 56 883 and in German Offenlegungsschrift (German Published Specification) 30 07 063. As a result of very high stretching, the filaments acquire high strengths and moduLi. Here it is the meta orientation and the oxygen atom which give rise to the increased solubil-ity. However, there is still a need for aramids which can be processed from known amide solvents to give fibers which h~ve high strengths and moduli.
It has now been found that selected aromatic copolyamides of high molecular w ight can be processed to give shaped structures which arP distinguished by surprisingly good mechanical properties, such as high tear strengths, high initial moduli and low elongation at break.
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The object on which the present invention i5 based is, therefore, to provide further aromatic copolyamides which are distinguished by good solubility in polyamide ~ solvents and by good gpinnability and which can be : 5 processed to give shaped structures which have good ; mechanical properties.
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The copolyamides according to the invention are charac- terized by the presence of selected aromatic diamine components in selected proportions.
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The present invention relates to aromatic copolyamides which are soluble in organic polyamide solvents and have an inherent viscosity of at least 3.5 dl/g, in particular at least 4.5 dl/g, measured at 25C in solutions of O.25 % by weight of copolymer in N-methylpyrrolidone, ~ 15 containing the recurring structural units of the formu-~ lae Ia, Ib, Ic and optionally Id ,' :
OC-Rl-CO-NH-R2 NH- I (Ia), .-' - O C - R I - C O - N H~ X~LN H
~.
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~-OC-RI-CO-NH ~ Y ~ r ~ NH3 :.
:: 20 ~ - Oc - Rl~ C 0 ~ N H - R3- N H ] (Id) " . ~
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in which at least 80 mol ~ of all radicals R1, with ~ respect to the amount of these radicals in the copolymer, - are an unsubstituted divalent aromatic radical, the ~alency bonds of which are in the para-posit$on or in a comparable coaxial or parallel position with respect to one another, and up to 20 mol ~ of all radicals R1, with respect to the amount of these radicals in the copolymer, are an unsubstituted divalent aromatic radical, the valency bonds of which are in the meta-position or in a comparable angled position with resp~ct to one another, R2 is an unsubstituted divalent aromatic radical, the valency bonds of which are in the para-position or . in a comparable coaxial or parallel position with - respect to one another, : 15 X is a group of the formula -S-, -SO2-, -CO- or, in particular, -O-, Y assumes one of the definitions given for X, in particular -O-, and R3 is a radical which differs from R2 and is of the formula II and/or of ~he formula III and/or of the formula IV and/or of the formula V
.. ~ _ (II), ~CO - NH~ (III), Hal .
~ (IY), ~ (v)l in which Hal is a halogen atom and R4 is Cl-C6-alkyl, Cl-C6-alkoxy and/or halogen, and the proportion of recurr-ing structural units Ia, Ib, Ic and Id, with respect to the sum of these structural units in the copolymer, is within the following limits:
- 5 ~
: recurring s~ructural unit of the formula Ia: 40 to 65 mol %, preferably 45 to 55 mol %;
-~ recurring structural unit of the formula Ib: 5 to 55 mol %, preferably 35 ~o 45 mol %;
recurring structural unit of the formula Ic: 5 to 35 mol ~, preferably 5 to 25 mol %; and recurring structural unit of the formula Id: 0 to 30 mol %, prefera~ly 0 or 5 to 20 mol %.
If a copolymer comprises radicals in the meta-position, : 10 such as radicals R1 or radicals of the formula IV in the meta-position, the amount of the recurring ~tructural units of the formula Ib preferably ranges within the lower range of the indicated amount, for example 5 to 30 mol %.
If the copolymer according to the invention comprises recurring structural units of the formula Id, in particu-lar those which comprise radicals of the formula IV, the :~ amount of said units is preferably 5 to 15 mol ~ and very particularly preferably 5 to 10 mol %, with respect to ~- 20 the sum of ~he structural units Ia, Ib, Ic and Id.
Structural units of the formula Id can also comprise different radicals of the formulae II to V, ~or example radicals of the formula III and V, IV and V or III, IV
:: and V.
If any radicals are divalent aromatic radicals the valency bonds of which are in the para-position ox in a comparable coaxial or parallel position with respect to one another, said radicals are mononuclear or polynuclear - aromatic hydrocarbon radicals or heterocyclic-aromatic radicals, which can be mononuclear or polynucl~ar. In the ~ case of heterocyclic-aromatic radicals, said radicals ; comprise, in particular, one or two oxygen, nitrogen or ; sulfur atoms in the aromatic nucleus.
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Polynuclear aromatic radicals can be fused with one another or linearly bonded to one another via C-C bonds ~ or via a -CO-N~- group.
- The valency bonds which are in a coaxial or parallel position with respect to one another are in opposing directions. An example of coaxial bonds in opposing directions are ~he biphenyl-4,4'-ene bonds. Examples of parallel bonds in opposing directions are the naphthalene 1,5- or 2,6-bonds, whilst the naphthalene 1,8-bonds are parallel and in the same direction.
Examples of preferred divalent aromatic radicals, the valency bonds of which are in the para-position or in a comparable coaxial or parallel position with respect to one another, are mononuclear aromatic radicals which have free valencies in the para-position with respect to one another, in particular 1,4-phenylene, or binuclear, fused aromatic radicals which have parallel bonds in opposing directions, in particular 1,4-, 1,5- and 2,6-naphthylene, or binuclear aromatic radicals which are linked Yia a C-C bond and have coaxial bonds in opposing directions, in particular 4,4'-biphenylene.
P~rticularly preferred radicals R1 and R2 are 1,4-phenylene.
If any radicals denote divalent aromatic radicals which have ~alency bonds which are in the meta-position or in ~ a comparable angled position with respect to one another, "! said radicals are mononuclear or polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals, which can be mononuclear or polynuclear. In the case of heterocyclic-aromatic radicals, said radicals comprise, in particular, one or two oxygen, nitrogen or sulfur atoms in the aromatic nucleus.
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Polynuclear aromatic radicals can be fused with one another or can be linked to one another via C-C bonds or via bridge groups, such as, for example, -O-, -CH2-~-CO-NH-, -S-, -CO- or -SO2-.
:
Examples of polynuclear aromatic radicals in which the valency bonds are in an angled position comparable to the : meta-position are 1,6-naphthylene, 2,7-naphthylene or 3,4'-biphenylene.
A preferred example of a mononuclear aromatic radical of this type is 1,3-phenylene.
~ Examples of Hal substituents in radicals of the formula II or Y ar~ bromine and in particular chlorine.
R4 is preferably methoxy, and in particular methyl.
: In order to prepare the copolyamides comprising the ~ 15 recurring structural units Ia, Ib, Ic and, optional-ly, Id, a dicarboxylic acid dichloride of the formula X
is appropriately reac~ed with a mixture of the diamines of the formulae VI, VII, VIII and, optionally, IX
CIOC-RI-COCI (X), H2N-R2-NH2 (VI), ~ ~ NH2 (VII) 2N ~ r ~ r ~ NH2 ~ H 2 N - R 3- N H 2(IX)~
in which the radicals Rl to R3 as well as X and Y have the meaning defined further above.
The dicarboxylic acid dichloride of the formula X and the individual diamine types can also be used in the form of - 8 - ~ a ~
mixtures.
For this reaction, the proportions of the diamines YI, VII and VIII and, optionally, IX are in each case to be chosen such that polyamides are formed which have the above-defined proportions of structural units of the formulae Ia, Ib, Ic and, optionally, Id.
It is self-evident to a person skilled in the art that the sum o~ all structural units derived from aromatic acids and the sum of all structural units derived from aromatic amines are essentially identical, i.e. that they differ by at most about 1 %, preferably by at most 0.2 ~, and in particular are identical within the framework of the practical measurement and metering possibilities.
The molecular weight of the polyamides formed can be controlled, inter alia, via t~e selection of ~he propor-~ions of aromatic acids to aromatic amines. These selec-tion criteria are known to those skilled in the art in the polycondensation field.
Examples of suitable aromatic dicarboxylic acids from which the dicarboxylic acid dichlorides of the formula X
are derived are naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid acid and in particular terephthalic acid.
~ Up to 10 mol ~ of the dicarboxylic acid dichlorides can -~ also be derived from divalent aromatic meta-radicals.
Examples of acids from which such dicarboxylic acid dichlorides are derived are naphthalene-1,6-dicarboxylic acid, naph~halene-1,7-dicarboxylic acid, naphthalene-~,7-dicarboxylic acid, biphenyl-3,4~-dicarboxylic acid and in particular isophthalic acid.
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Examples of suitable diamines of the formula VI are naphthalene-1,4-diamine, naph~halene-1,5-diami.ne, naph-thalene-2,6-diamine, benzidine and in particular p-phenylenediamine.
5 The diamines of the formula VII (3r4~-diaminodiphenyl ether) and of the formula VIII (1,4-bis-(4-aminophenoxy)-benzene) are known per se.
Examples of suitable diamines of the formula IX are 2-r chloro-1,4-phenylenediamine, 4,4~-diaminobenzanilide and 10 m-phenylenediamine, 3,5'-dimethylbenzidine, 3,5'-di-chlorobenzidine or 3,5~-dimethoxybenzidine.
The copolymeri2ation of the monomer compounds described above is generally carried out as solution polymerization.
: 15 To this end, the aromatic monomer compounds to be reacted with one another are as a rule dissolved in an organic solvent. The organic solvent preferably comprises at ; least one solvent of the amide type, such as, for ex-ample, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 20 tetramethylurea, N-methyl-2-piperidone, N,N'-dimethyl-ethyleneurea, N,N,~',N'-tetramethylmaleimide, N-methyl-caprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N'-dimethylpropionamide, N,N-dimethylisobutylamide, N-methylformamide or N/N~-dimeth-25 ylpropyleneurea. The preferred organic solvents N-methyl-2-pyrrolidone, N,N-dimethylacetamide and a mixture of these compounds are of importance for the process acGord-ing to the invention.
. .
- In a preferred embodiment of the solution polymerization, the aromatic monomer diamines are dissolved in an amide solvent. The solution thus obtained is then mixed with the at least one aromatic monomer compound in the form of an aromatic dicarboxylic acid dihalide, with vigorou6 , ..
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stirring, in order to initiate the copolymerization.
In this process the amide solvent is used not only as solvent for the aromatic monomer compounds and the aromatic copolyamide obtained therefrom but also as acid acceptor for a hydrogen halide, for example for hydrogen chloride, which is formed as a by-product of the copoly-merization of the aromatic monomer compounds. In some cases it can be advantageous to use an additive which promotes the solubility, for example a metal halide of one of the metals of Group I or II of the Periodic Table, which halide is added to the copolymerization mixture before, during or after the copolymerization.
Examples of such additives are alkali metal halides, such as lithium chloride, or alkaline earth metal hali~es, such as calcium chloride.
The polycondensation temperatures for the solution polymerization are usually between -20C and +120C, preferably between ~10C and +100C. Particularly good results are obtained with reaction temperatures of between +10C and +80~C.
~, ~i The sum of the concentrations of the aroma~ic monomer compounds in the polymerization mixture solution can be adjusted taking into account the desired degree of polymerization, the desired viscosity of the polymeriza-tion mixture, the nature of the aromatic monomer com-pounds used, ~he nature of the solvent used nd the desired polymerization temperature. The most fa~orable ; sum of the concentrations can be determined on th~ basis of a number of preliminary experiments for the course of the polymerization.
Polycondensation reactions are preferably ~arried out in such a way that 2 to 15, preferably 5 to 12, % by weight of polycondensation product are present in the solution .
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; ~ 2 ~ ~ 3 Il~J
after the reaction i5 complete. Particularly good results ; are obtained with concentrations of 5.0 to 8 % by weight.
r~ The molecular weight of the polymer, and thus also the ~- viscosity of the reaction batch, increase in the course ; 5 of the polycondensation reaction.
:;, An adequate molecule chain length is reached if the viscosity of the polymer solution obtained from the polycondensation reaction corresponds to an inherent viscosity of the polymer greater than 3.5, preferably ~` 10 greater than 4.5 and particularly preferably greater than S.0 dl/g, in particular 5.5 to 8.0 dl/g.
` Inherent viscosity is understood to mean the expression ~`
In ~rel " ~, ~7 inh c In this expression, ~rel iS the relative viscosity and c the concentration used, in g/100 ml.
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For the purpo es of the present invention, it is deter-mined for solutions of, in each case, 0.25 ~ of polymer in N-methylpyrrolidone at 25C.
;~' '.~
Insofar as it is used to prepare the aromatic polyamides according to the invention which have been described , above, ~he process for the preparation of aromatic polyamides which has been outlined and is known per se is ~' 25 also a ubject of the invention.
Y' If the polymer solution has reached the viscosity re-quired for further processing, the polycondensation reaction can be stopped in the conventional manner by ' adding monofunctional compounds, such as, for exampleJ
acetyl chloride. ~he hydrogen chloride formed, which is :, .
`
bound in salt form to ~he amide solvent, can then be neutralized by adding basic substances.
Substances suita~le for this purpose are, for example, lithium hydroxide and calcium oxide, but in particular calcium hydroxide.
. , The aromatic copolyamide obtained on carrying out the process according to the invention can be separated off from the copolymerization mixture by means of a separa-tion process, for example by precipitation. In order to prepare a solution for shaping the copolyamide, the aromatic copolyamide obtained in this way is then dis-solved in a suitable organic solvent, this process being designated the dissolving process for the preparation of the shaping solution.
., r'15 However, in those cases in which the solution polymeriza-tion process is used to prepare the aromatic copolyamide according to the invention, the copolyamide is completely -dissolved in the solvent for the polymerization, because it is outstandingly soluble in said solvent. Therefore, if the process according to the invention is used indus--~trially it is advantageous to use the mixture obtained from the polymerization immediately as shaping solution for the aromatic copolyamide.
.~ .
The aromatic copolyamide according to the invention is outstandingly soluble in an organic solvent, for example .~in organic solvents of the amide type, and has outstand-ing resistance to heat and superior resistance to chemi-cals. The aromatic copolyamide according to the invention is particularly useful for the production of diverse :~30 shaped articles, for example fibers, films and coatings, which are likewise a subject of the invention.
!Within the framework sf this description the term "fibers" is to be understood in its broadest meaning;
;, :
; thus, the term also covers, for example, filaments or staple fi~ers of any desired denier.
Within the framework of this description, the term "films is likewise to be understood in its broadest meaning; thus, it also covers, for example, embodiments of di~erse thickness, such as sheets or membranes.
The shaped structures not only have outstanding resist-ance to heat and resistance to chemicals but also have superior mechanical properties, for example in respect of the tensile streng~h, the abrasion resistance and the modulus of elasticity. The solution of the aromatic copolyamide can also be used in diverse ways, for example for the production of fibers, ~heets, sheet-like ele-ments, fibrous materials and other shaped articles.
The solvent used in the process for the preparation of ` the shaping solution of the aromatic copolyamide is preferably a solvent of the amide type, in particular the ` solvents of the amide type which have been mentioned further above, or a mixture of two or more of the said ; 20 compounds.
...
For the preparation of the shaping solution it is advant-ageous if the conc~ntration of the aromatic copolyamide is kept within a range between 4 and 15 % by weight, in particular between 5 and 12 % by weiyht. If necessary, the shaping solution can comprise an additi~e to promote the solubility, it being possible to use at least one metal halide of a metal of Groups I and II of the Periodic ~able, for example lithium chloride, calcium chloride or magnesium bromide, specifically in a concen-tration of between 0.2 and 10 %, preferably of between0.5 and 5 ~, with respect to the total weight of the shaping solution. The additive to promote the solubility also promotes the stability of the shaping solution at elevated temperature.
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- 14 ~ ~
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Shaping of the shaping solution to give a shaped article can be carried out by any suitable dry process, wet .` process or dry/wet process. In the cases in which a wet process is used in order to shape the shaping solution, for example to give filaments, the shaping solution or -in this case - the spinning solution is extruded through a die, for example a spinneret, into a coagulating liquid. ~ith this procedure it is usually advantageous if ~ the coagulation liquid is composed of water or of an ; 10 aqueous solution containing a polar organic solvent. The ` polar organic solvent can be selected from thie same amide solvents which are cus~omarily used for dissolving the ~ aromatic copolyamide.
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The polar organic solvent used in the coagulation liquid is preferably the same solvent as is contained in the ~` shaping solution. The coagulation liquid is preferably used at a tempera~ure between 0C and the boiling point : of the coagulation liquid under atmospheric pressure.
.,, The polar organic solvent is preferably present in the coagulation liquid in a concentration of less than 70 %
; by weight, in particular less than 50 ~ by weight.
.`~ The shaping process explained above is par~icularly;; suitable for the production of films or fibers from a shaping solution.
..;
When producing fibers from the aromatic copolyamide, the shaping or spinning solution is extruded through a spinning head which has multiple spin orifices, the ;. filament-form streams of the ~pinning solution being solidified in one of the coagulation liquids indicated above (wet process) or in an atmosphere promoting evapor-~; ation (dry process). A variant which is also suit~ble is the "dry jiet/wet spinning process", as is described, for example, in US-A-34 14 645. A conventional horiæontal or vertical wet spinning machine, a dry jet wet spinning , ' .
.
~ ~ ' , machine or a spinning machine in which the ma erial flow is downward under stress can be used for spinning.
In the case of wet spinning of an aromatic copolyamide according to the invention, the coagulation is preferably effected using a coagulation liquid containing an addi-tive to promote coagulation, this coagulation being followed by a further coagulation step, in the course of which the coagulating filaments of the aromatic copoly-amide are passed into a water bath which is kept a$ a temperature of between 0 and 100C.
,.~
The additional coagulation step serves to complete the coagulation by removal of the solvent. In addition, additives to promote coagulation, if such substances are used, are washed out of the coagulated filaments.
It is clear from the above description that the aromatic copolyamide according to the invention can be processed to give filaments without any problems, using conven-tional spinning processes and equipment, without a hazardous or harmful solvent, such as, for example, ~- 20 concentrated sulfuric acid, having to be used.
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Consequently, the risks for the operating personnel are ~ reduced. In addition, the filaments produced from the ; copolyamide according to the inYention have a dense internal structure.
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The shaping solution can also be processed to give a film using conventional fanning or extruding processes.
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Fibers or films which are produced by the shaping pro-~ cesses indicated above are usually subjected to a -~ stretching operation, by means of which not only the mechanical properties, such as, for example, the tensile strength and the modulus of elasticity, but also the thermal properties, such as, for example, the stability 16 2~"~
:
to heat, of the filaments or films produced in this way are improved.
Filaments composed of the aromatic copolyamides according to the invention are as a rule stretched in order to obtain a high mechanical strength and a high modulus of elasticity. The stretching ratio is usually about 1:6 to ; 1:20. The stretching temperature is as a rule between 250 and 550C, preferably between 350 and 500C.
~Stretching can be carried out in a single step, in two r~` 10 steps or in several steps and a hotplate or a cylindrical heating device can be used for heating. In addition, the ;stretched filaments or films can be subjected to a , further heat treatment at the same temperature or a higher temperature in order to Lmprove the crystalline structure. In this context it is pointed out that the `~aromatic copolyamide according to the invention is not only surprisingly advantageous with respect to its `solubility in conventional organic solvents but can also : be stretched under "mild" operating conditions without any problems after the production of the fibers or films.
;The fibers obtainable from the copolymers according to ;the invention are distinguished by high tear strengths and initial moduli and by low elongations at break.
:, A further preferred subject of the pre~ent invention comprises fibers composed of the copolymers according to the invention, which have a tear strength of about 90 to 250 cN/tex, in particular 150 to 250 cN/tex, an initial modulus, with respect to 100 ~ elongation, of about 25 ~o 60 N/tex, in particular 35 to 50 N/tex, and an elongation at break of about 3 to 7 ~, in particular 4 to 6 %.
It has been found, surprisingly, that fibers which have high transverse strength values not obtained hitherto for aramides and which have a combination of exceptionally ~,, .
. : , - 17 - 2~
high tear strength and transverse strength can be produced from the copolyamides according to the invention ; by using particular stretching conditions~ The loop ; strength (in accordance with DIN 53843) or the knot strength (in accordance with DIN 53842 Part 1~ can be used as a criterion for the transverse strengths.
Preferred fibers composed of the copolyamides according to the invention have knot strengths of 25 to 80 cN/tex, in particular of 50 to 80 cN/tex, and/or loop ~tren~ths of 40 to 130 cN/tex, in particular of 85 to 120 cN/tex.
.;, .
i Very particularly preferred fibers composed of the copolyamides according to the invention have tear strengths of more than 200 cN/tex, in particular of 200 to 250 cN/tex, and loop s~rengths of more than 80 cN/tex, in particular of 85 to 120 cN/tex.
These particularly preferred fibers are obtainable by ~ stretching the spun fibers at elevated temperature and ;~ using a spin finish preparation which is stable under the stretching conditions. Such preparations essentially ;~ 20 contain a particulate, inert inorganic material which lowers the sliding friction between the fibers during the stretching process. These preparations are usually applied to the fibers from an aqueous suspension and a ;uniform layer of said incrganic mat0rial is ~hen produced around the fibers by drying. Examples of suitable inorganic and inert particles are graphite, talc, colloidal silica, water-repellent silica, mica, hydrated magnesium silicate or aqueous dispersions containing magnesium ~ilicate and an aqueous gel-forming inorganic compound, such as aluminum silicate.
Examples of such preparations are describPd in JP-A-60-239,522, JP-A-60-239,523 and EP-A-121,132.
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Stretching of the aramid fibers pretreated in this way is generally carried out at fiber temperatures of higher than 300C, pre~erably at 350 to 550C. The degrees of stretching for the production of these particularly preferred aramide fibers are usually 1:8 to 1:20, prefer-ably 1:9 to 1:15.
The invention also relates to such fibers and a process for their production.
The fibers composed of an aromatic copolyamide according to the invention, which have outstanding m~chanical and ; thermal properties and are distinguished by a high stretchability, can be used industrially in very diverse ways, for example for reinforcing plastics, in particular as reinforcing materials for the fabric inserts in car tires and other rubber articles, as heat-resistant insulating materials, for the production of filter fabrics and as lightweight insulating materials. Films composed of an aromatic copolyamide according to the invention can be used as heat-resistant electrical insulating materials, in particular for ~he production of membranes, for example as support material for separation membranes.
Further features and advantages of the inven~ion are explained in more detail below with the aid of examples.
Howev~r, it is to be understood that the invention is not restricted to the illustrative examples. On the contrary, numerous possibilities for modifications and/or supple-ments are available to a person skilled in the art, taking the illustrative examples as a basis, without having to go beyond the basic concept of the invention.
-19~ 2~3~
Example 1 "
Aromatic copolyamide obtained from 100 mol % of tereph-thalic acid dichloride, 50 mol ~ of p-phenylenediamine, 25 mol % of 1,4-bis-(4-aminophenoxy)-benzene and 25 mol %
~;.5 of 3,4'-diaminodiphenyl ether.
;, 162.2 g (1.5 mol) of p-phenylenediamine, lS0.2 g (O.75 mol) of 3,4~-diaminodiphenyl ether and 219.3 g (O.75 mol) of 1,4-bis-(4-aminophenoxy)-benzene are .dissolved, under nitrogen, in 14042 g of N-methylpyr-rolidone and 607.3 g (3 mols) of terephthalic acid dichloride are added in the course of 20 minutes at between 35C and 55C. When ~he desired viscosity (~
= 5.5 dl/g) is obtained, the polycondensation reaction is stopped by adding 4.7 g of acetyl chloride and the ;~15 reaction mixture is then neutralized with 328.2 g of calcium oxide (55 % strength suspension in NMP). The solution is stirred further at 120C. Th~ solution is filtered, degassed and spun wet. To this end, it is spun at a rate of 16 m/min from a die which has 100 orifices each 0.1 mm in diameter into a coagulation bath compris-ing a 35 % solution of N-methylpyrrolidone in water, .;which is at 80C. The resulting filaments are stretched to 11 times their length through two water baths, a washing machine, via a drying godet and finally over a hot plate at temperatures of 400 to 440C.
. . .
The filament linear density is 1.91 dtex for a tear strength of 190 cN/tex, an elongation of 4 ~ and an initial modulus of 41 N/tex, with respect to 100 % elongation.
Examples 2 to 37 Further aromatic copolyamides are produced, spun and tested in accordance with the procedure described in Example 1. The diamines used, the proportions thereof, the solution viscosities of the resulting polymers, the .
- 20 ~
spinning conditions and properties of the resulting fibers are given in Table 1 ~elow. The following abbrevi-ations are used for the monomers in Table 1:
TPC = terephthalic acid dichloride IPC = isophthalic acid dichloride :`NDC = 2,6-naphthalenedicarboxylic acid dichloride PPD = p-phenylenediamine 3,4'-DADPE = 3,4'-diaminodiphenyl ether BAPOB = 1,4-bis-(4-aminophenoxy)-benzene ~,~10 4, 4 ' -DABA = 4,4'-diaminobenzanilide . Cl-PPD = chloro-para-phenylenediamine MPD = m-phenylenediamine DM~ = 3,5'-dLmethylbenzidine .; .
. .
:' :
.~.
.:~
. ~ .....
: , ~ - 21 ~
.' ~ . . ,..................... _...... .. I
Example No. 2 3 4 5 6 7 ¦ 8 9 . TPC (mol %) 100 100 100 100 100 100 100 100.~ S
IPC (mol %) 0 0 0 0 0 0 0 0 NDC (mol %) 0 0 0 . 0 0 0 0 0 ~' _ _ _ : 10 PPD (mol ~) 55 50 50 50 50 50 50 50 3,4'-DADPE (mol ~) 22.5 20 40 30 20 30 20 25 _ _ BAPOB (mol %) 22.5 30 10 20 20 10 20 25 .
Attempts have therefore been made to circumvent these difficulties by developing copolyamides which have good solubility in the known amide solvents and which can also readily be spun and the filaments of which, after stretching, are distinguished by high strength values and initial moduli.
Thus, for example, copolyamides obtained from tereph-thalic acid, p-phenylenediamine and 3,4~-diaminophenyl ether, which in amide solvents yield isotropic solutions which can readily be spun, have been described in German Patent 25 56 883 and in German Offenlegungsschrift (German Published Specification) 30 07 063. As a result of very high stretching, the filaments acquire high strengths and moduLi. Here it is the meta orientation and the oxygen atom which give rise to the increased solubil-ity. However, there is still a need for aramids which can be processed from known amide solvents to give fibers which h~ve high strengths and moduli.
It has now been found that selected aromatic copolyamides of high molecular w ight can be processed to give shaped structures which arP distinguished by surprisingly good mechanical properties, such as high tear strengths, high initial moduli and low elongation at break.
~_ 3 _ 2~
The object on which the present invention i5 based is, therefore, to provide further aromatic copolyamides which are distinguished by good solubility in polyamide ~ solvents and by good gpinnability and which can be : 5 processed to give shaped structures which have good ; mechanical properties.
.
The copolyamides according to the invention are charac- terized by the presence of selected aromatic diamine components in selected proportions.
~:`
The present invention relates to aromatic copolyamides which are soluble in organic polyamide solvents and have an inherent viscosity of at least 3.5 dl/g, in particular at least 4.5 dl/g, measured at 25C in solutions of O.25 % by weight of copolymer in N-methylpyrrolidone, ~ 15 containing the recurring structural units of the formu-~ lae Ia, Ib, Ic and optionally Id ,' :
OC-Rl-CO-NH-R2 NH- I (Ia), .-' - O C - R I - C O - N H~ X~LN H
~.
::;
':
~-OC-RI-CO-NH ~ Y ~ r ~ NH3 :.
:: 20 ~ - Oc - Rl~ C 0 ~ N H - R3- N H ] (Id) " . ~
~ .
in which at least 80 mol ~ of all radicals R1, with ~ respect to the amount of these radicals in the copolymer, - are an unsubstituted divalent aromatic radical, the ~alency bonds of which are in the para-posit$on or in a comparable coaxial or parallel position with respect to one another, and up to 20 mol ~ of all radicals R1, with respect to the amount of these radicals in the copolymer, are an unsubstituted divalent aromatic radical, the valency bonds of which are in the meta-position or in a comparable angled position with resp~ct to one another, R2 is an unsubstituted divalent aromatic radical, the valency bonds of which are in the para-position or . in a comparable coaxial or parallel position with - respect to one another, : 15 X is a group of the formula -S-, -SO2-, -CO- or, in particular, -O-, Y assumes one of the definitions given for X, in particular -O-, and R3 is a radical which differs from R2 and is of the formula II and/or of ~he formula III and/or of the formula IV and/or of the formula V
.. ~ _ (II), ~CO - NH~ (III), Hal .
~ (IY), ~ (v)l in which Hal is a halogen atom and R4 is Cl-C6-alkyl, Cl-C6-alkoxy and/or halogen, and the proportion of recurr-ing structural units Ia, Ib, Ic and Id, with respect to the sum of these structural units in the copolymer, is within the following limits:
- 5 ~
: recurring s~ructural unit of the formula Ia: 40 to 65 mol %, preferably 45 to 55 mol %;
-~ recurring structural unit of the formula Ib: 5 to 55 mol %, preferably 35 ~o 45 mol %;
recurring structural unit of the formula Ic: 5 to 35 mol ~, preferably 5 to 25 mol %; and recurring structural unit of the formula Id: 0 to 30 mol %, prefera~ly 0 or 5 to 20 mol %.
If a copolymer comprises radicals in the meta-position, : 10 such as radicals R1 or radicals of the formula IV in the meta-position, the amount of the recurring ~tructural units of the formula Ib preferably ranges within the lower range of the indicated amount, for example 5 to 30 mol %.
If the copolymer according to the invention comprises recurring structural units of the formula Id, in particu-lar those which comprise radicals of the formula IV, the :~ amount of said units is preferably 5 to 15 mol ~ and very particularly preferably 5 to 10 mol %, with respect to ~- 20 the sum of ~he structural units Ia, Ib, Ic and Id.
Structural units of the formula Id can also comprise different radicals of the formulae II to V, ~or example radicals of the formula III and V, IV and V or III, IV
:: and V.
If any radicals are divalent aromatic radicals the valency bonds of which are in the para-position ox in a comparable coaxial or parallel position with respect to one another, said radicals are mononuclear or polynuclear - aromatic hydrocarbon radicals or heterocyclic-aromatic radicals, which can be mononuclear or polynucl~ar. In the ~ case of heterocyclic-aromatic radicals, said radicals ; comprise, in particular, one or two oxygen, nitrogen or ; sulfur atoms in the aromatic nucleus.
:~
~ 6 - 2 ~
Polynuclear aromatic radicals can be fused with one another or linearly bonded to one another via C-C bonds ~ or via a -CO-N~- group.
- The valency bonds which are in a coaxial or parallel position with respect to one another are in opposing directions. An example of coaxial bonds in opposing directions are ~he biphenyl-4,4'-ene bonds. Examples of parallel bonds in opposing directions are the naphthalene 1,5- or 2,6-bonds, whilst the naphthalene 1,8-bonds are parallel and in the same direction.
Examples of preferred divalent aromatic radicals, the valency bonds of which are in the para-position or in a comparable coaxial or parallel position with respect to one another, are mononuclear aromatic radicals which have free valencies in the para-position with respect to one another, in particular 1,4-phenylene, or binuclear, fused aromatic radicals which have parallel bonds in opposing directions, in particular 1,4-, 1,5- and 2,6-naphthylene, or binuclear aromatic radicals which are linked Yia a C-C bond and have coaxial bonds in opposing directions, in particular 4,4'-biphenylene.
P~rticularly preferred radicals R1 and R2 are 1,4-phenylene.
If any radicals denote divalent aromatic radicals which have ~alency bonds which are in the meta-position or in ~ a comparable angled position with respect to one another, "! said radicals are mononuclear or polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals, which can be mononuclear or polynuclear. In the case of heterocyclic-aromatic radicals, said radicals comprise, in particular, one or two oxygen, nitrogen or sulfur atoms in the aromatic nucleus.
," ~
';
~, : ~ - 7 - 2~31~
Polynuclear aromatic radicals can be fused with one another or can be linked to one another via C-C bonds or via bridge groups, such as, for example, -O-, -CH2-~-CO-NH-, -S-, -CO- or -SO2-.
:
Examples of polynuclear aromatic radicals in which the valency bonds are in an angled position comparable to the : meta-position are 1,6-naphthylene, 2,7-naphthylene or 3,4'-biphenylene.
A preferred example of a mononuclear aromatic radical of this type is 1,3-phenylene.
~ Examples of Hal substituents in radicals of the formula II or Y ar~ bromine and in particular chlorine.
R4 is preferably methoxy, and in particular methyl.
: In order to prepare the copolyamides comprising the ~ 15 recurring structural units Ia, Ib, Ic and, optional-ly, Id, a dicarboxylic acid dichloride of the formula X
is appropriately reac~ed with a mixture of the diamines of the formulae VI, VII, VIII and, optionally, IX
CIOC-RI-COCI (X), H2N-R2-NH2 (VI), ~ ~ NH2 (VII) 2N ~ r ~ r ~ NH2 ~ H 2 N - R 3- N H 2(IX)~
in which the radicals Rl to R3 as well as X and Y have the meaning defined further above.
The dicarboxylic acid dichloride of the formula X and the individual diamine types can also be used in the form of - 8 - ~ a ~
mixtures.
For this reaction, the proportions of the diamines YI, VII and VIII and, optionally, IX are in each case to be chosen such that polyamides are formed which have the above-defined proportions of structural units of the formulae Ia, Ib, Ic and, optionally, Id.
It is self-evident to a person skilled in the art that the sum o~ all structural units derived from aromatic acids and the sum of all structural units derived from aromatic amines are essentially identical, i.e. that they differ by at most about 1 %, preferably by at most 0.2 ~, and in particular are identical within the framework of the practical measurement and metering possibilities.
The molecular weight of the polyamides formed can be controlled, inter alia, via t~e selection of ~he propor-~ions of aromatic acids to aromatic amines. These selec-tion criteria are known to those skilled in the art in the polycondensation field.
Examples of suitable aromatic dicarboxylic acids from which the dicarboxylic acid dichlorides of the formula X
are derived are naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid acid and in particular terephthalic acid.
~ Up to 10 mol ~ of the dicarboxylic acid dichlorides can -~ also be derived from divalent aromatic meta-radicals.
Examples of acids from which such dicarboxylic acid dichlorides are derived are naphthalene-1,6-dicarboxylic acid, naph~halene-1,7-dicarboxylic acid, naphthalene-~,7-dicarboxylic acid, biphenyl-3,4~-dicarboxylic acid and in particular isophthalic acid.
' .
, .
" ~ ~ J~
Examples of suitable diamines of the formula VI are naphthalene-1,4-diamine, naph~halene-1,5-diami.ne, naph-thalene-2,6-diamine, benzidine and in particular p-phenylenediamine.
5 The diamines of the formula VII (3r4~-diaminodiphenyl ether) and of the formula VIII (1,4-bis-(4-aminophenoxy)-benzene) are known per se.
Examples of suitable diamines of the formula IX are 2-r chloro-1,4-phenylenediamine, 4,4~-diaminobenzanilide and 10 m-phenylenediamine, 3,5'-dimethylbenzidine, 3,5'-di-chlorobenzidine or 3,5~-dimethoxybenzidine.
The copolymeri2ation of the monomer compounds described above is generally carried out as solution polymerization.
: 15 To this end, the aromatic monomer compounds to be reacted with one another are as a rule dissolved in an organic solvent. The organic solvent preferably comprises at ; least one solvent of the amide type, such as, for ex-ample, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 20 tetramethylurea, N-methyl-2-piperidone, N,N'-dimethyl-ethyleneurea, N,N,~',N'-tetramethylmaleimide, N-methyl-caprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N'-dimethylpropionamide, N,N-dimethylisobutylamide, N-methylformamide or N/N~-dimeth-25 ylpropyleneurea. The preferred organic solvents N-methyl-2-pyrrolidone, N,N-dimethylacetamide and a mixture of these compounds are of importance for the process acGord-ing to the invention.
. .
- In a preferred embodiment of the solution polymerization, the aromatic monomer diamines are dissolved in an amide solvent. The solution thus obtained is then mixed with the at least one aromatic monomer compound in the form of an aromatic dicarboxylic acid dihalide, with vigorou6 , ..
2 ~
stirring, in order to initiate the copolymerization.
In this process the amide solvent is used not only as solvent for the aromatic monomer compounds and the aromatic copolyamide obtained therefrom but also as acid acceptor for a hydrogen halide, for example for hydrogen chloride, which is formed as a by-product of the copoly-merization of the aromatic monomer compounds. In some cases it can be advantageous to use an additive which promotes the solubility, for example a metal halide of one of the metals of Group I or II of the Periodic Table, which halide is added to the copolymerization mixture before, during or after the copolymerization.
Examples of such additives are alkali metal halides, such as lithium chloride, or alkaline earth metal hali~es, such as calcium chloride.
The polycondensation temperatures for the solution polymerization are usually between -20C and +120C, preferably between ~10C and +100C. Particularly good results are obtained with reaction temperatures of between +10C and +80~C.
~, ~i The sum of the concentrations of the aroma~ic monomer compounds in the polymerization mixture solution can be adjusted taking into account the desired degree of polymerization, the desired viscosity of the polymeriza-tion mixture, the nature of the aromatic monomer com-pounds used, ~he nature of the solvent used nd the desired polymerization temperature. The most fa~orable ; sum of the concentrations can be determined on th~ basis of a number of preliminary experiments for the course of the polymerization.
Polycondensation reactions are preferably ~arried out in such a way that 2 to 15, preferably 5 to 12, % by weight of polycondensation product are present in the solution .
~ ' :' . , .
; ~ 2 ~ ~ 3 Il~J
after the reaction i5 complete. Particularly good results ; are obtained with concentrations of 5.0 to 8 % by weight.
r~ The molecular weight of the polymer, and thus also the ~- viscosity of the reaction batch, increase in the course ; 5 of the polycondensation reaction.
:;, An adequate molecule chain length is reached if the viscosity of the polymer solution obtained from the polycondensation reaction corresponds to an inherent viscosity of the polymer greater than 3.5, preferably ~` 10 greater than 4.5 and particularly preferably greater than S.0 dl/g, in particular 5.5 to 8.0 dl/g.
` Inherent viscosity is understood to mean the expression ~`
In ~rel " ~, ~7 inh c In this expression, ~rel iS the relative viscosity and c the concentration used, in g/100 ml.
. :, ,;~.
For the purpo es of the present invention, it is deter-mined for solutions of, in each case, 0.25 ~ of polymer in N-methylpyrrolidone at 25C.
;~' '.~
Insofar as it is used to prepare the aromatic polyamides according to the invention which have been described , above, ~he process for the preparation of aromatic polyamides which has been outlined and is known per se is ~' 25 also a ubject of the invention.
Y' If the polymer solution has reached the viscosity re-quired for further processing, the polycondensation reaction can be stopped in the conventional manner by ' adding monofunctional compounds, such as, for exampleJ
acetyl chloride. ~he hydrogen chloride formed, which is :, .
`
bound in salt form to ~he amide solvent, can then be neutralized by adding basic substances.
Substances suita~le for this purpose are, for example, lithium hydroxide and calcium oxide, but in particular calcium hydroxide.
. , The aromatic copolyamide obtained on carrying out the process according to the invention can be separated off from the copolymerization mixture by means of a separa-tion process, for example by precipitation. In order to prepare a solution for shaping the copolyamide, the aromatic copolyamide obtained in this way is then dis-solved in a suitable organic solvent, this process being designated the dissolving process for the preparation of the shaping solution.
., r'15 However, in those cases in which the solution polymeriza-tion process is used to prepare the aromatic copolyamide according to the invention, the copolyamide is completely -dissolved in the solvent for the polymerization, because it is outstandingly soluble in said solvent. Therefore, if the process according to the invention is used indus--~trially it is advantageous to use the mixture obtained from the polymerization immediately as shaping solution for the aromatic copolyamide.
.~ .
The aromatic copolyamide according to the invention is outstandingly soluble in an organic solvent, for example .~in organic solvents of the amide type, and has outstand-ing resistance to heat and superior resistance to chemi-cals. The aromatic copolyamide according to the invention is particularly useful for the production of diverse :~30 shaped articles, for example fibers, films and coatings, which are likewise a subject of the invention.
!Within the framework sf this description the term "fibers" is to be understood in its broadest meaning;
;, :
; thus, the term also covers, for example, filaments or staple fi~ers of any desired denier.
Within the framework of this description, the term "films is likewise to be understood in its broadest meaning; thus, it also covers, for example, embodiments of di~erse thickness, such as sheets or membranes.
The shaped structures not only have outstanding resist-ance to heat and resistance to chemicals but also have superior mechanical properties, for example in respect of the tensile streng~h, the abrasion resistance and the modulus of elasticity. The solution of the aromatic copolyamide can also be used in diverse ways, for example for the production of fibers, ~heets, sheet-like ele-ments, fibrous materials and other shaped articles.
The solvent used in the process for the preparation of ` the shaping solution of the aromatic copolyamide is preferably a solvent of the amide type, in particular the ` solvents of the amide type which have been mentioned further above, or a mixture of two or more of the said ; 20 compounds.
...
For the preparation of the shaping solution it is advant-ageous if the conc~ntration of the aromatic copolyamide is kept within a range between 4 and 15 % by weight, in particular between 5 and 12 % by weiyht. If necessary, the shaping solution can comprise an additi~e to promote the solubility, it being possible to use at least one metal halide of a metal of Groups I and II of the Periodic ~able, for example lithium chloride, calcium chloride or magnesium bromide, specifically in a concen-tration of between 0.2 and 10 %, preferably of between0.5 and 5 ~, with respect to the total weight of the shaping solution. The additive to promote the solubility also promotes the stability of the shaping solution at elevated temperature.
.
- 14 ~ ~
.
Shaping of the shaping solution to give a shaped article can be carried out by any suitable dry process, wet .` process or dry/wet process. In the cases in which a wet process is used in order to shape the shaping solution, for example to give filaments, the shaping solution or -in this case - the spinning solution is extruded through a die, for example a spinneret, into a coagulating liquid. ~ith this procedure it is usually advantageous if ~ the coagulation liquid is composed of water or of an ; 10 aqueous solution containing a polar organic solvent. The ` polar organic solvent can be selected from thie same amide solvents which are cus~omarily used for dissolving the ~ aromatic copolyamide.
,,.,~
The polar organic solvent used in the coagulation liquid is preferably the same solvent as is contained in the ~` shaping solution. The coagulation liquid is preferably used at a tempera~ure between 0C and the boiling point : of the coagulation liquid under atmospheric pressure.
.,, The polar organic solvent is preferably present in the coagulation liquid in a concentration of less than 70 %
; by weight, in particular less than 50 ~ by weight.
.`~ The shaping process explained above is par~icularly;; suitable for the production of films or fibers from a shaping solution.
..;
When producing fibers from the aromatic copolyamide, the shaping or spinning solution is extruded through a spinning head which has multiple spin orifices, the ;. filament-form streams of the ~pinning solution being solidified in one of the coagulation liquids indicated above (wet process) or in an atmosphere promoting evapor-~; ation (dry process). A variant which is also suit~ble is the "dry jiet/wet spinning process", as is described, for example, in US-A-34 14 645. A conventional horiæontal or vertical wet spinning machine, a dry jet wet spinning , ' .
.
~ ~ ' , machine or a spinning machine in which the ma erial flow is downward under stress can be used for spinning.
In the case of wet spinning of an aromatic copolyamide according to the invention, the coagulation is preferably effected using a coagulation liquid containing an addi-tive to promote coagulation, this coagulation being followed by a further coagulation step, in the course of which the coagulating filaments of the aromatic copoly-amide are passed into a water bath which is kept a$ a temperature of between 0 and 100C.
,.~
The additional coagulation step serves to complete the coagulation by removal of the solvent. In addition, additives to promote coagulation, if such substances are used, are washed out of the coagulated filaments.
It is clear from the above description that the aromatic copolyamide according to the invention can be processed to give filaments without any problems, using conven-tional spinning processes and equipment, without a hazardous or harmful solvent, such as, for example, ~- 20 concentrated sulfuric acid, having to be used.
"~
Consequently, the risks for the operating personnel are ~ reduced. In addition, the filaments produced from the ; copolyamide according to the inYention have a dense internal structure.
~..
The shaping solution can also be processed to give a film using conventional fanning or extruding processes.
;~
Fibers or films which are produced by the shaping pro-~ cesses indicated above are usually subjected to a -~ stretching operation, by means of which not only the mechanical properties, such as, for example, the tensile strength and the modulus of elasticity, but also the thermal properties, such as, for example, the stability 16 2~"~
:
to heat, of the filaments or films produced in this way are improved.
Filaments composed of the aromatic copolyamides according to the invention are as a rule stretched in order to obtain a high mechanical strength and a high modulus of elasticity. The stretching ratio is usually about 1:6 to ; 1:20. The stretching temperature is as a rule between 250 and 550C, preferably between 350 and 500C.
~Stretching can be carried out in a single step, in two r~` 10 steps or in several steps and a hotplate or a cylindrical heating device can be used for heating. In addition, the ;stretched filaments or films can be subjected to a , further heat treatment at the same temperature or a higher temperature in order to Lmprove the crystalline structure. In this context it is pointed out that the `~aromatic copolyamide according to the invention is not only surprisingly advantageous with respect to its `solubility in conventional organic solvents but can also : be stretched under "mild" operating conditions without any problems after the production of the fibers or films.
;The fibers obtainable from the copolymers according to ;the invention are distinguished by high tear strengths and initial moduli and by low elongations at break.
:, A further preferred subject of the pre~ent invention comprises fibers composed of the copolymers according to the invention, which have a tear strength of about 90 to 250 cN/tex, in particular 150 to 250 cN/tex, an initial modulus, with respect to 100 ~ elongation, of about 25 ~o 60 N/tex, in particular 35 to 50 N/tex, and an elongation at break of about 3 to 7 ~, in particular 4 to 6 %.
It has been found, surprisingly, that fibers which have high transverse strength values not obtained hitherto for aramides and which have a combination of exceptionally ~,, .
. : , - 17 - 2~
high tear strength and transverse strength can be produced from the copolyamides according to the invention ; by using particular stretching conditions~ The loop ; strength (in accordance with DIN 53843) or the knot strength (in accordance with DIN 53842 Part 1~ can be used as a criterion for the transverse strengths.
Preferred fibers composed of the copolyamides according to the invention have knot strengths of 25 to 80 cN/tex, in particular of 50 to 80 cN/tex, and/or loop ~tren~ths of 40 to 130 cN/tex, in particular of 85 to 120 cN/tex.
.;, .
i Very particularly preferred fibers composed of the copolyamides according to the invention have tear strengths of more than 200 cN/tex, in particular of 200 to 250 cN/tex, and loop s~rengths of more than 80 cN/tex, in particular of 85 to 120 cN/tex.
These particularly preferred fibers are obtainable by ~ stretching the spun fibers at elevated temperature and ;~ using a spin finish preparation which is stable under the stretching conditions. Such preparations essentially ;~ 20 contain a particulate, inert inorganic material which lowers the sliding friction between the fibers during the stretching process. These preparations are usually applied to the fibers from an aqueous suspension and a ;uniform layer of said incrganic mat0rial is ~hen produced around the fibers by drying. Examples of suitable inorganic and inert particles are graphite, talc, colloidal silica, water-repellent silica, mica, hydrated magnesium silicate or aqueous dispersions containing magnesium ~ilicate and an aqueous gel-forming inorganic compound, such as aluminum silicate.
Examples of such preparations are describPd in JP-A-60-239,522, JP-A-60-239,523 and EP-A-121,132.
' ~3~
Stretching of the aramid fibers pretreated in this way is generally carried out at fiber temperatures of higher than 300C, pre~erably at 350 to 550C. The degrees of stretching for the production of these particularly preferred aramide fibers are usually 1:8 to 1:20, prefer-ably 1:9 to 1:15.
The invention also relates to such fibers and a process for their production.
The fibers composed of an aromatic copolyamide according to the invention, which have outstanding m~chanical and ; thermal properties and are distinguished by a high stretchability, can be used industrially in very diverse ways, for example for reinforcing plastics, in particular as reinforcing materials for the fabric inserts in car tires and other rubber articles, as heat-resistant insulating materials, for the production of filter fabrics and as lightweight insulating materials. Films composed of an aromatic copolyamide according to the invention can be used as heat-resistant electrical insulating materials, in particular for ~he production of membranes, for example as support material for separation membranes.
Further features and advantages of the inven~ion are explained in more detail below with the aid of examples.
Howev~r, it is to be understood that the invention is not restricted to the illustrative examples. On the contrary, numerous possibilities for modifications and/or supple-ments are available to a person skilled in the art, taking the illustrative examples as a basis, without having to go beyond the basic concept of the invention.
-19~ 2~3~
Example 1 "
Aromatic copolyamide obtained from 100 mol % of tereph-thalic acid dichloride, 50 mol ~ of p-phenylenediamine, 25 mol % of 1,4-bis-(4-aminophenoxy)-benzene and 25 mol %
~;.5 of 3,4'-diaminodiphenyl ether.
;, 162.2 g (1.5 mol) of p-phenylenediamine, lS0.2 g (O.75 mol) of 3,4~-diaminodiphenyl ether and 219.3 g (O.75 mol) of 1,4-bis-(4-aminophenoxy)-benzene are .dissolved, under nitrogen, in 14042 g of N-methylpyr-rolidone and 607.3 g (3 mols) of terephthalic acid dichloride are added in the course of 20 minutes at between 35C and 55C. When ~he desired viscosity (~
= 5.5 dl/g) is obtained, the polycondensation reaction is stopped by adding 4.7 g of acetyl chloride and the ;~15 reaction mixture is then neutralized with 328.2 g of calcium oxide (55 % strength suspension in NMP). The solution is stirred further at 120C. Th~ solution is filtered, degassed and spun wet. To this end, it is spun at a rate of 16 m/min from a die which has 100 orifices each 0.1 mm in diameter into a coagulation bath compris-ing a 35 % solution of N-methylpyrrolidone in water, .;which is at 80C. The resulting filaments are stretched to 11 times their length through two water baths, a washing machine, via a drying godet and finally over a hot plate at temperatures of 400 to 440C.
. . .
The filament linear density is 1.91 dtex for a tear strength of 190 cN/tex, an elongation of 4 ~ and an initial modulus of 41 N/tex, with respect to 100 % elongation.
Examples 2 to 37 Further aromatic copolyamides are produced, spun and tested in accordance with the procedure described in Example 1. The diamines used, the proportions thereof, the solution viscosities of the resulting polymers, the .
- 20 ~
spinning conditions and properties of the resulting fibers are given in Table 1 ~elow. The following abbrevi-ations are used for the monomers in Table 1:
TPC = terephthalic acid dichloride IPC = isophthalic acid dichloride :`NDC = 2,6-naphthalenedicarboxylic acid dichloride PPD = p-phenylenediamine 3,4'-DADPE = 3,4'-diaminodiphenyl ether BAPOB = 1,4-bis-(4-aminophenoxy)-benzene ~,~10 4, 4 ' -DABA = 4,4'-diaminobenzanilide . Cl-PPD = chloro-para-phenylenediamine MPD = m-phenylenediamine DM~ = 3,5'-dLmethylbenzidine .; .
. .
:' :
.~.
.:~
. ~ .....
: , ~ - 21 ~
.' ~ . . ,..................... _...... .. I
Example No. 2 3 4 5 6 7 ¦ 8 9 . TPC (mol %) 100 100 100 100 100 100 100 100.~ S
IPC (mol %) 0 0 0 0 0 0 0 0 NDC (mol %) 0 0 0 . 0 0 0 0 0 ~' _ _ _ : 10 PPD (mol ~) 55 50 50 50 50 50 50 50 3,4'-DADPE (mol ~) 22.5 20 40 30 20 30 20 25 _ _ BAPOB (mol %) 22.5 30 10 20 20 10 20 25 .
4,4'-DABA (mol %) O O O O O O 10 O
Cl-PPD (mol %) 0 0 0 0 10 10 0 0 Spinning solution 6 6 6 6 6 6 6 6 concentratlon ( % ~ _ Inherent viscosity 6.2 6.5 6.3 4.6 6.5 5.8 6.0 5.9 (dl/g) in NMP
0.25 % strength at 25~C
.
~ Strength (cN/tex) 143 134 184 160 124 170 163 190 , _ . _ _ 30 Elongation (%) 3.4 3.8 3.5 3.4 3~0 3.3 3.7 4.0 . __ ~ . , . _ _ . Modulus (N/tex) 41 34 50 44 41 52 41 41 _ _ ._ Stretching 1: 8 9 10 15 14 10 14 14 3~ _ _ ~ _ _ _ _ _ _ _ 22 2 ~
. _ _ _ _ 10 11 12 13 ~4 15 16 l7 ':. _ _ TPC (mol %) 100 100100 100 100 100 100 100 "~ 5 _ IPC (mol %) 0 0 0 0 0 0 0 0 : NDC (mol %) 0 0 0 0 0 0 0 0 PPD (mol %) 50 60 50 50 45 40 45 45 3,4'-DADPE (mol %) 17.5 10 45 35 40 50 45 50 B~POB (mol %~ 17.5 30 5 15 15 10 10 _ 4,4'-DABA (mol %) 15 O 0 0 0 0 0 O
Cl-PPD (mol %) 0 0 0 0 0 0 0 0 : 20 Spinning solution 6 6 10 8 10 10 6 12 concentration (~) _ Inherent viscosity 6.4 6.1 4.5 4.6 3.6 3.8 6.1 6.3 . (dl/g) in NMP
at 25C
,''~ .
Strength (cN/tex) 16498 203 197 la3 lB4 165 17 ;~ 30 Elongation (%) 3.3 4.33.8 3.7 3.5 3.5 3.4 3.
_ _ . . .. _ _ . Modulus (N/~ex)45 27 52 48 52 50 4B 55 .: Stretching 1: 7 4 14 12 11 18 9 13 :, 35 ~ ~ _ ~ _ _ _ ~ _ :
.
.
,' ' ~
; - 23 - 2~
. ~ le Ro. 19 19 20 21 22 23 2425 _ TPC (mol %) I00 B0 85 85 80 80 75100 IPC (mol %) 0 20 15 15 10 10 10 0 NDC (mol %) 0 0 0 0 10 10 15 0 PPD (mol %) 50 60 60 60 60 65 6040 3, 4 ' -DADPE (mol % ~22 . 5 10 10 15 15 10 1055 . . _ _ _ BAPOB (mol %~ 22.5 30 30 25 25 25 30 5 . _ _ 4, 4 ' -DABA (mol % ) 5 0 0 0 0 0 0 O
Cl-PPD (mol % ) 0 0 0 __ 0 0 0 Spinning solution 6 6 6 6 8 6 6 12 concentration (%) _ _ _ Inherent viscosity 7 . 0 6 .1 6 .1 5.6 5.4 5.8 6 .1 6 . 3 (dl/g) in NMP
0.25 % strength at 25C _ _ _ _ Strength (cN/tex) 169 99 94 94 96 94 95 182 Elong~tion (%) 3.8 4.8 4.3 4.2 3.9 3.B 4.3 3.~
. . _ . _ Modulus (N~tex) 40 24 27 29 30 29 27 55 ~ c~lr~ 1~ 15 5 4.5 4.5 4 6 5.3 4 2 l8 3 1 ~ ~
~ - 24 -_ __ , . ___ , . _ , , _ Example No. 26 27 28 29 30 31 32 3~
_ _ _ TPC (mol ~) 100 100100 100 100 100 100 100 _ _ IPC ~mol %) 0 0 0 0 0 0 0 0 ._ . ........ ~ _ _ .
. NDC (mol %) 0 0 0 0 0 0 0 0 _ _ _ PPD (mol %) 50 50 45 45 45 50 45 45 3,4'-DADPE (mol %) 35 35 50 35 30 30 30 30 .' . . .
BAPOB (mol %) 15 15 5 15 15 10 10 5 _ 4,4'-DABA (mol %) 0 0 0 0 0 0 0 O
. _ MPD (mol %) O O O 5 10 10 15 20 . . _ _ Spinning solution 6 8 10 6 6 6 6 6 concentration (%) : . _ _ : Inherent viscosity 6.8 5.01 4 5 . 4 4.8 4.5 5 5.1 (dl/g) in NMP
. _ _ Strength (cN/tex) 248 223 203 210 188 202 160 170 _ _ ~ Elongation (%) S 4.4 3.8 5 5.4 5.6 5 5.2 . _ __ ~ 30 Modulus (N/tex) 50 48 52 42 36 38 35 36 .
; Stretching 1: 12 ~ 1 D 9 5 8 7 10 10 Loop strength 114 85 87 84 42 (cN/tex) ~not strength 69 59 53 63 27 (cN/tex) l _ ~ _ _ _ 2 ~
__ ........ _ . . ..
~; Example No. 34 35 36 37 ~ ... _ TPC (mol %) 100 100 100 100 IPC (mol %) 0 0 0 0 NDC ~mol %) 0 0 0 0 . _ PPD (mol %) 45 35 40 45 3,4'-DADPE (mol %)30 30 25 25 _ .
.~ BAPOB (mol %) 10 10 5 5 4,4'-DABA (mol %) 0 5 5 0 , _ ._ . .__ .~ MPD (mol %) O S O
DMB (mol %) 20 20 20 25 .' .
. Spinning solution 6 6 6 6 concentration (%) .
Inherent viscosity 6.32 6.10 6.30 6.33 (dl/g) in NMP
, .
Strength IcN/tex)189 174 198 146 _ -................ _ Elongation (%) 3.5 3.2 3.6 2.5 .
: Modulus (N/tex) 59 60 b0 67 .
Stretching 1: 7 11 10 7 _ __ __ __ __ __ _____________________________
Cl-PPD (mol %) 0 0 0 0 10 10 0 0 Spinning solution 6 6 6 6 6 6 6 6 concentratlon ( % ~ _ Inherent viscosity 6.2 6.5 6.3 4.6 6.5 5.8 6.0 5.9 (dl/g) in NMP
0.25 % strength at 25~C
.
~ Strength (cN/tex) 143 134 184 160 124 170 163 190 , _ . _ _ 30 Elongation (%) 3.4 3.8 3.5 3.4 3~0 3.3 3.7 4.0 . __ ~ . , . _ _ . Modulus (N/tex) 41 34 50 44 41 52 41 41 _ _ ._ Stretching 1: 8 9 10 15 14 10 14 14 3~ _ _ ~ _ _ _ _ _ _ _ 22 2 ~
. _ _ _ _ 10 11 12 13 ~4 15 16 l7 ':. _ _ TPC (mol %) 100 100100 100 100 100 100 100 "~ 5 _ IPC (mol %) 0 0 0 0 0 0 0 0 : NDC (mol %) 0 0 0 0 0 0 0 0 PPD (mol %) 50 60 50 50 45 40 45 45 3,4'-DADPE (mol %) 17.5 10 45 35 40 50 45 50 B~POB (mol %~ 17.5 30 5 15 15 10 10 _ 4,4'-DABA (mol %) 15 O 0 0 0 0 0 O
Cl-PPD (mol %) 0 0 0 0 0 0 0 0 : 20 Spinning solution 6 6 10 8 10 10 6 12 concentration (~) _ Inherent viscosity 6.4 6.1 4.5 4.6 3.6 3.8 6.1 6.3 . (dl/g) in NMP
at 25C
,''~ .
Strength (cN/tex) 16498 203 197 la3 lB4 165 17 ;~ 30 Elongation (%) 3.3 4.33.8 3.7 3.5 3.5 3.4 3.
_ _ . . .. _ _ . Modulus (N/~ex)45 27 52 48 52 50 4B 55 .: Stretching 1: 7 4 14 12 11 18 9 13 :, 35 ~ ~ _ ~ _ _ _ ~ _ :
.
.
,' ' ~
; - 23 - 2~
. ~ le Ro. 19 19 20 21 22 23 2425 _ TPC (mol %) I00 B0 85 85 80 80 75100 IPC (mol %) 0 20 15 15 10 10 10 0 NDC (mol %) 0 0 0 0 10 10 15 0 PPD (mol %) 50 60 60 60 60 65 6040 3, 4 ' -DADPE (mol % ~22 . 5 10 10 15 15 10 1055 . . _ _ _ BAPOB (mol %~ 22.5 30 30 25 25 25 30 5 . _ _ 4, 4 ' -DABA (mol % ) 5 0 0 0 0 0 0 O
Cl-PPD (mol % ) 0 0 0 __ 0 0 0 Spinning solution 6 6 6 6 8 6 6 12 concentration (%) _ _ _ Inherent viscosity 7 . 0 6 .1 6 .1 5.6 5.4 5.8 6 .1 6 . 3 (dl/g) in NMP
0.25 % strength at 25C _ _ _ _ Strength (cN/tex) 169 99 94 94 96 94 95 182 Elong~tion (%) 3.8 4.8 4.3 4.2 3.9 3.B 4.3 3.~
. . _ . _ Modulus (N~tex) 40 24 27 29 30 29 27 55 ~ c~lr~ 1~ 15 5 4.5 4.5 4 6 5.3 4 2 l8 3 1 ~ ~
~ - 24 -_ __ , . ___ , . _ , , _ Example No. 26 27 28 29 30 31 32 3~
_ _ _ TPC (mol ~) 100 100100 100 100 100 100 100 _ _ IPC ~mol %) 0 0 0 0 0 0 0 0 ._ . ........ ~ _ _ .
. NDC (mol %) 0 0 0 0 0 0 0 0 _ _ _ PPD (mol %) 50 50 45 45 45 50 45 45 3,4'-DADPE (mol %) 35 35 50 35 30 30 30 30 .' . . .
BAPOB (mol %) 15 15 5 15 15 10 10 5 _ 4,4'-DABA (mol %) 0 0 0 0 0 0 0 O
. _ MPD (mol %) O O O 5 10 10 15 20 . . _ _ Spinning solution 6 8 10 6 6 6 6 6 concentration (%) : . _ _ : Inherent viscosity 6.8 5.01 4 5 . 4 4.8 4.5 5 5.1 (dl/g) in NMP
. _ _ Strength (cN/tex) 248 223 203 210 188 202 160 170 _ _ ~ Elongation (%) S 4.4 3.8 5 5.4 5.6 5 5.2 . _ __ ~ 30 Modulus (N/tex) 50 48 52 42 36 38 35 36 .
; Stretching 1: 12 ~ 1 D 9 5 8 7 10 10 Loop strength 114 85 87 84 42 (cN/tex) ~not strength 69 59 53 63 27 (cN/tex) l _ ~ _ _ _ 2 ~
__ ........ _ . . ..
~; Example No. 34 35 36 37 ~ ... _ TPC (mol %) 100 100 100 100 IPC (mol %) 0 0 0 0 NDC ~mol %) 0 0 0 0 . _ PPD (mol %) 45 35 40 45 3,4'-DADPE (mol %)30 30 25 25 _ .
.~ BAPOB (mol %) 10 10 5 5 4,4'-DABA (mol %) 0 5 5 0 , _ ._ . .__ .~ MPD (mol %) O S O
DMB (mol %) 20 20 20 25 .' .
. Spinning solution 6 6 6 6 concentration (%) .
Inherent viscosity 6.32 6.10 6.30 6.33 (dl/g) in NMP
, .
Strength IcN/tex)189 174 198 146 _ -................ _ Elongation (%) 3.5 3.2 3.6 2.5 .
: Modulus (N/tex) 59 60 b0 67 .
Stretching 1: 7 11 10 7 _ __ __ __ __ __ _____________________________
Claims (14)
1. An aromatic copolyamide which is soluble in organic polyamide solvents and has an inherent viscosity of at least 3.5 dl/g, in particular 4.5 dl/g, measured at 25°C in solutions of 0.25 % by weight of copolymer in N-methylpyrrolidone, containing the recurring structural units of the formu-lae Ia, Ib, Ic and optionally Id [ -OC-R1-CO-NH-R2-NH- ] (Ia), (Ib), (Ic), [ -OC-R1-CO-NH-R3-NH- ] (Id) in which at least 80 mol % of all radicals R1, with respect to the amount of these radicals in the copolymer, are an unsubstituted divalent aromatic radical, the valency bonds of which are in the para-position or in a comparable coaxial or parallel position with respect to one another, and up to 20 mol % of all radicals R1, with respect to the amount of these radicals in the copolymer, are an unsubstituted divalent aromatic radical, the valency bonds of which are in the meta-position or in a comparable angled position with respect to one another, R2 is an unsubstituted divalent aromatic radical, the valency bonds of which are in the para-position or in a comparable coaxial or parallel position with respect to one another, X is a group of the formula -S-, -SO2-, -CO- or, -O-, Y assumes one of the definitions given for X, and R3 is a radical which differs from R2 and is of the formula II and/or of the formula III and/or of the formula IV and/or of the formula V
(II), (III), (IV), (V), in which Hal is a halogen atom and R4 is C1-C6-alkyl, C1-C6-alkoxy and/or halogen, and the proportion of recurring structural units Ia, Ib, Ic and Id, with respect to the sum of these structural units in the copolymer, is within the following limits:
recurring structural unit of the formula Ia: 40 to 65 mol %;
recurring structural unit of the formula Ib: 5 to 55 mol %;
recurring structural unit of the formula Ic: 5 to 35 mol %; and recurring structural unit of the formula Id: 0 to 30 mol %.
(II), (III), (IV), (V), in which Hal is a halogen atom and R4 is C1-C6-alkyl, C1-C6-alkoxy and/or halogen, and the proportion of recurring structural units Ia, Ib, Ic and Id, with respect to the sum of these structural units in the copolymer, is within the following limits:
recurring structural unit of the formula Ia: 40 to 65 mol %;
recurring structural unit of the formula Ib: 5 to 55 mol %;
recurring structural unit of the formula Ic: 5 to 35 mol %; and recurring structural unit of the formula Id: 0 to 30 mol %.
2. The aromatic copolyamide as claimed in claim 1, wherein X and Y are -O-.
3. The aromatic copolyamide as claimad in claim 1, wherein at least 90 mol % of all radicals R1, preferably 100 mol % of the radicals R1, with respect to the amount of these radicals, are 1,4-phenylene and up to 10 mol % of all radicals R1, with respect to the amount of these radicals, are 1,3-phenylene.
4. The aromatic copolyamide as claimed in claim 1, wherein R2 is 1,4-phenylene.
5. The aromatic copolyamide as claimed in claim 1, wherein at least 90 mol % of all radicals R1, preferably 100 mol % of the radicals R1, with respect to the amount of these radicals, are 1,4-phenylene and the proportion of recurring structural units Ia, Ib, Ic and Id, with respect to the sum of these structural units, is within the following limits:
recurring structural unit of the formula Ia: 45 to 55 mol %;
recurring structural unit of the formula Ib: 35 to 45 mol %;
recurring structural unit of the formula Ic: 5 to 25 mol %; and recurring structural unit of the formula Id: 0 or 5 to 20 mol %.
recurring structural unit of the formula Ia: 45 to 55 mol %;
recurring structural unit of the formula Ib: 35 to 45 mol %;
recurring structural unit of the formula Ic: 5 to 25 mol %; and recurring structural unit of the formula Id: 0 or 5 to 20 mol %.
6. The aromatic copolyamide as claimed in claim 1, wherein R3 is a radical of the formula IV and wherein the proportion of the recurring structural unit of the formula Id is 5 to 15 mol %, very particularly preferably 5 to 10 mol %, with respect to the sum of the structural units Ia, Ib, Ic and Id.
7. A process for the preparation of the copolyamide as claimed in claim 1, wherein a dicarboxylic acid dichloride of the formula X is reacted with a mixture of the diamines of the formulae VI, VII, VIII and, optionally, IX
ClOC-R1-COCl (X), H2N-R2-NH2 (VI), (VII), (VIII), H2N-R3-NH2 (IX), in which the radicals R1 to R3 as well as X and Y
have the meaning defined in claim 1 and wherein the molar proportions of the diamines of the formulae VI
to IX, with respect to the sum of the proportions of these diamines, are selected within limits such that a copolyamide having the proportions of recurring structural units of the formulae Ia, Ib, Ic and Id defined in claim 1 is formed.
ClOC-R1-COCl (X), H2N-R2-NH2 (VI), (VII), (VIII), H2N-R3-NH2 (IX), in which the radicals R1 to R3 as well as X and Y
have the meaning defined in claim 1 and wherein the molar proportions of the diamines of the formulae VI
to IX, with respect to the sum of the proportions of these diamines, are selected within limits such that a copolyamide having the proportions of recurring structural units of the formulae Ia, Ib, Ic and Id defined in claim 1 is formed.
8. A shaped structure composed of an aromatic copolyamide as claimed in claim 1.
9. The shaped structure as claimed in claim 8, which is a fiber, film or coating.
10. The shaped structure as claimed in claim 8, which is a fiber which has a tear strength of about 90 to 250 cN/tex, an initial modulus, with respect to 100 % elongation, of about 25 to 60 N/tex and an elongation at break of 3 to 7 %.
11. The shaped structure as claimed in claim 8, which is a fiber which has a tear strength of more than 200 cN/tex, in particular of 200 to 250 cN/tex, and a loop strength of more than 80 cN/tex, in particular of 85 to 120 cN/tex.
12. A process for the production of fibers as claimed in claim 11, comprising the measures:
i) production of fibers composed of an aromatic copolyamide as claimed in claim 1, ii) application of an aqueous suspension of a preparation which is stable under the stretching conditions and which essentially comprises a particulate, inert inorganic material which lowers the sliding friction between the fibers during the stretching operation, iii) drying of the fibers pretreated in this way, so that a layer of said inorganic material forms around the fibers, and iv) stretching the fibers pretreated in this way at temperatures of higher than 300°C, in particular 350 to 550°C.
i) production of fibers composed of an aromatic copolyamide as claimed in claim 1, ii) application of an aqueous suspension of a preparation which is stable under the stretching conditions and which essentially comprises a particulate, inert inorganic material which lowers the sliding friction between the fibers during the stretching operation, iii) drying of the fibers pretreated in this way, so that a layer of said inorganic material forms around the fibers, and iv) stretching the fibers pretreated in this way at temperatures of higher than 300°C, in particular 350 to 550°C.
13. The use of fibers composed of an aromatic copolyamide as claimed in claim 1 to reinforce plastics, in particular to reinforce elastomers.
14. The use of a film composed of an aromatic copolyamide as claimed in claim 1 for the production of membranes.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4202165.0 | 1992-01-27 | ||
| DE4202165A DE4202165A1 (en) | 1992-01-27 | 1992-01-27 | Aramid copolymer with high tensile strength, modulus and elongation - useful for moulding, coating, film e.g. for membrane or fibre, e.g. for reinforcing elastomer |
| DE19924228619 DE4228619A1 (en) | 1992-08-28 | 1992-08-28 | Aromatic co-polyamide(s), esp. for high-performance fibres prodn. |
| DEP4228619.0 | 1992-08-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2088115A1 true CA2088115A1 (en) | 1993-07-28 |
Family
ID=25911270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002088115A Abandoned CA2088115A1 (en) | 1992-01-27 | 1993-01-26 | Aromatic copolyamides, processes for their preparation and structures formed therefrom |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0553755B1 (en) |
| JP (1) | JPH05339369A (en) |
| AT (1) | ATE180806T1 (en) |
| AU (1) | AU654611B2 (en) |
| BR (1) | BR9300290A (en) |
| CA (1) | CA2088115A1 (en) |
| CZ (1) | CZ383792A3 (en) |
| DE (1) | DE59309617D1 (en) |
| ES (1) | ES2134222T3 (en) |
| MX (1) | MX9300408A (en) |
| SK (1) | SK383792A3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4334004A1 (en) * | 1993-10-06 | 1995-04-13 | Hoechst Ag | Aramid fibers of high strength and high titer, process for their production and their use |
| JP4563926B2 (en) * | 2005-12-01 | 2010-10-20 | 帝人テクノプロダクツ株式会社 | Aromatic copolyamide fiber |
| JP4563925B2 (en) * | 2005-12-01 | 2010-10-20 | 帝人テクノプロダクツ株式会社 | Method for producing aromatic copolyamide fiber |
| WO2014098330A1 (en) * | 2012-12-21 | 2014-06-26 | 제일모직 주식회사 | Copolymerized polyamide resin, method for manufacturing same, and molding comprising same |
| JP6356463B2 (en) * | 2014-04-01 | 2018-07-11 | 帝人株式会社 | Totally aromatic polyamide fiber |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4525384A (en) * | 1983-03-07 | 1985-06-25 | Teijin Limited | Process for producing wholly aromatic polyamide filaments heat-treated under tension |
| EP0199090B1 (en) * | 1985-03-23 | 1990-10-03 | Hoechst Aktiengesellschaft | Shaped articles of aromatic copolyamides, and process for their manufacture |
| JPH03234731A (en) * | 1990-02-09 | 1991-10-18 | Teijin Ltd | Wholly aromatic polyamide and its molding |
| ATE140708T1 (en) * | 1991-02-14 | 1996-08-15 | Hoechst Ag | AROMATIC COPOLYAMIDES, METHOD FOR THE PRODUCTION THEREOF AND STRUCTURES FORMED THEREFROM |
-
1992
- 1992-12-22 CZ CS923837A patent/CZ383792A3/en unknown
- 1992-12-22 SK SK3837-92A patent/SK383792A3/en unknown
-
1993
- 1993-01-25 AU AU31995/93A patent/AU654611B2/en not_active Ceased
- 1993-01-26 BR BR9300290A patent/BR9300290A/en not_active Application Discontinuation
- 1993-01-26 EP EP93101114A patent/EP0553755B1/en not_active Expired - Lifetime
- 1993-01-26 DE DE59309617T patent/DE59309617D1/en not_active Expired - Fee Related
- 1993-01-26 AT AT93101114T patent/ATE180806T1/en not_active IP Right Cessation
- 1993-01-26 MX MX9300408A patent/MX9300408A/en unknown
- 1993-01-26 CA CA002088115A patent/CA2088115A1/en not_active Abandoned
- 1993-01-26 ES ES93101114T patent/ES2134222T3/en not_active Expired - Lifetime
- 1993-01-27 JP JP5011627A patent/JPH05339369A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0553755B1 (en) | 1999-06-02 |
| ES2134222T3 (en) | 1999-10-01 |
| EP0553755A2 (en) | 1993-08-04 |
| DE59309617D1 (en) | 1999-07-08 |
| AU654611B2 (en) | 1994-11-10 |
| AU3199593A (en) | 1993-07-29 |
| EP0553755A3 (en) | 1994-04-13 |
| MX9300408A (en) | 1993-07-01 |
| JPH05339369A (en) | 1993-12-21 |
| BR9300290A (en) | 1993-08-03 |
| SK383792A3 (en) | 1995-02-08 |
| ATE180806T1 (en) | 1999-06-15 |
| CZ383792A3 (en) | 1993-08-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |