DE1669518B2 - CRYSTALLINE, ORIENTED THREAD MADE OF A POLYAMIDE OF HIGH MOLECULAR WEIGHT AND A PROCESS FOR MANUFACTURING THE SAME - Google Patents

Description

NC- (CH ₂ ^ -C-

in the m the number of carbon atoms in the molecule of the dicarboxylic acid

HOOC - (CH ₂ ) "- COOH

and S is the trans ^ rans stereoisomeric content of the Bis (p-aminocyclohexyl) methane in percent means stretched to a total of at least 3.5 times, wherein the stretching in the second process stage is at least 1.05 times he follows.

The invention relates to a crystalline, oriented thread made of a polyamide of high molecular weight, at least 90 percent by weight of repeating structural units of the general formula

HO

-N— HC- H ^X -NC- (CH ₂ ) "- C-

in which η is an integer from 9 to 14, 65 being 10 percent by weight from other recurring

at least 70 percent by weight of the diaminocompo structural units.

nent of the recurring units in the stereoiso-

mers trans, trans-configuration are present, and up to see patent 668,704, such threads are made of one

Dodecanedioic acid having a molecular weight of at least 8000 are known in which the diamine component contains at least 70 ° / ₀ of the trans, trans-stereoisomers, and having a birefringence of at least 0.025 polyamide of bis (p-aminocyclorie \ yl) methane and .

The drawing of these threads for the purpose of orientation and increasing the strength takes place in the same way as for polyamide threads usual way.

It has now been found that, under certain working conditions, it is possible to use those mentioned at the beginning To give polyamide threads a new crystal structure, thanks to which they have a particularly high strength, have a particularly high initial modulus and a particularly low shrinkage capacity, so that they are particularly suitable for the production of tire cord.

According to the invention this technically advanced features having polyamide filaments of the aforementioned composition are characterized in that the polyamide chains of up to 86 ° / ₀ of its theoretical, fully extended length is at least stretched and the thread a crystal spacing in the transverse direction from 4.3 to 4.7 Å , determined from the strongest equator reflections in the Bragg X-ray diffraction diagram.

According to a preferred embodiment of the invention, the thread is characterized in that it consists of at least 70 percent by weight of recurring structural units of the general formula I, in which π has a value in the specified range, and up to 30 percent by weight of mixed polyamide components of the general formula I, in which η has a different value in the specified range. According to another embodiment of the invention, the thread consists of a polyamide composed of recurring structural units of the general formula I in which η is only a single value in the specified

ίο range, preferably the value 10.

Threads of the type mentioned, which are characterized by particularly high strength and a particularly low shrinkage capacity with a high initial modulus, are characterized in that the polyamide chains up to at least 98 °; _O are stretched to their theoretical, fully extended length.

The theoretical, fully extended length can easily be found from Stuart and Brieglet models Technically easy to understand working methods

determine oo (see "International Tables For X-ray Crystallography", Vol. Ill, especially p. 276, Kynoch Press, Birmingham, England [1962]).

The method of manufacturing which is characterized by the above parameters and mechanical properties Characteristic polyamide threads according to the invention are characterized in that threads are made from a polyamide, at least 90 percent by weight of repeating structural units of the general formula

HO

N - H - C - H - N - C - (CH ₂ ) 1 - C - H

in which η denotes an integer from 9 to 14, with at least 70 percent by weight of the diamine component of the recurring units being present in the stereoisomeric trans, trans configuration, and up to 10 percent by weight consisting of other recurring structural units, in a first stage at a lower temperature and in a second stage at a temperature greater than

290 + 5- 15 w - 20 (-I) - -C,

in the m the number of carbon atoms in the molecule of the dicarboxylic acid

HOOC - (CH,) "- COOH

and 5 the trans ^ rans stereoisomeric content of bis (p-aminocyclohexyl) methane in percent means stretched to a total of at least 3.5 times, with the stretching in the second process stage at least 1.05 times.

In the following description, for the sake of brevity, bis (p-aminocyclohexyl) methane is used as "PACM", the trans, trans isomer content with "tt" and the dicarboxylic acid involved in polyamide formation with the number of their carbon atoms, so that "PACM-12" is a polyamide made from PACM and dodecanedioic acid means.

It has been found that each of the homopolyamides of the general formula (I) up to 30% PACM-II bis -16 as mixed polyamide components »tolerates * without significantly impairing the desired properties will. Such compatibility does not occur with nylon-66 mixed polyamides. Must be here rather, the repeating units must be exactly the same (e.g. oo / oT mixed polyamide, where T Terephthalic acid means) so that isomorphism can occur.

Except for the PACM-III-bis mentioned above -16 mixed polyamide units should contain the mixed polyamide components whether the foreign constituent replaces the amine, the acid, or both, preferably be limited to about 10 percent by weight (calculated as the weight per 100 g of polyamide of

PACM-X, Y -

or Z,

where X refers to the acid residue in the foreign ingredient, Y refers to the amine residue, and Z refers to refer to an amino acid component).

Diamines, which are suitable as radical Y in the foreign constituents for copolymerization with (I), are diprimary or disecondary diamines, especially the aliphatic A.cj diamines with 2 and preferably 6 to 14 carbon atoms, such as hexamethylenediamine, 2-methylhexamethylenediamine, tetramethylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, di (aminopentyl) ether and di (aminopentyl) sulfide. Usable cyclic diamines are, for example, piperazine, substituted piperazines, such as Dimethylpiperazine, m- or p-xylylenediamine, 4,6-dimethylxylylenediamine, p-phenylenediamine ^ ö-dimethylp-phenylenediamine, 4,4'-diaminodicyclohexylpropane-2,

5 6

1,4-Diaminometh> lcyclohexane, 1,4-Dianiino-2,3-di- have been stretched, an X-ray diffraction pattern, methylcydohexane, 1,4-cyclohexanediamine and bis- in which the strongest equatorial reflection is a Bragg- (2-sulfo- 4-aminocyclohexyl) methane. Dicarboxylic acids, "d" value of about 4.3 to 4.7 Å, and which, as PACM-X components for the mixed poly- also have other characteristic differences that are suitable for merization with (!), Are aliphatic v > Dicar- 5 the presence of a new and different type of carboxylic acid with 2 to 16 carbon atoms; Show aromatic polymorphs, which are referred to here as "HT" -crystalline dicarboxylic acids, such as terephthalic acid, isophthalic form. Filaments according to the invention of acid, sulfonated isophthalic acid, p-phenylenediacid-high strength produce an X-ray diffraction diacid, bibenzoic acid, 2-methylterephthalic acid and grams, which is represented by a 1,4-cyclohexanedicarboxylic acid in two blackening spots; 5,5'-Thiodivalerian- io separate Bragg "cal meridional reflection labeled acid; 5,5'-oxydivaleric acid; di- (4-carboxycyclo- net is. The distance between these blackening hexyl); 3ir .- (4-c.irbox> cyclche \ yl) -methane and bis-spots increases with increasing thread orientation O-methyl ^ -carboxycyclohexyD-methane.Typical ami- in the more stretched threads of higher strength acids (or the corresponding lactams, if they are increased. Which exist due to these meridional spots in the X-ray ) The crystal structure marked with (1) as Z components for the mixed polymerisation diagram are, for example, λ, «- amino acids with is typical but not essential for the» high-voltage 2 to 12 carbon atoms between the nitrogen «- or» HT «crystal form, which is so called, and the carbonyl carbon atom; typical intermediate because they are prescribed by heating the threads to a pyrrolidone, 6-aminohexanoic acid, i-Cabene temperature under such high tension arises, prolactam, 11-aminoundecanoic acid and 12-amino-20 that a permanent elongation takes place. With even height dodecanoic acid. The meridional amino acids, such as 4-piperidinecarboxylic acid, m- or spots, also merge cyclic and / or more aromatic degrees of orientation and reappear as a stripe (in the p-aminobenzoic acid, ^ -aminocyclohe.xanacetic acid length stretched spot), and it forms a new crystal form known as and 4'-amino-4-bisphenylcarboxylic acid, 4-amino- >> EC "crystal.
4'-carboxy (dicyclohexyl) methane; 4-aminocyclo- 25 The best known polyamides polyhexahexanoic acid or 3-aminocyclohexanoic acid, methyleneadipamide, polyhexamethylene sebacin can be used. acid amide and polycaprolactam (nylon 66, 610 and 6)

In the polyamide chain, mixed polyamide units can have a crystal structure with a constant th contain the divalent organic radicals "c" -axis distance, which corresponds to the number of carbon with Have 4 to 20 carbon atoms, which 30 atoms in the repeating structural unit of the is directly proportional via amino and / or carbonyl radicals as an integrating polyamide chain. In contrast Components inserted into the linear polyamide chain are among these and most other polyamides are. Among divalent organic radicals are the PACM-Ll to -16 polyamides of the "c" axis to understand that the distance about carbon is shorter than that from the Stuart and Brieglet amino or carbonyl residues are bound and calculated beforehand. For example, this is predominantly Represent hydrocarbon residues, but by an average increase in chain length in the case of the added heteroatoms, like oxygen or sulfur, in which add two CH., - units to the acid not like Chain can be interrupted and / or would be expected by 2.54 Å, but only 1.96 Å, from which Groups such as the sulfonate, sulfate, phosphate, phosphate, it is concluded that the chains in the "c" -axis phinate, Hydroxyl or acyl group, its substituted 40 direction are not fully stretched. About that can. Preferably, the inventive also changes in the inventive threads Threads made from a homopolyamide; possibly preceded with »HT« crystal form the »c« -axis distance with the existing mixed polyamide components are preferably the degree of orientation of the thread in such a way that with organic hydrocarbon residues. increasing orientation this crystal dimension

If threads from the reaction product of PACM 45 also increase, which gives these polyamides a unique

and aliphatic dicarboxylic acids with 11 to 16 cohorts.

The HT crystal form is formed when the

nissen are stretched, they result in an X-ray polyamide chains in the crystal up to at least

radiation diffraction pattern that is stretched at the equator by about 86 ° / _{0 of} its theoretical length

single diffuse aura is characterized, giving a 50 (i.e. elongated). When the chains are on about

indicates a noticeable lack of lateral order. It is stretched to 98 ° / _{0 of} its theoretical length

a single, very sharp meridional reflection occurs before both the HT and the EC crystal form;

indicates the longitudinal order. With increasing orientation - up to a chain-

essentially non-crystalline in the sense that it extends from about 99 ° / _{0 of} the theoretical length -

show no three-dimensional order. When these 55 there are more crystals in the EC form. Such

Threads in a manner known per se at constant length Threads have maximum strength,

or in the free state, so that they come together- To distinguish the forms are careful

can draw, heat-treated, they become and detailed X-ray diffraction methods

highly crystalline and show an x-ray diffraction pattern. As noted above, the EC form shows

pattern with very strong meridional reflection first and 60 »cfl-axis repetition, which is almost the length of the full

second and weak meridional reflection of third continuously stretched models, i.e. 26.5 Å for PACM-12,

Order. The distinguishing feature of this kri- corresponds. A distinction from other HT cases

stable form is that its strongest equatorial reflection is best determined by observation

corresponds to a "d" value of about 5.1 to 5.2 Å. made of the third layer line. This layer line

This crystal shape is referred to here as the "A" crystal shape 65 distance for the EC shape does not show the above for the

designated. HT form indicated variability. The EC form

In contrast to the "A" -K.ri- described above, it shows a very strong equatorial diffraction at 4.3 Å im

Stall patterns have threads that, according to the invention, contrast with the 4.5 Å spacing that is used for the HT

7 8

Shape is characteristic. Furthermore, there is the presence of the method described. Any conventional heating

EC-form by discrete long-period diffraction in medium can be used, e.g. B. a heated mandrel

Small-angle X-ray diffraction diagram marked tube, a heating plate, a liquid bath, radiating

draws. Heat or a hot jet of gas or steam, if applicable

Just like all thread-forming polyamides, only the threads become elastic when stretched beyond their 5 also spun the PACM-12 threads and extend the prescribed temperature by connecting them to the limit oriented. The stretching is made easier, enough. This final stretch at high if it is on a heated stretching rod (frictional temperature usually forms part of a verelement), one or both of a hot plate is performed a stretching process in which the threads become an orien. A suitable arrangement is in the USA publication 2,533,013. With yarn draw a draw ratio of at least 3.5 Temperatures of up to approx. 180 C / own which is achieved.

threads practically no lateral order, l ^{r. in} oxidative degradation at melting temperatures

but crystallization can be caused by heat treatment should also be avoided. This is achieved

at constant length and / or by hot expansion 15 by placing in an inert gas such as nitrogen

tion, as explained above, with generation of the A-Kri- or water vapor, spun. Particularly useful

stall shape can be brought about. If one tries, the use of a hot inert gas is

the strength of the non-heat-treated filaments by providing an environment in which the

by using higher drawing ratios melted threads with minimal orientation and

to increase, the threads are through transverse cracking 20 maximum uniformity of cooling up to

Dull and weakened and thus refined for the technical spinning denier or undrawn denier

Use worthless. can be. This method delivers threads that are stronger

A yarn that can be drawn with the crystal structure according to the invention than one that already has at, has better properties (e.g. strength, spinning, and elongation) than a non-crystalline yarn that at that one Technical yarn with the most advantageous intrinsic draw ratio is usually produced using a PACM (see Example 2). When non-crystalline yarns are obtained under BiI- with the highest tt-isomer content. The "A" crystal structure can also be heat-treated, resulting in a loss of strength due to the use of a polyamide with a high degree of moisture. Yarn with HT crystalline weight improves the properties, the shape is not only greater than a yarn with an “A” crystalline shape. 18,000, and higher molecular weights are it can also be;! I \ i :! teaser vcr :: rcc! c; n, ·: .ο CxZ \ '.: l noz'r vo.- ;; ^- !!: af: .—. Praixtiächc Tr.vügur.gcn in To higher drawing ratios can be achieved in connection with the high melt viscosity of the yarn, whereby yarns with strength values of up to polyamides can be made using polyamides with 9 or more g / den. 35 molecular weights from 25,000 to 35,000.

The production of the threads according to the invention within the general range of process

follows by two-stage stretching of the initial conditions, which result in the generation of the

threads, the drawing temperature i :; suitable for the appropriate whisker structure, the

second level is higher than in the first. The preferred conditions are those under which the threads

correct stretching temperature in the second stage 40 at the prescribed elevated temperatures

essential. It has been found empirically that are stretched at least 5 ° / _0th Even a very short

Threads in the second stage a thread temperature in the early action of the elevated temperatures

⁰ C should be achieved, which has the threads indicated by the expression (1!) In order to achieve the desired

Crystal structure proved to be suitable. Heating times

/ ( ^c C) = 290 S - 15m f-20 (- l) "<(II) 45 from 10 to 50 milliseconds at the elevated temperature have given good results.

exceeds the defined value. Herein means into which the yarns according to the invention are particularly useful on such Ange Official number of carbon atoms in the predominant wendungsgebseten where high Festig-dicarboxylic acid and S ergehalt the trans, trans-of stereoisomers ness, high modulus and low shrinkage (tt) content of the PACM in Percent (see USA.-Pa- 50 are desired. These areas of application include document 3,347,917, in which the production of PACM, the reinforcement of mechanical rubber wadings, of various tt contents is described). These tires (especially for low pressure in the equation serves as a guideline for the selection of the standing), belts, plastics, laminates, seat belts, stretching temperature, even if sometimes canvas, ropes, sewing threads etc. The threads have small amounts of the HT crystal form already something 55 can form in the form of continuous threads, monofilaments or below the indicated temperature. multifilament yarns can be used. Including temperatures that are 10 to 20 ^° C. above the temperature defined by threads with a titer of 1 to 50 den as also the equation (II), monofilaments with a higher titer, for example those with are preferably at higher (z. B. 6) V'erstrek diameters from 0.12 to 1.25 mm. The threads used. 60 nen also used in flake or staple fiber form

An upper limit is that the stretching becomes. Other threads or fibers cannot be so high that the temperature should be combined with the thread for strengthening purposes.
stretched without directly proportional orientation. If the threads are used as tire corci; "viscous flow draw" must therefore usually be avoided as used for nylon 66. "Drawing in viscous must" 65 processing conditions are used. Accession occurs when the thread temperature is too close to the polyamide's softening point, for example a standard cord construction. The hexamethylene adipamide used in US Pat

is dipped into a resorcinol-formaldehyde latex adhesive and dried for ^{2 minutes at a tension of 0.9 kg at 150 ° C.} The cord is then stretched by 5 to 13% at 1% to 220 ° C. for 30 seconds to 1 minute. The tire is cured under the conventional conditions used for nylon 66.

Test methods and standard working methods

The calculations of the lateral distance (d-distance) and the "c ^ -axis dimension are carried out in the usual way (cf. HP Klug and LE Alexander in" X-ray Diffraction Procedures ", Verlag John Wiley and Sons, Inc., New York , 1954, especially pages 88, 89, 333, 334, 335, 567 and 568). The "c" center-to-center distance, or T , used by the authors is the vertical dimension of the unit cell.

When reference is made to the yarn module, the "initial module" is meant.

The »breaking strength« (Τ ;,) listed in the tables is that of the titer of the yarn at the break point related strength; It provides a useful way of assessing the potential durability of yarns which different strengths and elongations have to be compared. She becomes out of the relationship

T _b = T (I t- 0.01 £)

calculated, in which T is the normal strength in g / den and E is the elongation at break of the yarn in percent.

The viscosities of the polyamides given here are relative viscosities (RV), as they are in the USA patent 2 385 890 are defined. Unless otherwise specified, the viscosity is based on a Solution determined in a mixture of equal parts of formic acid and phenol.

Strength, elongation at break and modulus are determined with the Instron tensile tester at an elongation rate of 60 ° / ₀ / min. The yarn is relaxed before the examination 24 hours at 24 'C and 55 ° / _o strength relative humidity.

example 1

A mixture of 8.2555 kg bis (4-aminocyclohexyl) -methanmit70 ° / ₀ igemtrans, trans-Stereoisomerengehalt, 9.0357 kg of dodecanedioic acid and 17.2 kg of water is heated with stirring in an autoclave. The temperature is increased to 135 ° C., held at this level for 30 minutes, and then 12.5 kg are distilled off at atmospheric pressure. Then 47 g of 25 ° / ₀ acetic acid solution (as a stabilizer) and 39.6 g of a 2 ° / _o solution of ManganIl hypophosphite be entered as a catalyst in the autoclave. The autoclave is then heated to 285 ° C. at 30 at, and the pressure is released to atmospheric pressure in the course of 90 minutes with a further increase in temperature to 3C0 ° C. The autoclave is kept at 300 ° C. for 90 minutes, after which the polyamide is extruded, cooled and cut into flakes.

The polyamide has a relative viscosity (RV) of 115, determined in 98 ° / _o formic acid (defined in the USA. Patent 2,385,890). The polyamide is dried, melted in a screw cutter and spun at 295 ° C. to form a 34-thread yarn. The yarn has an RV of 212. The yarn is stretched 3.56 times ^{over a stretching pin heated to ICO 0 C.} It then runs in a helical winding around a tube, the temperature of which increases in the direction of the yarn path from 150 to 190 C until a total draw of 4.0 is reached. The yarn titer is 260 den. The yarn properties are given in Table I. In an attempt to increase the yarn strength, the total draw ratio is

Lo ratio increased gradually to 5.24; the properties these yarns are also listed in the table.

Table I.

Ver
search Ver
stretching
relationship Fixed wedge
(g / den) fracture
strain
(· / «) T _h
(g / den) 1
2
3
4th
5
6th 4.0
4.25
4.5
4.75
5.0
5.24 4.8
5.2
5.5
5.0
5.1
5.1 15.9
14.9
14.2
11.2
10.6
10.5 5.6
6.0
6.3
5.6
5.6
5.6

It can be seen that the strength does not progressively increase with the draw ratio. At the higher draw ratios, the yarn is broken by tears that run around the periphery of the yarn, increasingly dull, and stretch breaks often occur.

However, when the drawn yarn to 4.0 times of the experiment 1 over a hot pin at 150 ⁰ C and at 200 and 210'C 2 heated zone plate further on the l, 49 times is stretched, is obtained a yarn having a Strength of 6.4 g / denier and an elongation at break of 10.9 ° / ₀ (Tt, = 7.1). At plate temperatures above about 215 ° C., the achievable yarn strength drops because of the drawing in the viscous flow and the resulting poorer orientation. The total draw ratio for the 6.4 g / denier yarn is thus 6; the X-ray diffraction study shows that the yarn has the HT crystal structure. The diffraction diagram shows that the crystal has a "d" distance of 4.6 A, a "c" axis dimension of 24.1 A and two blackening spots at the first meridional reflection. The yarn has a 7 value which is 13 ° / ₀ higher than that of the best yarn in Table I. Since the calculated "c" axis dimension for this polyamide is 26.5 Å, the warps in this yarn are 91 ° / ₀ fully stretched.

Example 2

A polyamide made from PACM-12 with a tt isomer content of 90% is melted and spun into a yarn. The yarn has a relative viscosity of 141 and a birefringence of 0.0153. The yarn (1) is in a heated to 15O ⁰ C pin to 3.0 times and then in a second process stage cm at 10 three long panels, which are heated in sequence at 160, 170 and 180 ^c C, at 1 , Stretched 33 times. The total drawing ratio is 4.0; the speed of the feed roller is 1.2 m / min. The X-ray diffraction diagram typical for this yarn shows practically no lateral order. If following the road

In addition, a hot plate is placed around the yarn (total contact distance 0.8 m) Annealing at a constant length at 230 ° C. results in a yarn (2) which has the "A" crystal shape.

If an attempt is made to Increasing the draw ratio to (3) 4.25 and (4) 4.5, the yarn strength initially increases and then off. The yarn (4) contains transverse tears, and many yarn breaks occur during drawing. The procedural conditions and yarn properties are in table !! specified.

In contrast, if the same starting yarn on the 150 ⁰ C hot pin and the pin on 210,

Sheets heated at 230 and 240 C are stretched 4.0 times and then heat-treated at 240 C Yarn (5), which is better than yarn (I) or (2) in terms of strength and elongation, although the same draw ratio is applied. This yarn has the HT crystal form.

The draw ratio series is, as shown in Table II, continued until a yarn with a strength of 8 g / den is obtained at a draw ratio of 5.2. This yarn is predominantly in the EC crystal form. The process conditions and yarn properties are given in Table II listed.

Table II

Attempt no.
I 4 I.

Total draw ratio

Plate 1 ( ⁰ C)

Plate 2 ( ⁰ C)

Plate 3 ( ⁰ C)

Tempering ^{temperature (0} C)

Birefringence after drawing

Crystal shape

Firmness (g / den)

Elongation at break (° / ₀ )

Module (g / den)

4.0 4.0 4.25 4.50 4.0 5.0 160 160 160 160 210 210 170 170 170 170 230 230 180 180 180 180 240 240 - 230 - - 240 240 0.0494 0.0461 0.0456 - 0.0495 - no A. no no HT HT / EC 5.9 5.8 5.8 5.7 6.8 7.6 10 13.3 12.4 11.8 13.2 9.4 44 38 40 40 41 58

5.2 210 230 240 '240

A yarn that has the HT crystal structure is as is evident from the birefringence of the drawn yarn, evidently inherent in the same itself Stretching ratio and the same level of orientation more firmly (test 5 eecen over test 1).

Example 3

PACM-12 yarns with various tt isomer content are drawn according to Table III. The yarns have the properties and specified in the table Structure. The stretching conditions are chosen so that the HT crystal form is produced in each case

Table IH
Improved yarns as a result of increased »eo center distance

attempt
THE

° / o tt isomer

Draw ratio.

Maximum stretching

temperature ( ⁰ C)

Yarn properties:

Firmness (g / den)

Elongation at break (%) ...

Module (g / den)

"D" -space (A)

"C" distance (A)

Chain expansion (° / o)

70 70 70 70 70 85 92 3.4 3.8 4.0 5.1 6.0 6.0 6.0 165 to 200 to 190 to 210 to 210 to 200 to 190 to 210 to 210 210 220 220 210 210 237 2.4 3.5 3.4 5.2 6.4 7.0 6.3 Il 15th 11th 12th 10 11th 12th 29 35 35 40 46 51 44 4.6 4.6 4.6 4.6 4.6 4.6 4.6 22.9 23.3 23.5 23.4 24.1 23.8 23.8 86 88 89 88 91 90 90

215 to

It can be seen that the strength and initial modulus of the yarn with increasing "C \" - axis distance gain weight.

Example 4

From polyamides from PACM and aliphatic dicarboxylic acids with Π to 16 carbon atoms becomes a number of yarns spun and under different ones Stretched conditions, process conditions, crystal forms,> d «values (strong reflection) and» c «- Axis dimensions are summarized in Table IV. The yarns with an "A" crystal shape become Development of this crystal structure annealed at constant length. This stage is used with the yarns

with "HT" structure not required, although the percentage of crystalline content by a performed on the yarn under drawing tension Heat treatment is increased.

Table IV

C, ι c _l2 dicarboxylic acid
IC ₁₃ IC ₁ , j

C, o

dd-salary (%)

Draw ratio

Maximum stretching temperature

CC)

Tempering ^{temperature (0} C)

Crystal shape

"D" value (A)

»Cxi-axis distance (A)

90
5.0

225

HT

4.4

23.5

6.5
8.2
64

70
4.0

190

220
A.

4.8 16

Yarn properties:

strength

Elongation at break (%)

Module (g / den)

*) Determined on heat-treated polyamide flakes.

Example 5

Similar to Example 1, a PACM-12 (90 ° / ₀ tt) polyamide with a relative viscosity of 182.4 is produced. The dried flakes are spun into threads in a spinning device with a screw melter at a spinneret temperature of 335 ° C. The yarn (RV 150) is stretched on a heated to 155 ° C draw pin to 3 times, and then stretched again while running in helical coils around a pipe, which at the input end to 205 ⁰ C, in the center at 215 ° C and is heated ^{to 245 °} C. at the exit end. The total draw ratio is 5.9. This yarn is then stretched in accordance with 2 533013 Patent derUSA. by passing it over a heated draw pin to 160 ° C and then heated to 24O ⁰ C plate in addition to the l, 05fache. The yarn now has a tenacity of 9.1 g / den. The »ca axis dimension is 26.4 Å, which corresponds to about 99 ⁰ Z _{0 of} the theoretical length. The »d« distance is 4.4 A. Both the HT and the EC crystal form are available.

Example 6

A polyamide from PACM-12 (tt-lsomerengehalt 90 ° / ₀₎ is melted in a screw melter at 33O ⁰ C and spun through a filter pack and a 17-hole spinneret in a superheated steam atmosphere at 33O ⁰ C and then cooled in air. A lubricating finish is applied to the threads, which are then conveyed to a drawing zone by means of a feed-separation roller combination at a speed of 90 m / min. The yarn has a relative viscosity of 137.

The threads run around a 7.62 cm stretching pin, which ^{is heated to 150 °} C., then around a pair of driven stretching rollers connected in between, and from there in two helical turns around a tube, the individual sections of which in the direction of the yarn run to 210.230 and heated to 240 ° C. Then, the yarn passes in 18 turns around a pair of heat-treatment rollers, which are heated to 240 ⁰ C. The filaments then travel to a pair of conveyor rollers rotating at the same speed as the heat treatment rollers and from there to a winder. Yarns are produced with two different draw ratios.

90
4.0

180
230

5.8
13.3
38

90
4.0

240
240
HT

6.8
13.2
41

97
3.1

200

HT

4.6

24.7

5.5
13th
42

97
3.1

200

HT

4.6
24.9

3.1
14th
26th

100
170

A.
5.0

25.2

1.9
85

70
3

170

HT

4.6
25.9

4.2

32

70

A *)
5.0

25.8

The process conditions, yarn properties and crystal structures are listed in Table V.

Table V

attempt 1 2 Total draw ratio
30 in the annex »
Crystal shape
Yarn strength (g / den)
Yarn break elongation ( ⁰ I ₀ )
Initial modulus (g / den) 4.0
HT
7.4
13.6
41 4.8
HT / EC
1.9
12.7
48

Take threads made of mixed polyamides if they are drawn according to the invention at the appropriate temperature also show the HT crystal structure. This embodiment is illustrated in Example 40 below.

Example 7

Filaments are spun from various mixed polyamides and listed in Table VI 45 conditions stretched. The threads are examined for their crystal structure. The results are in Table VI shown.

50 attempt Table Vl 2 Main poly 1 amide component . PACM-12 (90 tt) 55 Next to PACM-12 (70 U) component . PACM-10 (90 tt) Weight PACM-i *) relationship .. 70/30 60 Maximum 90/10 stretching temperature ( ⁰ C) 240 Crystal shape .. 210 HT "D" spacing HT "5 (A) 4.6 4.6

') 1 means isophthalic acid.

Claims (6)

Patent claims: 1. Crystalline, oriented thread made from a high molecular weight polyamide that is at least 90 percent by weight from recurring structural units of the general formula —N— H —C- H— HO O N -C - (CH ₂ ) ,, - C- in which η is an integer from 9 to 14, with at least 70 percent by weight of the diamino component of the repeating units in the stereoisomeric trans, trans configuration, and up to 10 percent by weight of other repeating structural units, characterized in that the polyamide chains up to at least 86% of their theoretical, fully extended length are stretched and the thread has a crystal spacing in the transverse direction of 4.3 to 4.7 Å, determined from the strongest equatorial reflections in the Bragg X-ray diffraction diagram. 2. Thread according to claim 1, characterized in that it consists of at least 70 percent by weight of recurring structural units of the general formula I, in which η has a value in the specified range, and up to 30 percent by weight of mixed polyamide components of the general 30 my formula I consists in which /) has a different value in the specified range. 3. Thread according to claim 1, characterized in that it consists of a polyamide composed of recurring structural units of the general formula 1, in which η has only a single value in the specified range. 4. Thread according to claim 3, characterized in that /; has the value 10. 5. Thread according to claim 4, characterized in that the polyamide chains up to at least 98% of their theoretical, fully stretched length are stretched. 6. A method for producing the threads according to claim 1 to 5, characterized in that threads are made of a polyamide that consists of at least 90 percent by weight of recurring structural units the general formula —N- H —C— H - in which η denotes an integer from 9 to 14, with at least 70 percent by weight of the diamine component of the repeating units being in the stereoisomeric trans, trans configuration, and up to 10 percent by weight consisting of other repeating structural units, in a first stage at a lower temperature and in a second stage at a temperature greater than 290 + S- 15 / «- 20 (-l) - ^c C, HO O