DE2030741A1 - Mixed polyamide - Google Patents

Description

Toray Industries, Inc.

2, Nihonbashi-Muromachi 2-Chome

Chuo-Ku, Tokyo, Japan Mixed polyamide

Priority »dated June 24, 1969 based on Japanese Patent Application 49 36O / 69

-rom July 10, 1969 based on Japanese patent application 54 085/69

rom July 28, 1969 based on Japanese Patent Application 59009/69

dated October 1, 19 ^ 9 based on Japanese Patent Application 77 789/69

dated November 17, 1969 based on Japanese Patent Application 91 600/69

The invention relates to new mixed polyamides which are useful as textile fibers, films and other moldings and made from (a) terephthalic acid, (b) hexahydroterephthalic acid and (e) Polymethylenediamine with 6-12 carbon atoms can be synthesized.

The invention is concerned with a new mixed polyamide -mnu textile fibers, films and other forms thereof with τ-he * hi em Tevng-Medul, improved dimensional stability wnl heh.r strength. + * + ***, ** +. ·.

BADORlQINAt

At present, aliphatic polyamides such as polyhexamethylene adipamide, polyhexamethylene sebeamide, polyeaproamide and polyundeoamide are industrially produced. These aliphatic polyamides have various advantageous properties than fibers, films and other moldings. In particular, they apply to many other synthetic polymers in terms of strength, abrasion resistance, and dyeability. On the other hand, they own aliphatic polyamides, however, have a comparatively low Young's modulus and poor dimensional stability, and In in this relationship they are inferior to polyethylene terephthalate, which is one of the best synthetic polymers.

So far, various methods have been proposed to increase the Young's modulus of the aliphatic polyamides and improve their dimensional stability. A typical method for this was to introduce cyclic members, such as aromatic rings, into the polyamide chain. For example, the British patent 1 © 70 kl6 describes a poly (polymethylene) terephthalamide which is made up of synthetic resin polymers of pelymethylenediastine and terephthalic acid according to a similar method, as used in the manufacture of pelyhexamethylene adipamide. The® Polyterephthalamiae from the British Pateataoiirift have good properties, such as high Young's medication and improved dimensional stability, which the aliphatic * Pelyanides have. Ks was every oh emh.tf ± ®T ± $ ₉ WwTm ₉ Film®. «Md -« change -,. ■ Feratlimge from it dvuroh 8eh »el8Bffigiiam®a ®d« z> aa9k emämxmn- ~ . -fehmelnvermmngeverfahsOa mn «rfemlt®», um ikr® '

BAD ORlOiNAL

koeittt is unstable. When the British patent polyterephthalamide was molded at or above its son's point, that polyamide had a tendency to its Melt viscosity & t la increase over time, and it was found that it is impossible to shape this polyamide in the final stages Problem of discoloration when deforming on

In order to overcome these problems of polyterephthalamides, a copolymerization method by copolymerizing a polyterephthalamide and an aliphatic polyamide has been proposed Melting point and a decrease in the Sohmelzviskosit & t des Mixed Polymers (Japanese Patent Publication 42-27 575) However, this method always resulted in neon unsolved problems

As an aliphatic polyamide with a polyterephthalamide Was copolymerized, it was found that the resultant Young's modulus and the dimensional stability of the mixed polymer decreased depending on their misoh polymerization ratio · Therefore, this process has not been considered industrial considered applicable.

The object of the invention was therefore to find new polyamides with increased Young's modulus and improved dimensional stability and at the same time with other beneficial properties in the Compare with those of many other known aliphaticians To obtain polyamides. Another aim of the invention is to develop a new mixed polymer of polyterephthalamide with stab!

G09862 / 2124

To get better oil viscosity. Other goals and Advantages of the invention will become apparent from the description below.

· It has been found that mixed polyamides are necessary for a molding have sufficiently low melting points and sufficiently low melt viscosity, from (1) a repeating unit of terephthalamide of the general formula

- OC - V y - CONH (OH ₂ ) _a NH -

and (2) a repeating unit of hexahydroterephthalaaid of the general formula

- OC - / H) - CONH (CH ₉ ) NH -

-O-

2'n

be constructed know who ln η and η integers in area are from 6-12 and know to be the same or different from one another.

Fig. T is a graph showing the melting point (denoted by -0-0-) and the ulasühergangstenperaturem (denoted by - <^ j - ^^ J -, ^) of fat polyamides, which are built up from fenethylene terepkttaalamidunits and units ven Nenanethylenhexahvdrotorephthalamid.

_BAD original

Fig. 2 is a graphical representation! dl · the changes of melt viscosities of the mixed polyamides made up of nonamethylene terephthalamide and nonamethylene hexahydroterephthalamide when heated to 330 ° C.

The problem on which the invention is based was achieved by creating mixed polyamides "the (1) repetitive Units of terephthalamide of the general formula (A)

- 'OO - ^ Y-COKH (CH ₉ ) MH- (a)

and repeating units of hexahydroterephthalamide of formula (B)

-Θ-

- OC - <H) - CONH (CHo) _HH - (b)

2'n

comprise, wherein the content of each unit of the formulas (A) and (b) is at least 5 mol- ^ ₁ based on the total amide units of the polyamides. The molar ratio of (a) to (B) is selected with respect to the particular composition Ύοη (α) and (B) se that the copolymer is moldable, where m and η are the same or different numbers and are in the range tos 6-12.

Therefore, the terephthalate used according to the invention is! preferably one from the group of the following compounds HexamethyXemterephthalamid, Heptamethylenenterephthalsj | id ₉ tctamethylenenterepathalamid, NoAamethylemterephthalaaiii, B ··· -

VadeeametkylemterejilithalAiilA wnA -

BATH ORIGINAL

Dodeoamethylene terephthalamide. Because * is hexahydroterephthalamide preferably one from the group of the following compounds * Hexamethylenehexahydroterephthalamide, Heptamethylenehexahydroterephthalamide, Ootamethylenehexahydroterephthalamide, Nonamethylenehexahydroterephthalamide, Deoamethylenehexahydroterephthalamide amide, undeoamethylene hexahydroterephthalamide and dodecamethylene hexahydro terephthalamide.

However, for best results, should the mixing? pelymerisatlons-rerhULtnis of the mixed polyamide according to the invention can be determined as follows

(i) When m in formula (A) is the same number as η in Formula (B) or greater, the mixed polyamide roped about 20-95 MeI- * terephthalamide of Formula (A) and about 80-5 mol-jl hexahydroterephth & l & mid of the formula (B).

(il) Venn m smaller than η 1st, roped da® misehpelyamide im essential from about 5-80 M®l- £ terephthalamide Formula (A) and about 95-20 MoI- ^ Hexahydroterephthalamid of the formula (B) exist.

In addition, the single nisohpolyanides are concerned with these Invention of the cowardly Mlsohpolyaralde

(a) Nisekpelyamide, which in w® »®» il ± qhe » « on about 15 -Μ · 1 -) (Hexamethyleneenter «phtlialaiBi <il mad mtmm, 83 <-> 20

(b) mixed polyamides consisting essentially of about 10-60 moles-56 hexamethylene terephthalamide and about 90 kO moles- # undeeamethylene hexahydreterephthalamide.

(c) Mixed polyamides, which essentially consist of about 5 - 7 mol-56 Hexamethylene terephthalamide and about 95 - 30 HeI- ^ dodecamethylene hexahydroterephthalamide consist

(d) mixed polyamides, which essentially consist of about k5 - Nonamethylene terephthalamide and about 55-10 moles of hexamethylene hexahydroterephthalamide exist.

(e) mixed polyamides consisting essentially of about 90 -nonamethylene terephthalamide and about 10-70 mol- ^ nonamethylene hexahydroterephthalamide.

(f) mixed polyamides consisting essentially of about 20-70 mole-ft Nonamethylene terephthalamide and about 80-30 mol $ dodecamethylene hexahydroterephthalamide.

(g) mixed polyamides, which essentially consist of about 20 - Undeoamethylene terephthalamide and about 80-10 moles of amethylene hexahydroterephthalamide.

(h) Mivoholyamides, which essentially consist of about 60 - Dodeeamethylene terephthalamide and about kO - 5 MoI- ^ Hexa- ■ lethylenehexahydroterephthalamid consist ·

82/2124 ^BAD ORiQ, _NAL

(i) Mixed polyamides, essentially ams about 3.0 - 95

Dodecamethylene terepwialasiid and about 70-5 M0I-5 & Nona methylenehexahydroterephthalamide exist «.

(j) mixed polyamides consisting essentially of about 95-50

Dodecamethylenterephthalaaid mnd about 5-50 mol ^ Dodeeamethylenhexahydroterephthalamid 'consist _e This is the most preferred Mi3chp © lyaimid after

Copolyamides according OCE invention are synthesized by ®in © rh @ Fk8iimalichen methods similar Method © ^ as si © is in Ziar ™ epielsweise HerstellTang v © a Mylon 66 v © RXF © friend w @ Ta®no Especially FolyiaethylendlaBln with water irorraisoiit uad & nT about 80 - 90 ° C heated. Powdered Tereplithalsämr © is to this mixture sia ^ © setat ₉ raad - this will hold about 3 Miraatssi at this temperature with stirring ₀ A clear, transparent, aqueous h'uBvmg 'of the Sal © s ₀ F © lyia is obtained © tByl © ii = diammonium tereplitlialate is precipitated by cooling the LUsTsmg. «The preferred Wassenaeng © in oli © s © Ba process b © i production of the nylon salaes from Polyieetiiyl © ndiasam @ iaiiffl! Iter®pSit hai at is about 3 - 15 weight s parts, b®a © g © a assf the _6 © ~ weight of the r © eultier®nd Salaes »

! 10 weight parts "Ieopr © © © a pylaXk l part by weight of Hesaliydroterep hthalsfiur © stigGQotst dae mixture is heated with stirring for about 60 -. 7® 6 © RHIT-zt IsopropylalkohollOeungf DI®
contains j is added to ra Q-einiscia _f and SaIa is precipitated. The reaction can be j © d @ © M © twa

ÖA ό ή ο ο / οι ι /

Minutes at the temperature of 6 (5-70 ° C with stirring and then cooled to room temperature.

The salt consists of two types of crystals, the stereoisomers are, polymethylenediamine-ois-hexahydroterephthalate and polymethylene diammoniura-trans-hexahydroterephthalate will get. The two stereoisomeric salts that one so obtained are mixed with the former salt. The mixing ratio should be in the range of the Misohpolyraerlsatlonsbereich lie according to the invention. The mixture is polymerized according to the usual method, for example for the production of aliphatic polyamides such as nylon 66, is applied.

When m equals η, it often turns out to be useful ^ terephthalic acid and hexahydroterephthalic acid to a P © lymethylenediamine containing solution to be added to form their salts and to polymerize the salts thus obtained by conventional methods.

■ As an alternative method, raöglieii, Älkylostör can also use these two dicarboxylic acids as a -Polyaeriftationereaktionspartaer together with PolyMethylenediamine au. This Pali However, it is necessary dan in polymer! Remove the alcohol that has formed. . For example, the alcohol is removed from the resulting mixture, which is threatening. Poly "erisation a polyamide" with "lnam- b" etLauit 'n Fixl # rt' n Polymerisationegrad formed wurd _"$ TSSI <l ■ eo-then. Continuing polymerization, the Semiβoh ·

0 Ö Ö 8 © 2/2 1 2 Λ

Various additives, such as freezing agents, antioxidants, Stabilizers, light stabilizers and antistatic agents, can become suffeijebon to the polymeriBationsgemiseh, if the "required 1st". However, these funds should be used in the Polymerization temperature to be stable.

In order to reduce the melting point of the mixed polyamides, it is also possible to use other highly soluble components, such as aminoca, arainolaurin lactams, hexamethylenediammonium adlpat and hexamethylenediammonium sebaoate, the quantities of which should always be small ₉ Since their unique purpose in this mixed polymerisation is to reduce the melting point,

The equipment used in the manufacture of the Misohpolyaaids Is not limited to any particular device » All equipment used in conventional methods is useful. Either can, masa a continuous apparatus Manufacture of the nylon salt with the formation of the mixed polyamides or use an ohargenwelse .arboitende apparatusa »

The Folyeserisation, is at © twa 260 - 350 'G mater

Pressure of 0 kg / cm toi « $ 0 kg / ®sa dureh ^ e takes ₉ nnd _s weaia

ferderlieii ₈ are used Waeser camouflage elm »Ee ist

not exidi * re "" IeII Atia © opkär® as StickstofTeasg, wihremd the polymerization fealt®iio 1st © iiaigen case is ®ã geous that let

dortoBi Bruok

Bio

- ti - 203Ό741

Reaction kettle is normally about 2 <- 20 hours · The amount of inert gas that is blown into the reaction kettle is 0.001 - 5.0 «J · minute _f based on the volume of the reaction mixture (m) ₀ Ea is, however, also possible, a much larger amount of inert gas. a polymer with a large degree of polymerisation is not obtained.! »

The composite polyamide mo obtained is in. A Kiililzoiie to form a ribbon-like material or streifenartlgen * (or-.irgendeines otherness shaped material, such as filaments, etc.) extrudiert'und un- to a surface temperature. "ternalb 100 ° C. chilled after then powdered or -granulated ·

Since '' powdered or granulated wird- copolyamide _'t formed as required by the -Sinäselfall. "For example, fibers or continuous threads can be spun through Sohmeltspinnen at a temperature of about 2S> 0 - '360- G ₉ voratiifeweiee τοπ about

"ow ground;. \

■ 290. -. 335 ■ C preserved IJIe undisputed Faeersa or Ffiden, ■ .with. a spinneret are spun, for example at a speed of I50 - 1.0QO m per 'minute'

wound up.

The threads are normally stretched over one .Thorn and / or a flat · that is on a. Temperature .below 250 ° C are heated · The threads are in a 'ratio d · «about '» 2.5 - 6.0 times that of their - original Lilrnffe

m stretches. . " ^: . '..

The films can also be gevinaieno duroh extruder molding. En

009 882/2 12Λ

It may be preferable to orient the file m © n®axial © eggs biasially. Besides' you can
or extruderforareuag obtained c

Since the mixed polyamide according to the invention has cyclic links in the polymer chain, such as the Beaaolrimg of the Terephtlialaiaideiiiheit and the Cyelefeessamrinig of the Hexakydrotoreplitlial- aiaidelnheit ₉ , aeia © Hlrto (module) is larger than the range of aromatic PolyasidOj, alioiechiselsvea © Myclisiervea © Myclisiervea © right 3b. © 3h © Sehmelsprailst © for males Formen »Das MiseSipolyaisid nach. ü®r Ez-tlndvai & ß however. ö.bex'raselieadlex'iiyQiso © iiaosa SehEsslspiEisAtp tJi © weise tmterlaalb JQQ G ^

rich Verforaeia isto Ba di © LSlmgs mad F © ffiü3 ύ®α ρ .re β te β der

h. © xylejarcst © ffl dor

the crystallization

owns a MiseMp © Iysao2? doo KHoekpolyoieids a high Kristellinitoto ^ ado Ia diooGjr H ± aiQi © Mt Eaat se® Misclip © iyaaidl a IfeiataIIimltSltsg ^ adu d @ r ηεοΜθξτει ο © high istj like jeaer des T © ^{EaiH 5} oplatI ©] ⁱ D © dos ⁵ dos

The MSieclipoIysunid naoä der IS ^ fladlmaig will _f Innenauestattaa

Iioi

were and for other ©

Based on the examples

009882 / 212Λ

example 1

183 kg of water were added to 10 kg of dodecamethylenedii 'and the mixture was heated to 80.degree.-0.degree. .8,3 kg of terephthalic acid were pulverized au & ®m mixture eye © β did t _f, and this was kept 30 minutes under stirring at this temperature. This gave a transparent aqueous © XBsiing of S _a lze. The solution was cooled to 20 ° C and a salt precipitated. 17.95 kg of the salt with a melting point of iron 158 ^° C. were obtained by filtration and drying.

On the other hand, 176 kg to 8.6 kg Iβοpropylalkohol hexahydro terephthalic acid were added, and the mixture was heated to 60 - 70 ⁰ C heated. .20 kg of isopropyl alcohol solution with a. A content of 5% by weight oodeamethylenediamine was added to the mixture with stirring, and the salt was precipitated at this temperature. The reaction mixture was kept at this temperature for 30 minutes with stirring and then at 20 ° C Filtration and drying gave * 18.2 kg of 'd®8 salt. The® salt consisted of the trane isomer with a * melting point * of 201 ° C. and then cia-xaomer with a melting point * of 17 ° C. Both types of sala were mixed with one another. E ".were 7 Genie oh typ ·" herg "" t "llts (a) of f 5. MoI- ^ Dod" eaXtBethylendianuBOniuuter "phthalate and 5 'Dodeeamethylendiammoniumhexahydroterephthalat (as 95 ^ λ b «s« iehn «t) ₉ ■ (b) • ln'Gtoaiiieh'-8OJL ₁₂ ^ OB ₁₂ , (β)« in Gemiieh-65A ₁₂ / 35B _i2 i '(d)' «la O * aiaoh'50A ₁₂ / 50B ₁₂ , (·) «in Oenlteh 35A ₁₂ / 65B ₁₂ * ' (t) min- Cleiiieoli 20Α _Ί2 / 80Β ₁₂ and (ar) an Oemlaeh 10A ₁₂ / 90B ₁₂ t'-'Je -d ·· di «« «r 7 G» nle.oh · * became · polyai * ri «l« rt · ■■ ...

ÖÖÖ882 / 21U ^: '

ν. The polymerization was carried out as follows

(i) Dae salt © the mixture of salts was mixed with 50% by weight of water and with 33 »3 mol of Bemeo © SaMTO ₁ , based on the SaIa or Salagemiscli»

(££) In the first stage, the ice cream obtained in this way was heated to 2 to 180 ° C. for hours under an overpressure of 0-10 kg / cm

(iii) In the second "Stef © tf" rd @ dass

Hours under © ineia overpressure voa 10

three 180

250 ° C.

(iv) In the third stage, this became

Hours further to 250 - 300 ° C © 3? 2a ± t2s.t ₉ . wlkread the pressure gradually on AtBaosphäroasLdLruek goseakü; Water was removed _c νακά daiaia -was eiae 'Straad © on

300 ° C content «,

individually exinadiert, külilt vmd Die SeSsiEolsptmkto

diö »© £ 'Folyeiaicie srardoia

Tg wta ^ ale ua & lt
there -ssiii

ßoaGDSGias Bao Folymor

© isaea P @ lya © s "f ilEa. A \ a

form. 'The dynamic loss of the eo obtained flmee was

the '

according to the known method and apparatus * "VIBROH ^B " (trade name of the Toyo Sohuki Company), gemeeeea and the Tg of the polymer was determined according to "the peak temperature of the main spreads of dynamic loss" .

.Table I shows the. Results" · . . '.

Tabel. I ...

Heat saturation and glass transition temperatures of approx

\ y mixed poly ■ 100/0 95/5 80/20 65/35 50/50 \ perisation-. ■ N. molar ratio 297 29% 291 288 295 Eigen'-Ny .nie of 122 121 121 121 121 scliaftenv A ₁₀ / B ₁₉ M.P. (° C). Te (° c). . ■. .

N. Misclipoly- 35/65 20/80 - * ΙΌ / 90 0/1 © 0 .xmeri sation- ■ X. Molverhait- 305 312 318 . 32% Eigen-x. never iron 122 122 127 ■ ■ 128 BchaftenV A ₁ -ZB ₁ J ₃ , M.P * (° C). ■■ τβ ( ^e ο) '*.

In Table I means

form·!*

- NH (CH ₂ ) ^

008082 / 2Ί2Α

and B ₁ - the formula

- NH (CH ₂ I _{12 NHOC}

.0.

CO -

Further measurements were made for the ratio of residence time to melt viscosities at melting points of 5 types of polyamides selected from the above blends. These measurements show that the method from the standpoint suitable for stability. Table II shows these results.

Table II Change in Sohm Melt Viscosity (Poisen)

2.45 10 20th 40 60 90 850 120 ^. Time
MolverV ^r ^ "^
membershipV 2.39 1200 5400 638OO not possible 83Θ to eat 100/0 2.35 800 850 840 840 155O 860 80/20 2.41 800 820 830 830 820 65/35 2.37 1550 I5OO 1550 1550 I6OO 35/65 2050 350 © 65OO 47800 impossible to measure 10/90

In Table II, b denotes the relative viscosity of the

^v r

Polymers before remelting. The relative viscosity was measured using the following method!

009682 / 212A

The polymer was dissolved in concentrated sulfuric acid,

and the concentration of the polymer was adjusted to 1.0 $

The relative viscosity was measured at 25 ° C.

Table II shows that the copolyamides of the invention are suitable for molding processes. Especially the copolymers in the range of a molar ratio of 80/20 to 35/65 have excellent properties for deforming.

Example 2

65 parts by weight of the salt obtained from dodecamethylenediamine and terephthalic acid were mixed with 35 parts by weight of the salt obtained from dodecamethylenediarain and hexahydroterephthalic acid. The mixture was dissolved in water to form an aqueous solution containing 8% by weight of the salt mixture. As a viscosity stabilizer, 1/33.3 (mol / mol salts) benzylamine was added to the aqueous solution. This mixture was added to the reaction kettle and the air in the kettle was displaced by nitrogen.

DiA polymerization was carried out under the following conditions 1

1st stage 1 polymerization with increasing de. » Overpressure® · from 0 to 10 kg / cm and increasing the temperature from 25 to 180 ° C for two hours.

2nd stage: Polymerization while maintaining an excess pressure of 10 kg / cm and increasing the temperature from 180 to 250 ° C. for two hours.

3 «stage t polymerization under decreasing overpressure from 10 to 0 kg / cm through opening to the atmosphere and increasing the temperature from 250 to 300 ° C for two hours,

k. Stage t Polymerization under atmospheric pressure and nitrogen gas for one hour at 300 ° C. '

The thus obtained polyamide was extruded and, after cooling, pulverized or granulated. This® mixed polyamide had a melting point of 233 ° G ₉ an If) of 2.40 in Sohwe »

Feic acid (measured according to the method described in Example 1) and 0.15% by weight of water-soluble components.

This mixed polymer was melted at 330 ° C., extruded through Elm's spinneret with 2k orifices, each of which had a diameter of 0.25 n ™, and wound up at a rate of kQQ m per minute to form undrawn threads. The 0O Fäd®m obtained were then m to 3.5 times its ursprüngllernen Läng® over a heated to 90 C "· mandrel and a erhltsten at 19 ° C © plate at a rate of koq per minute

Four types of verutr® © kt * r P »« t * rn <, Diee * four Aryans were obtained using the same method as obeai _{0 but using different types of polyamides}

! 82/2124

drawn fibers had the following chemical structures!

Comparative Experiment 1-A The polymer had a chemical structure of the formula!

-OC - ^^ \ -GONH (CH ₂ ) ₁₂ ΝΗ · ί · / -OC (CH ₂ ) ^ CONH (CH ₂ ) ^ NH- = 8o / 2O ^ = / I 12th

(Molar ratio).

Comparative experiment T-B The polymer had a chemical structure of the formula

-CONH (CH ₂ ) ₁₂ NH- / -OC (CH ₂ ) ^ CONH (Ch ₂ ) ₁₂ NH- = 50/50 (molar ratio).

Comparative experiment 2 , The polymer had a chemical structure of the formula

, CONH (CH ₂ ) ₁₂ NH- = 70/30

-OC- ^ ^ -CONH (CHg) ₁ , (molar ratio).

Comparative experiment ^ The polymer was nylon 6.

(-0C (CH ₂ ) -NH- - 100)

069882/212 ^

Table III shows the comparison for those according to the invention obtained fibers and the comparative experiments, those obtained above.

Table III
Fiber properties "* -"

properties Fiber after
the inventor
manure Comparison © experiments fiber
1-A fiber
1-B 2 fiber
3 denier 70.4 70.1 72.0 71.1 70.8 Tg (° C) 121 - 98 113 38 Strength (g / d) 5.8 4 _f o 4 1 '5.3 Elongation ($) 20 "2 12.2 24 4 . 15 ₉ O 27.3 Young module (g / d) 79.6 5O _f o 41j7 50.0 »5.0 Shrinkage in
boiling water
(*) 3.3 4.7 4.1 13.6 13.4

For Table III, the shrinkage in the boiling point was calculated! Water measured as follows! A yarn sample in a relaxed state was boiled in water for 30 minutes "Die Läng ©" tee Garaes ύοτ and after the treatment it was measured and the degree of vigor was calculated.

The Tg of fiber 1-A was measured as niolite.

0ÖÖ882 / 2124

Table III shows that the fiber of the invention has a higher Young's modulus and better dimensional stability than the other fibers possessed, (dimensional stability is due to the shrinkage shown in boiling water.)

Example 3

30 kg of an aqueous solution containing 30 weight ^ of hexamethylenediamine were heated to 60 - 7O ⁰ C heated, and 12.88 kg of powdered terephthalic acid were added under stirring to the solution · The mixture was kept 3 ° min under stirring at this temperature . A transparent aqueous solution of the salt was obtained. 21.21 kg of the salt with a melting point of 184 ° C. were obtained in this way by cooling the transparent solution with precipitation of the salt and then filtering and drying.

This salt was mixed with another salt called one from hexahydroterephthalic acid and dodecamethylendlamine in various Mixing ratios received. IDs became 10 Mix types obtained. These 10 Misohung Types, the First® Salt itself and the latter salt itself became one in Presence of 50% by weight of water and 1/50 (mol / mol des Salt or salt mixture of benzoic acid polymerized0 The polymerization was carried out according to the dar jjlelchaüi Method® as in Example 1, j «but carried out with the exception that at 320 ° C. in a nitrogen gas atmosphere as the 4th stage b * i 300 ° C was polymerized. So were 12 polyamide products obtain. Di · melting point · and

ΟΟίίβί / 21-24

Doors «read polyamides were made after the same. Method like measured in example 1. Table IV shows the results «

Table IV Melting points and glass transition temperatures of the polyamides

Mixed poly
merization-
Molar ratio
^B 1 ₂ / ^A 6 100/0 95/5 85/15 75/25 65/35 M.P. (° C) 3Zk 299 275 263 281 Tg (° C) 128 128 128 128 128

Mixed poly
merization-
Molar ratio
^B 1 ₂ / ^A 6 55Λ5 ^ 5/55 35/65 27/75 15/85 M.P. (° C) 299 302 305 3O8 313 Tff (° C) 128 130 129 131 133

Mixed poly
meriaation-
Molar Ratio®
^B 1 ₂ / ^A 6 .Ιή / 99 0/100 M.P. (° C) 332 370 T * (° C) 137 ifc5

00 ^ 88272124

In Table IV, B ₁₂ denotes the amide unit of the formula - NH (CH) NHOC - / H> * CO - '

2 '12

-0-

and Ag is the amide unit of the formula - NH (CH ₂ X ₅ NHOC- & \ , CO -

In addition, there were 5 types of polyamides obtained above about the speed of a change in visual ease over time .at 33 ° C asu determine the quality of the Polymers and its process stability in spinning processes determine. Tabel. V shows the results »Venn * dae product, was insoluble, none occurred. Recording. If the product becomes soluble, corresponding information appears. In the. Columns' of table V.

0 0 9 8 8 2/21 2k

Table V Adjustment of the scallop viscosity over time (poisen)

^ s. Time
_, ^ s_ (minutes)
Molver- ^ y.
ratio \
^B 12 / ^A 6 \ ^ 15th 20th 30th 60 135O 100 95/5 i ^ L _r ^ 2.30) 1350 I3OO I3OO 1330 940 1350 (soluble) 75/25 (* l _r = 2 _s % 5) 950 950 950 940 1400 930 (iSalich) 55A5 (1 _r = 2.3i) IkQQ I37O I38O 14O © 5500 1450 (soluble) 25/75 ( ^l i _r = 2 _e 2i) 15 © 0 I65O 2400 4000 17OOO (soluble) 15/85 (* L _r «2.O9) 2540 4900 15000 unbelievable. to. measure (Qmellnng)

INJ CD (JO CD

- ² ^ - ■■■ 203074 ί

In Table V, the term "soluble" means that 1 gram of polyamide was dissolved in 100 cm- 'sulfuric acid, and the expression "swelling" means that the polyamide did not dissolve in concentrated sulfuric acid because it gelled or otherwise

chemically modified. The "χ" was made using the same method measured as in example 1.

Table V shows that the polymer with a molar ratio (B ₁₂ / A ₆ ) "m 95/5 <*» 50/70 has good quality and process stability for spinning processes, since its melt viscosity changes only little over time.

example k

Nine types of * mixtures were prepared, consisting of the salt (Ag), which had been obtained by reacting nonamethylene diamine and terephthalic acid in an equimolar ratio, and the salt (Bq), which was obtained by reacting nonamethylenediamine and hexahydroterephthalic acid in one equimolar ratio had been obtained passed. The molar ratios of these mixtures A ₀ / Bq were 1/9 ^"2/8" 3/7 "5/5 V'6 _t» 6 / k, 7/3, 8/2 and 9 / i. These mixtures, the salt (Al) and the salt (B-) were dissolved in water to form aqueous solutions containing 60% by weight salt or salts, and 1/23 (mol / mol salt or salts) benzoic acid became added to any aqueous solution. Each mixture thus obtained was individually placed in an autoclave, and the air in the autoclave was replaced with nitrogen gas. All autoclaves were under the same during the polymerization

Ö04Ö82 / -21U

Conditions kept. The polymerization consisted of the following, four levelsχ

1st stage t Polymerization under increasing overpressure of 0-10 kg / cm and increasing temperature of 25-180 ° C for two hours.

2nd stage : polymerization under one. Overpressure of 10 kg / e *. and at a temperature of 180-280 ° C for two hours.

3rd stage ; Polymerization under decreasing overpressure of

2
10 to 0 kg / cm by opening to the atmosphere and

at 280 - 33O ⁰ C for two hours.

k. Stage ; Polymerization under AtmosphM.r®ndruok at 280 to 330 C while nitrogen gas was passed over the reaction mixture.

The 11 types of polyamides thus obtained were used to form Ribbons with a cross section of 3 πωι · 300 mm extruded « Each strip was cut into 3mm x 3mm x 3mm cubes.

The melting points and glass transition temperatures. were in the same ¥ _e ise measured as in Example 1 .. W ± g * 1 shows the results. The polyamides were roughly the same

In addition, the TaränderunfSfrad was used for dios · polyamides

0ÖÖ882 / 2124

Schmelzviskoait t with time at 27O - 350 ° C measured ... Figure 2 shows the change in melt viscosity with time at 33O ⁰ C. The polyamide having a melting point of more than 300 C had a greater change in melt viscosity with time and. did not have good spinnability »

Three of the mixed polyamides obtained above were eohmelzge sponnge * (a) mixed polymer from 90 Mo-%

co -

(A ₉ ) and 10 mol #

■ 0-

- NH (CH ₂ ) oNH0C - (H V- CO-

(B ₉ ), (b) mixed polymer of 60 mol $ (A.) and 40 mol-f (bJ and (c) mixed polymer of 30 mol $ (A ₉ ) and 70 -M0I-9 & (B ₉ ). Each tmdrawn fiber obtained in this way was then stretched to 3 «5 times its original length with the aid of a hot mandrel at 90 ° C and over a hot plate at 180 ° C.

On the other hand, as a Vergleioheversuch Misohp'olyamid from 60 mol% Nonamethylenterephthalamideinhelten and kO .M 1- © ^ ^ -Caprοamideinheiten by polymerizing a mixture of 60 $ of Mo1- obtained from nonamethylenediamine and terephthalic acid salt and ^ O mole ~ $ £ -Caprolactara manufactured. Nacla. stretched fanera of this mixed polyamide were obtained by the same method as above * Table VI shows the results.

0ÖÖ882 / 21 24

Table VI

20307A1

Mixed polymer
sations Molver
ratio A _Q / B _Q Firm
speed
AROUND) strain
(*) Young
module
(β / d) CR value Fibers after 90/10
of the invention 6O / 4O
3O / 7O 6.05
5.49
5.78 24.3
26.5
25.4 80.1
78.5
81.2 50.1
49.2
53.2 Ver 60 (A ₉ ) fiber /
_f X.I. at- " _{0 (Bylon 6)} 4.01 27.1 35.2 32.1

In Table VI, in Figs. 1 and 2 means terephthalamide unit

the nonamethylene

(- NH (CH ₀ ) _Q NHOC A. y

- CO -)

and Bq the nonamethyleaahexahydroterephthalamide unit

(- NH (CH ₂ ) _Q NHOC - (H \ -CO-)

The CR value means the crimp stiffness of precautionary twisted fibers and is the parameter of a reoccurrence® of a crimp of voluminous, provisionally twisted fibers «The value is derived from the formula (iL ^ / L ..)» 100 ,, In this formula L ₁ and L di © values (fiber length) ₈ which are measured according to the following method · A pae © r _s on which a certain load is attached is given in the "water wosi ~ 25 C g © at ₈ and two minutes later the length is measured in dles @ m example L ₁ mg using -from 250 mg / D © iai © r and L "using 5 / denier load

00ÖÖ8 2/21 2Λ

Example 5

138.2 kg of isopropanol became 8.6 kg of hexahydroterephthalic acid added, and the mixture was heated to 6O - 70 C, 1.6 kg of isopropanol solution with a content of 50, Hexamethylenediamine by weight was added to this mixture with stirring. The salt suddenly fell out. The reaction mixture However, was 30 minutes with stirring on the Maintained the same temperature and then cooled to 20 C. Filtration gave from the reaction mixture and Drying 13f8 kg of the salt. The salt consisted of the trane isomer with a melting point of 213 C and the cis isomer having a melting point of 108 ° C as measured by differential heat analysis.

The salt thus obtained and that from the reaction of dodecanomethylenediamine Salts obtained with terephthalic acid were mixed together in the ratio shown in Table VII » 50% by weight of water and 1/50 (mol / mol of the salts) benzoic acid were added to this brine sauce. The polymerization the mixture thus obtained was carried out with the following stages:

1st stage » Polymerization by E ₃ JtIi ta on from room temperature to 180 ° C and increasing the overpressure from 0 to 10 kg / cm for two hours

2, stage »» Polymerization by heating. 180 to 250 ° C and maintaining an overpressure of 10 kg / cm for two hours. ' _{M Λ} . ,

OOQSS 2/212 A

3. Stage polymerization by heating from 25 ° to 300 ° C

2 lind while reducing the overpressure from 10 to 0 kg / cm

for two hours.

k. Stage t Polymerization by heating from 300 ° C to 320 ° C in a nitrogen gas atmosphere during a. Hour. The melting point and the glass transition temperature of the mixed polyamide obtained in this way were measured. Table VII shows the results.

0 β 8 2/2 1

Φ H H Φ

IA
“A
“A
Jt CM
T-
CA 122 “A
Jt
“A O
CA ZZl 65/35 ZlZ CA
CVl 75/25 CM
“A
CM 121 85/15 CM
t- «·
CM 122 95/5 00
CVl 122 93/3 CM
On
CM 122 100/0 On
CM 122 I.
I U
• Η Φ
»Η a
a ο ο
> .ac>
HI
O W »
ft d Ή VO
Λ ο ti ffl
O -rl + »\
«+» H CM
• H (d W »* -
X MA M O
O
dd
X O
O
to

0/100 379 O
“A Q
ON 365 ON
CA OO
> ■■ ο
“A
CA CVJ
CA 27/75 O
«A 128 35/65 O
CA
CA CA
CM
Τ I.
1 U
• Η Φ
Φ H Ö
a ο ο
ha r>
HI
o m m
A CJ Ή VO
Λ ο around
O -ri 4 * \
«+» H «M
• ri «1« J- ; - O
O
X Ο
O
δ

OOÖ 882/212

In Table VII, A ₁₂ © in® means repeating unit

of dodeeamethylene terephthalamide

(- NH (CHg) ₁₂ NHOC - #> Ä- CO -)

and B _£ a repeating unit of hexamethylene hexao

hydroterephthalamide

(- NH (CHg) ₆ NHOC - / H \ -CO-)

Table VII shows that $ when the component A ₁₂ of the copolyamide in an amount of 55 mol - was $> or less is present _v, the melting point of the copolymer is higher than 3 °°° C and rapidly increased and at the same di © glass transition temperature also increased. This phenomenon shows that it is often not preferred to use a mixed polyamide which consists of less than 35 Mo1- $ ^ ₁₂ and more than 65 Mo1- $ B ^ for the purposes mentioned, in order to achieve the main objectives aimed at according to the invention .

Example 6

80 parts by weight of the salt obtained in the reaction of dodecamethylenediamine with terephthalic acid and 20 parts by weight of the salt obtained in the reaction of hexamethylenediamine with hexahydro terephthalic acid were mixed together, and 100 parts by weight of the mixture thus obtained were mixed together with 35 parts by weight of water and 1/50 ( mol / mol mixture) was added to the kettle R _e action. The air in that

009882/2124

Reaction vessel was displaced by nitrogen gas »

The polymerization was carried out according to the following stages:

1st stage t polymerization with heating from room temperature to 180 ° C. and increasing the overpressure from 0 to 10 kg / cm for two hours.

2. Stages polymerization with heating from 180 to 250 ° C and while maintaining the overpressure of 10 kg / cm for two hours.

3 "Stages polymerization with heating from 250 to 300 ° C" and reduction of the overpressure from .10 to 0 kg / cm by opening to the atmosphere for two hours.

k . Stage t Polymerization while maintaining the temperature of 300 C under atmospheric pressure for one hour.

The mixed polyamide thus obtained was extruded and pulverized after cooling. This mixed polyamide had a melting point of 252 ° C., a relative viscosity (* X _r ) in sulfuric acid of Z _t kk _t - measured according to the method described in Example 1, and 0.12% by weight of the water-soluble compound.

This polymer was mixed ·· ffeeohmolaen at 295 ° C, openings through a spinneret having Zk of which ed j · a diameter

009862/2124

_ 3Λ - 2Ü30741

of 0.25 mm, - extruded, and forming undrawn filaments at a speed of. 400 m per minute wound. The threads thus obtained were then stretched over a hot mandrel at 90 ° C. and over a hot plate at 180 ° C. at a speed of 400 m per minute to 3.5 times their original length.

A drawn one was made by the same spinning process as above Thread of nylon 6 and a drawn thread of polyethylene terephthalate manufactured.

Various properties of these three threads were measured. Table VIII shows the results.

Table VIII Properties of the drawn fibers

, «_ Crazy
Eieen - ^ "^" ^^^
shafts ^ ** ^ - «^^ After
invention Nylon β Polyethylene »
terephthalate denier 70.8 70.5 70.1 Tg (° C) * 121 38 79 Tensile strength
(e / d) 550 535 456 Stretching in dry
in a state ($) 22.7 27.3 22.6 - Yeung module (g / d) 70.8 25.0 112.1 Shrinkage in
■ loading water (7 I) ^ ² 13, h 6.9

. 35-203Ü7 41

Example 7

One mole of terephthalic acid was reacted with 1 mole of undecamethylenediamine in 2,100 cm ^J water at 9 ° C. for about 3 ° minutes of gentle stirring in order to obtain a transparent solution of the salt. The solution was cooled to room temperature _for the salt to precipitate. The salt obtained in this way in a yield of $ 96.5 had a melting point of 2 ^ 0 C.

On the other hand, one mole of hexahydroterephthalic acid was 1 mole Undecamethylenediamine in the 3 x 600 cm isopropanol at 70 ° C. reacted for 3 ° minutes with stirring. The salt caught my eye once off, but the reaction mixture was cooled to room temperature. The yield of the salt was $ 93 »6 · the salt consisted of Cis-Isonier with a melting point of 173 C and Trans isomer with a melting point of 203 ° C by differential heat analysis.

Various mixtures of these two types of salt have been made. Each mixture of these salts was dissolved in water to obtain a aqueous solution containing 60% by weight of the mixture, and each of these solutions contained 1/50 Mole / mole benzoic acid as a polymerization control agent.

The polymerization was carried out with the following stages «

1st stage t polymerization with heating from 25 to 180 ° C. and increasing the overpressure from 0 to 10 kg / cm for two hours.

0 9 6 8 2/2 12 Λ ORIGiNAL INSPECTED

2nd stage: polymerization with heating from 180 to 250 ° C. and maintaining the overpressure at 10 kg / cm 2 for two hours.

3rd stage polymerization with heating from 250 to 300 ° C and reduction of the overpressure from 10 to 0 kg / cm during

• ■ -

two hours by opening to the atmosphere.

4th stage: Polymerization by maintaining the temperature

O
temperature to 300 C in a nitrogen gas atmosphere during

one hour. . ·

The melting points of the mixed polyamides thus obtained were measured.

Undrawn filaments were obtained from these polyamides using a small spinning machine. The undrawn Threads were then triple over a hot mandrel at 80 ° C and over a hot plate at 160 ° C stretched to its original length. Table XX shows the results.

009882/2124

Table IX

Mixed polymerisation molar ratio A,

M. P. (o C)

Λ,

Temperature of spinning (° C)

Suitability for spinning processes

Properties of the drawn threads

Tensile strength
ability (g / d)

strain

Young module (g / d)

100/0

289

2.04

320

80/20

271

2 _f 14

300

1.09

23.0

39.7

60/40

255

2.01

290

3.1

26.2

38.5

40/60

20/80

0/100

261

28?

305

2.19

2 _S 11

290

32O

32Ο

3.7

1 _f 6

15.8

21.3

43.2

O GO CD

In Table IX, the designation "(TJj)" means that the mixed polyamide had excellent E ± ga, wa.g for © in spinning, the designation ^a y \ "that the copolymer was still suitable for spinning, but majaotaaal the phenomenon of Fiber breaks during processing, and the designation "X", indicated that it was impossible to continuously spin the fibers because of frequent fiber breaks, and A ₁₁ denotes a nonamethylene teremphthalamide unit of the formula

-OC-

and B _{11 is} a nonamethylene hexahydroterephthalamide unit of the formula

- / H \ - CONH (CH ₂ ) _1. , NH -

- OC

The relative viscosity (* L) became that of the same Method as measured in example 1.

Example 8

Following the procedure of Example 2 , three kinds of monofilament yarns were made from the following polyamides

(l) A mixed polymer of 65 mol »# mlnrnv Dodeoasaethyleiiterephthalamldeinheit of the formula

- OC - f ^ - CONH (CH ₂ ) ₁₂ NH -

009882/2124

and a dodecamethylene hexahydroterephthalamide unit the formula

- OC - (H V- CONH (CH-) ₁₅ NH-

(according to the invention)

(ii) A copolymer of 80 mol- # dodecamethylene terephthalamide unit and 20 Mo1- $ Dodecamethyleneuberamid der formula

- OC (GH ₂ ) ₆ CONH ((comparative comparison 1).

(iii) Nylon 6 (Comparative Run 2). Table X shows the Spinning conditions and the properties of the fibers.

009682/2 1 2

Table X

ο co οο

Spinning temperature (C)
Stretching temperature (C)
Vers treck ratio s After
invention 18.3
18, 1 Comparison
example 1 Comparison
example 2 Procedural conditions
worked Denier (d) 305
150
4.0 "*> 1: 5? 300
150
4.0 270
60
4.0 441 4.3 442 440 Tensile strength (dry) / ι \ 5.21
(moist) ^ ⁸ &quot; 5.16 0.80 4.96
^, 93 5.40
4.80 Properties Elongation (dry) / ^ n
(wet) ^κη ° ' 17.6
17.8 20.0
19.8 the fiber Knot strength (dry) /
(wet) ^U 3.75
3.72 3.93
3.66 Shrinkage in boiling
WSsser (#) 5.5 10.8 Dimensional stability, / Jr ^
Ratio VP) 1.52 2.95

CD CO CD

In Table X the ratio of the dimensional stability was measured as follows: A sample whose length was measured was charged with 5OO g of a charged thereto hanging weight and treated in silicone oil at I3O ⁰ C. After 100 Hinuten the length of the thus treated Prob © was again measured, and the ratio of the dimension stability was calculated using the formula t

Ratio of dimensional stability = 'χ 100

^L 1

where L is the original length of the sample and L _{2 is} the length of the sample after treatment.

Table X explains that this mixed polyamide appears to be a possesses excellent dimensional stability, even after it had been formed into a monofilament yarn which usually does not have good dimensional stability because of its large denier would have.

Example 9

Following the procedure of Example 1, a copolymer was obtained also contains 65 mol of a dodecamethylene terephthalamide and 35 Mol- # of a dodecamethylene hexa & ydro tarephthalaaidei ~ nhe.it manufactured. This polyamide was formed with the formation of Cutlets with a diameter of 2 mm and a length of 3 bub shaped. Dloae schnitzel became the cylinder of an extruder fed, which is heated to 260 - 285 ° C with a The tendon was fitted and heated to 80 C.

009882/2124

Screw was equipped, and heated asu © iner to 80 ° C Shape with a cross section of 30 am '3 mm and a length extruded from 220 mm. The ao- 'shaped object was in

the

Submerged in water, then kept at room temperature for a month became.

A nylon 6 molding was prepared by the same method as above, and this was also immersed in water kept at room temperature for one month
became.

The dimensional stability of these two moldings was measured. Table XI shows the results.

Table XI

Removal from the After
invention 07 - Nylon 6 53 Shrinkage after
Shape (%) Longitudinal direction ($) 1 | 13th 1, 93 Stretching after
Dive into Cross direction ($.) O, 11 1, 03 Water during
• one month Equilibrium water absorption
(at 25 ° C, 60 $ relative © Feuch
activity) O ₉ • 2, 5 . · ■ 4,

In Table XI, the means

Inferred from the form "the length of the object" s _v

immediately after removal from the mold

009 882/2 124

Generally, a polyamide exhibits a characteristic after molding Shrinkage. Especially a molded IBLyamid article, taken from a mold cooled to room temperature usually shrinks. If on the other hand If polyamide is immersed in water, polyamide absorbs water and this causes swelling. Therefore owns a polyamide with a higher degree of shrinkage and greater degree of swelling, lower dimensional stability.

The mixed polyamides of this invention were found to be excellent in terms of dimensional stability.

In addition, the mixed polyamide of this example was measured for various mechanical properties. It it was found that there is a yield strength of 660 kg / cm, an elongation at the yield point of $ 10, a breaking strength of 592 kg / cm and an elongation at the breaking point of $ 14 owns.

009882/2124

Claims (1)

Claims 1. Mouldable mixed polyamide, characterized in that it repeating terephthalamide units of the general formula (a) - CONH (CH ₂ ) _m NH - and repeating hexahydroterephthalamide units of the general formula (b) .0. - OC - (H) - CONH (CH) NH - 2'n comprisesι wherein the content of each of the units (a) and (B) is at least 5 mol $, based on the total amide units of the polyamide and m and η are numbers in the range from 6-12 and can be the same or different · 2. MischpοIyamid according to claim 1, characterized in that that it consists essentially of 20-95 moles- $ of the repeating Unit of formula (a) and 80-5 mol # of the repeating unit of formula (b) and m is equal to or greater than η. 3. Mixed polyamide according to claim 1, characterized in that it consists essentially of 5-80 mol $ of the repeating unit of the formula (A) and 95-20 mol # of the repeating unit of the formula (b) and that m smaller al. ftföfa _2/2 1 2 Λ ORIGINAL INSPECTED ■ .- ■ 45- ^: 2 03G741 k, mixed polyamide according to claims 1-3, characterized in that it has a melting point below 300 ° C. 5 mixed polyamide according to claim 1, characterized in that that it consists essentially of 15-80 mol $ hexamethylene terephthalamide and 85-20 moles- # nonamethylene hexahydroterephthalamide consists. 6. Mixed polyamide according to claim 1, characterized in that it consists essentially of 10-60 mol- $ hexamethylene terephthalamide and 90 - kO mol- $ undecamethylene hexahydro-terephthalamide. 7. Mixed polyamide according to claim 1, characterized in that it consists essentially of 5-70 mol- $ hexamethylene terephthalamide and 95-3 ° mol- $ dodecamethylene hexahydroterephthalamide consists. 8. mixed polyamide according to claim 1, characterized in that that it consists essentially of 45-90 mol- ^ nonamethylene terephthalamide and 55-10 mole percent hexamethylhexahydroterepjt / hthalamid consists. . 9. Misohpolyamid according to claim 1, daduroh in that · ■ essentially of 90-30 MOI ^ thyl Noname η- · terephthalamide and 10-70 MOI ^ thyl Nonarne enhexahydroterephthalamid exists. 009882/2124 10. Mixed polyamide according to claim 1, characterized in that it consists essentially of 20-70 mol ~ $ nonamethylene terephthalamide and 80-30 mol- # dodecamethylene hexahydrο-terephthalamide. 11. Mixed polyamide according to claim 1, characterized in that that it consists essentially of 20-90 mol- $ undecamethylene terephthalamide and 80-10 mol- # undecamethylene hexahydro-terephthalamide. 12. Mixed polyamide according to claim 1, characterized in that it consists essentially of 60 - 95 mol% dodecamethylene terephthalamide and k0 - 5 mol% hexamethylene hexahydro-terephthalamide. 13 * mixed polyamide according to claim 1, characterized in that that it consists essentially of 30-95 mol- ^ dodecamethylene terephthalamide and 70-5 mol- # Nonanethylenehexahydrο-terephthalamide. Ik, mixed polyamide according to Claim 1, characterized in that it consists essentially of 95-50 mol-56 dodecamethylene terephthalamide and 5-50 mol- # dodecamethylene hexahydroterephthalamide. 15. Use of a mixed polyamide according to claims 1-14 for the production of shapes, preferably threads, Fibers and films. 009882/2124 16.Use according to claim 15 for the production of moldings by injection molding process. 009882 / 212A Hi Blank page