DE1570259A1 - Process for making polyamides - Google Patents

Description

Folder 20153 - Dr _e F / hr
Case Bo 423

DESCRIPTION to the patent application of

BEITISH NYLON SPINÄERS LIMI2SD, Pontypool, Momouthehire, Great Britain,

concerning;
"Process for the production of polyamides" »

Priority : April 21, 1964 - Great Britain

The invention relates to synthetic elastomers and to a method for producing the same and in particular to those elastomers which consist of H-substituted polyamides with a special degree of U-substitution, soirie on from it produced threads and a process for producing the latter

Linear polyamides made by heating substantially equimolecular proportions of a diaraine and a dibasic Acid are synthesized, for example from hexamethylenediamine and adipic acid, are usually high melting point, crystalline Compounds that are insoluble in the usual solvents «The high degree of crystallinity of such polyamides is attributed to the well-developed polar coordination

009813/163?

BATH ORIGINAL

duroll hydrogen bond, which is present in these compounds (see, for example, the article by Biggs, Frosch and Erickson in Industrial and Engineering Chemistry, Vol. 38, No. 10). It is known that the progressive replacement of the hydrogen atoms of the JLaid groups. of polyamides causes a change in the original properties of the polyamides through Khlenwaaseratoffgruppen. In particular, the flexibility of the polymer increases with a certain degree of substitution of the hydrogen hydrogen atoms (also referred to below as merely degree of substitution), so that it results in a gumai-like elasticity. However Vie given in the aforementioned article, the increased Bieg is "stsüceit achieved at the expense of certain other properties, for example _o the Wassereopfindlichkeit, the general stability, especially with regard to ordinary Lösungsaittel, and Erweiohungepunktee which Bigenschaften reversed bit of the Srhöhung the H-substitution to grow.

In the search for synthetic elastomers for the production of elastic adenes, attention was drawn to I-substituted polyamides during the 1940s and early 1950s because of the guaBni-like flexibility mentioned above, which they provide with an "adequate H -Degree of substitution · Despite considerable research, which occurs through a number of very tangible publication occasions, the N-substituted polyamides as far as is known have not achieved any significant importance in the manufacture of elastic threads · They certainly do not have that of the possible attractiveness of the fabrics In this task, the importance given to the bait of the "angel an success in the application on page 397 4er 4" edition of the Buohes Han-Kade fibers by E * W. Mcnorieff, e avenem lieited at Heywood and Company, London " 10 «3, co-opted irfe. _BAp original γ 009113/1637

μ * 3 ■

The reasons for the past failure of N-substituted Polyamides for the particular application are undoubtedly diverse and complex »but it is assumed that a a major factor which reduced the usefulness of N-substituted polyamides as elastic threads, the reduced softening point and the greater water sensitivity and solubility was in common solvents, which occurred as a result of the required degree of N-substitution, to the favorable to achieve elastomeric properties in threads «, The properties the softening point, the chemical stability. to solvents and - the hydrolytic stability, the latter reflect the sensitivity to water are critical with respect to the use of threads in fabrics with regard to the ability of such fabrics to be subjected to repeated washing and ironing and those associated therewith. to withstand standing processes such as bleaching and cleaning «

For an explanation of the state of the art with regard to the relationship between the degree of N-substitution and the elastomeric property, reference is made to an article by WH "Charch and J" C. Shivers pointed out with the Xitel Elastomeric Condensation Block Copolymers, on pages 536 to 540 in the Textile Research Journal, July, 1959, in which on pages 536 to 537 H-substituted polyamides with various degrees of H-substitution are described, which are described by reacting sebacic acid with hexamethylenediamine, N-isobutylhexamethylenediamine and S, H -diisobutylhexamethylenediamine in various ratios. The curve shown in FIG. 1 of the relevant article shows the changes which occur in the progressive substitution of the amide hydrogen atoms from 0 to 10O i * , the N-substituted polyamides with elastomeric properties having a degree of substitution of the amide hydrogen of 40 to 64 % . "

009813/1637

Si has now been found 'that: blank erreiohen calibration favorable elastomeric properties oit H-sutstitulörten Polyaniden in which 15 groups of up to 34 + the Aaldwaeeeratoffatoae by Eohlenwaseeretoff or substituted hydrocarbon substituted "are, in particular with alkyl groups and leave from these N-substituted polyamides passendenreiee to By means of a SchmelB spinning process, elastic threads are obtained, in which the relatively low degree of H substitution results in a higher softening point, greater resistance to hydrolytic attack and better general chemical stability to common solvents, compared to H-substituted polyasides with a higher degree of H substitution.

Also rewarded are elastic threads of H-substituted polyamides with an M-substitution degree of 15 to 34 % compared to other synthetic elastonic threads, in particular polyester urethane threads based on aroaatic diisocyanate, due to advantageous properties. Thus "· £ · the S-Bubetttierte polyamide threads retain their elastic Mgensohaften Οχιά their whiteness under the influence of light to a higher degree than the last-genanate fabric ·· From β earth" these become yellow when bleached with old hot latent chloride solution and other bleaching agents and age «atm, which at then the first-mentioned substances is not the case.

! • before the invention is described in more detail, should still l «griffsb« «ti * Bungen listed earthen, the» ur dar n «uart4 # ee nuten i * following rervMaet w * rd« i

The extensibility compensates for the enlargement of the "length" ouch «· - drÖokt in Pro sent en the original length, do die die f ^ Ldeti can be stretched, Wed they tear.

009113/1637 BADORiGlNAL

strength

The strength is the breaking load of the threads in grams per denier,

Initial module

The initial module of the threads should be the quotient from the speaifisohen Tension (specific stress) and der.Dehnung (strain) »if the latter is one percent of the original length, bejseiohnerio (Specific voltage is defined on page 138 of the Book (Textile Terms and Definitions ", 4th edition, des Textil Institutes; Manchester, and can be expressed in grams per denier will).

Elastic recovery

The elastic recovery of the threads is expressed by the Breakage, obtained by dividing the length the threads are stretched when tension is applied by the length to which the threads tighten again after the tension is removed, is given · The fraction is usually given in percentages. ^

Work rest

The work recovery of the threads is expressed by the breakage, by dividing the energy expended to stretch the threads when tension is applied by the energy required to retract the threads to their original dimensions when Haohlasse »the tension is given recovered energy» The fraction is usually expressed as a percentage

The tension decay of the threads is expressed by the breakage obtained by dividing the amount required to stretch the threads by a given percentage of their original length

00981 3/1 837

Tension required by the sub-eyes of the same stretch 8p * nnung do Sud · a vorbeetiaaten time given lot, whereby the ·· stretch is maintained during the entire time. The fraction is usually given in proe values.

Relßteoweratirr

This means the lowest temperature at which the pads tear "if one touches one bit at this temperature placed on the smooth surface

Resistance to light

The light resistance of the threads is tested by exposure to light the thread bits of a lenon arc lamp wound on a strip during 300 hours · They have elastic properties and color der'Jaden become, gate and beetimt after the exposure.

'i. ■ '■ ■

Blelohbefltftndigkait

Si · Bleiohbestaajigkeit of the threads is determined by immersing it for 43 min in an aqueous solution containing ₉ O I Oew.-Jt latriuaohlorit and 0.5 * whether contains per liter Eieeaaig at 85 ⁰ O ₁ so DIE Löeung a pH Vert of 4 has. You parbe of threads is bestiumt before and after the lead treatment »

The inner Auedruok · Viscosity denotes the dual logarithm of the quotient of the viscosity bsi 25 ⁰ C a solution of 0.5 0EW "-0T per Voluasn of polyamides, which in. 90 wt. ** a"? aqueous PhenolÖBTfng is dissolved as a solution, by the Viekoii ^ ät the solvent at the same T. The Vietoeitätsmeseungen are in an Oetwald ~ Viske * i * ete * auee «leads ·"'^'' ^!? '

■ -fi ■ ... _: «BAD ORIGINAL

- (X- i

The expression "degree of substitution" means "of dl · in Prosen · * th expressed looks! iron AAid hydrogen atoms, dl · through Hydrocarbon or substituted carbon dioxide groups in which polyamide is replaced »

The term “threads” also includes yarns, fibers and the like, except for continuous adene, with the exception of other specified.

The products according to the invention therefore form! "- substituted polyamides" in which the H-Substitutionagrad "Irish 15 and 34 H is, whereby threads or the like can be produced from these polyamides which have a strength of at least 0.2 g per denier, Preferably clay at least 0.4 gp * o denier, an elastic recovery of at least 85 % with ZtjgrunAelegang τοη 50 % elongation, a work recovery τοη at least 40 Ji on the basis of τοη 50 Jfc elongation and no infiltration or xenon arc when exposed When bleaching with sodium chloride in accordance with the tests described above for light resistance and lead-acidity.

The subatituated poles and those made from them Threads kSttmen consist of segments with a polymer τοη low molecular weight, what with Toller Polymerieatiom, So that at a fasea ^ ilA foreign lemopolymer represents a relatively high soteelsfemlct att * v * Uen wttrde, sewte «m« m «es tHgmemtem, who in a lüaioher way as Tim a TolUHaHj »#ljrmerieiert Homopolymer τοη mitM teseelsvernkt ssgileWith mmtssehen. can be. The first named are in the skin friction Segments ale hardness segments and the latter as soft segments

009813/1637

BATH

refers to »and the related expressions appearing in the description are to be understood in this sense *

G-emäfi a further feature of the invention, the hard, present in the H-eubötituierten polyamides segments and yarns made therefrom from lactams of Aminocarboacyleäuren prepared, and the soft segments of the polyamides mm N-aubetituierten Aminocarboiylsäuren having at least 7 carbon atoms.

Lactams, which are preferable to the threads both in terms of availability and the desired textile properties, are caprolactam, enontholactam and caprylic lactam.

The invention also comprises a process for the production of spinnable, synthetic substituted polyamide elastomers, in particular duroh melt spinning in filaments, using heat and in the presence of a polymerization catalyst a reaction between a lactam, an amino acid and an N-substituted mega-aminocarboxyl acid with At least 7 carbon atoms are brought about, the reactants being brought together in such amounts that the molar ratio of the omega-aminocarboxylic acid to the lactam component is between 0.177: 1 and 0.50: 1. This area the molar ratios of the reactants in question H-substituted polyamides with the degree of H-substitution that corresponds to the creates a unique combination of properties that characterize the threads made from these fabrics.

The upper limit of the Η-substituted Ctoega aminocarboxylic acid measured in molar measure is just slightly lower than that theoretical value for a degree of H substitution in the

009813/1637

Polyamide of 34 % is required, since small losses of lactam through volatilization and incomplete reaction have to be accepted.

A preferred range of omega-aminocartoic acid to the lac-bam, expressed in molar hatred, is, from the point of view of xünachena- * 'werfer textile properties in the threads made of such U-substituted polyamides, a ratio between 0.25 s 1 to 0.43 * 1 «This range corresponds to an approximate degree of H substitution of $ 20 to $ 30> *

That the polymerization of a lactam and an H-substituted Omega-^ minocarbozylic acid N-substituted polyamides with valuable elastomeric properties and a lower N-substitute degree of tution, when it was previously regarded as compatible with the properties in question, can be explained by the fact that in the Laotam aminocarboxylic acid system there is a division of the blocks of hard and soft segments goes with entrainment of a certain part of the lactam component ale the hard segment in the soft N-substituted C & ega-aminocarboxylic acid segment "

However, the effectiveness of the inventive muddled depends in no way on the correctness or otherwise from the above explanation, the iat theoretically be regarded as purely _o

If, from the standpoint of availability, the most suitable lactams to be used for the method according to the invention epsilon-caprolaotam, omega-snontholactam and omega-capryllactam, mixtures of these lactams can also be used.

In the method according to the invention, any H-

009813/1637

BATH ORIGINAL

use substituted Ctaega-Aminooarboxylic acid, which toehr intermolecularly condensed as intramolecularly. Favorable as H-substituted omega-aeinocarboxylic acid is an aliphatiache (Mega aninocarboxy acid of the general formula

HSH (0H ₂ ) _x CO ₂ H

where ι J> 6 and R is a hydrocarbon or substituted Kohlenwaeeeratoffradikal «

Suitable substituents on the nitrogen atom are for the purpose of the invention ever.B. the groups: alkyl, cycloalkyl or aralkyl. Suitable alkyl and cyoloalkyl groups are the groups Methyl, ethyl, propyl, ieopropyl, butyl, xsobutyl, secondary Butyl, Aeyl, Deoyl, Cyclohexyl or Hexadeoyl called. An example of a suitable aralkyl group is the Geieia-Pheiiylpropfjgnippe.

Mixtures of N-substituted substituents can be obtained Use carboxylic acid. In the case of eolohe rent, they can Aainoic acids different polymethylene chain lengths and / or have different alkyl, cycloalkyl or aralkyl group neubetituents

The polymethylene chain can also contain side chains or Heteroatoms, like ».Β * oxygen, sulfur or silicon, or the polyethylene chain can be interrupted by a cycloheyl group

Example of suitable Os »ga- * Mt nooarboyl acids: (swi κλ bsi I TinhentuTirthirir ■

BATH ORIGINAL

009813/1637

(taegesminoundecanoic acid and Omegaaninododecanoic acid »

When producing the ISF-substituted polyamides, the laotame and the Η-substituted omega-aminoarboxylic acids in any one brought together in the usual way, provided that the Pick ratio of. Reactants within the specific Grease lies, cLho e.g. that the temperature is high enough for a reaction o So that the lactarns take part in the polymerization reaction take part, it is necessary to use small amounts of a polymer! aationskatalysators apply «, Suitable polymerization catalysts are neutral and acidic catalysts, as they are for the Polymerization of Laotams, are known. For example such Catalysts are strong mineral acids such as phosphoric acid, Sulfuric acid or hydrochloric acid. Examples of neutral catalysts are dicarboxylic acid salt of the aliphatic diamines, for example Hexamethylene dianmonitunadipamide, Octamethylene diamaoniTaaseDaoaoid, Amino-carboxylic acids, such as omega-aminocaproic acid, omega-amino-undecanoic acid and water.

An acidic catalyst, such as phosphoric acid, also helps Polymerization of the aminocarboxylic acids. The polymerization * Catalysts, which also include the catalysts for promoting lactam polymerization and / or Cteega-aminocarboylic acid polymerization, are generally in amounts Between 0.01 to 2% - ^, Torssugweise from 0.05 "to 0.2% by weight based on the weight of the polyamide-forming components.

One way of carrying out the method according to the invention is to see that the lactam is mixed with the N-substituted omega-amino-arboxylic acid and the mixture is then

0 0 9813/1637

1S70259

Was a polymerization catalyst until about 250 ⁰ O it is necessary, at which temperature the reaction temperature is kept as long as possible. To increase the intrinsic viscosity of the oil, that is, the molecular weight of the polymer is generally preferred, Maintain the sobmelee in the vacuum for a further period of time at a bucket temperature of about 250 to 300 ⁰ ".

The response is predicted under a. inert atmosphere executed, ZoB. under nitrogen, about an oxidation of the polymer coraponents also avoid »An effective mechanical mixing of the partners is very desirable

The process according to the invention differs in an advantageous manner from the previously described process for the production of N-substituted polyamides, in which a dibaoic carboxylic acid is reacted with a mixture of primary and secondary diamines, in several respects, possibly on What is most significant is that the polymer produced has a better uniformity of properties, apart from the general simplification of the work with one rather than three reactants.

Another advantage of the process of the invention is that of the generally less volatile nature of the amino-carboxyl acids compared to diamines, is that the tendency to change the degree of N-substitution by Evaporation of the component in question decreases 1st «as each Molecule of amino-carboxylic acid one amino group and one Has carboxyl group, possible evaporation of this component, if it occurs at all, does not change that stoichiometric ratio of the reaction mixture in this

009813/1637

Respect is based on analyzes of the N-substituted polyamides of the invention confirms that the degree of N-substitution is in reasonable agreement with that based on the reacted Monomer amounts will be expected to be »

Additives can be added to the reactants used to produce the M-substituted polyamides according to the invention are »pigments, plasticizers,« delusterants (delusional) and / or stabilizers »

In certain cases it may be appropriate to include a crosslinking agent in the. To give polyamide-forming reaction mixture »Suitable Crosslinking agents are bis-gamma-isobutyl-aminopropylamine, Bis-Qamraa-aminopropylamine and trimesic acid (benzene-1,3,5-tri-carboxylic acid)

The H-substituted polyamides according to the invention preferably have a molecular weight corresponding to an intrinsic viscosity of 0.5 to 1.5 _o

A preferred method for producing threads from the N-substituted polyamides is the melt-spinning process, and the invention also includes the production of the threads and the threads themselves from these materials _e As a method to any arbitrary melt spinning method is <> Me thus manufactured Threads have elastic properties, a well-developed general chemical stability, especially with regard to common solvents, a low sensitivity to water and accordingly a good resistance to hydrolytic action, and also a high resistance to bleaching agents, when exposed to a Xenoxi iron lamp or when bleached with B sodium chlorite according to

0 0 9 8 13/1637

BATH ORIGINAL

the light resistance or bleach resistance test described above does not show any color bleeding. As a precaution, the threads are pulled to two to five times their original length when they are solid. This will the elasticity of the threads is reduced and their loss of tension and the elastic properties are improved and the toughness (tackiness) of the threads decreased. The south are usually subjected to tempering prior to use, and this can be done in the catfish happen that the threads of a hot wet treatment be undersogea, e.g. old boiling water during the tinting or fieinigena before commercial use.

A suitable tempering treatment comprises treating the threads with hot water for a certain period of time. The threads wound on a bobbin are immersed in water at 6O ⁰ C and the temperature of the water is gradually increased to 10O ⁰ C, for example during 1/2 to 3/4 hours rather remain free and essentially separated from adjacent threads,

In certain cases it is desirable to use the threads preferably immediately after solidification with a non-stick agent treat, with about finely divided talc being particularly suitable is. It is generally dusted up.

The threads made of H-substituted polyamide are used for manufacturing suitable for so-called corsetry, such as corsets »elastic cover, e.g. sweaters, ski pants and also for medical elastic hosiery and bandages ,,

BIe also lousy themselves in the manufacture of woven and Sohwimmersuits, stockings, bras and pajamas worked

009813/1637

use "The threads are equally suitable for use in]? ύηα of staple fibers, in particular if they are separated from wool, cotton or polyhexamethylene adipamide" The threads made of N-substituted polyamide according to the invention can also be incorporated into elastic yarns were "Z ₀ B ₀ by introducing the same all continuous threads together with one or more strands of staple fibers, such as polyethylene terephthalate, wool or cotton, in a conventional spinning" or drawing frame ", in the form of staple fibers or continuous fibers or yarns made from them can the Η-substituted polyamides be used for the production of non-woven fabrics of various types «,

The N-alkyl substituted polyamides are also suitable for Manufacture of schmela-spun hetero threads, from which they form one component while the other component (s) one different fiber-forming polymer. As an elastomeric component, they can be unique to heterofilaments and give useful properties «,

The invention is additionally described below with the aid of examples

example ]

438 s of H-IBObutyl-toega-aminoundecanoic acid are mixed with 565 g of epsilon-caprolaetam in a molar ratio of the components of 0.333: 1 or _o serves the lactam "

The mixture was placed in a 4 l autoclave which

009813/1637

■ The nitrogen has been purged and sealed. The temperature of the Reaktionsmisohung was raised einea.Oiii ^ testoffuberdrück gradually to 285 ⁰ C "The mixture t * billion> feei the same temperature for another 2 hour s uiagerührt. ll & read this time the pressure was reduced in the autoclave to A1aioßphäreii & jerk and the reaction mixture then for 3 hours at a temperature of 285 ⁰ C under a vacuum VOA 10 on fig held was then allow the mixture under nitrogen of atmospheric pressure to cool ,,

The polyamide produced, which has about 25 # of nitrogen atoms Isobutyl substituents had a corresponding degree of 5 substitution of about 25 # »had an intrinsic viscosity of 0.783ο

The EF-substituted polyamide was processed into five mden in the melt-spinning process at a temperature of 22O ⁰ C with a total denier of about 450 _o J? Aeden were dusted with talc and then m on a spool at a speed of 40 wound per minute

The threads had a breaking temperature of 161 ⁰ C, and the Erholungeeigenschaften can be found in the following table:

characteristic Elongation in % Elastic recovery
Work rest 25 50 100 94 92 86
72 64 46

009813/1637

They filaments were then hiteebehandelt by immersing the spool on which the yarns were wound up in water at 6O ⁰ O and increasing the water temperature to about 100 ⁰ O for about 50 minutes. The heat-treated threads had the following properties:

Tenacity 0.401 grams per denier

Modulus at an elongation of 100 # 0.104 grams per denier

Elongation 722 %

Tear temperature 161 ⁰ C

Elastic recovery at 25 i> elongation 91 56

Elastic recovery at 50 # stretch 92 #

Elastic recovery at 100 1 * elongation $ 86>

Work recovery at 25 % elongation 66 &

Work recovery at 50 % elongation 65 #

Work recovery at 100 # stretch 45 &>

Example 2

A to 25 # N-substituted polyamide, which according to Example 1 was made into threads in the melt-spinning process spun and this to three times its original length

moved out"

A number of filaments were heat treated by the procedure described in Example 1. The filaments were as follows Properties listed in the table:

009813/163 7

not treated with heat would have been treated - 66% Tear temperature 143 ⁰ O 164% shrinkage through Sieve ehnnd 1 un & f, 7 % Voltage drop at 35.2 % (15 minutes) 57.4 Jl (15 mins) 25 lb stretch 49.1 % (16 hours) 50.8 % {\ S hours) Elastic recovery at 25 5 * elongation 99 * 99% KLaetieche recovery at 50 % elongation 94 % 93 * Work recovery at 25 % elongation 79 * 81 % Work recovery at 50 i> elongation 61 yr

Beipp ^ el 3

Se is an H futatituiertes Polyaaid was prepared according to Example 1, except that the initial mixture 77 g of N-iBObutyl-Oeega-Aminoundecaneäure, 136 g of epsilon-Oaporolaotam (ie the monomers varen * m molar ratio of 0.25: 1 present) , 0.2 g of phosphoric acid and 10 ml of water, and the polyaerization reaction was carried out in a 1 liter autoclave «.

The polyamide produced, * of the nitrogen atoms Isobutylsubstituenten contributed to about 20, had an inherent viscosity of 0.977 · This N-substituted polyamide was spun in melt-spinning method at a! Eemperatur of 260 ⁰ C au threads and letsstere had after an elongation of 100 * an elastic recovery of 75 * and a work recovery of 45 #

009813/1637

The experiment was repeated, but here the threads were ^{drawn out to four times their uraprün & lichen length 3} during the pulling process and then heat-treated as in Example 1. The threads produced in this way, which shrank in the 2.6 $> during the heat treatment, showed an elongation of $ 50> an elastic recovery of $ 90> and a work recovery of 53 &

Example 4

Bs, a N-substituted, it polyamide prepared as described in Example 3. except that the initial mixture 77 g of N-isobutyl-omega-aminoundecanoic acid and 68 g of epsilon-öaprolactam contained, that is, _0, the monomers were in a molar ratio of 0 , 5: 1 available

The polyamide produced, in which about 33.3 $> nitrogen atoms carried isobutyl substituents, had an intrinsic viscosity of 0.738. This N-substituted polyamide was processed in a melt-spinning process at a temperature of 260 ⁰ O into threads which had the recovery properties below :

characteristic Elongation in # Elastic recovery
Work rest 25 50 100 94 93 91
72 70 55

Example 5

12.85 g (0.05 M) Nn-butyl-omega-aminoundecanoic acid was added to 16.9 g (0.15 M) epsilon-caprolactam to form a mixture in which the molar ratio of the components was 0.333 x 1

0 09813/1637

This mixture was 0.02 si orthophosphoric acid and 0.75 β Ctoega-aminoundeoanoic acid specified, which as catalysts for the subsequent polymerization of the amino-carboxyl acid and lactams were used.

The mixture was then heated to a temperature of 265 ° C. for 4 hours with constant stirring. The semi-finished polymer was then obtained by heating in an oil bath under a nitrogen atmosphere for one hour at one temperature. Clay 285 ⁰ Cy followed by further heating for 2 1/2 hours at a temperature of 300 ⁰ C and final heating for 1 1/2 hours at 30O ⁰ C under a slight vacuum. The vacuum was released and the polymer cooled under a nitrogen atmosphere.

The polyamide produced had a degree of substitution of about 25 1 *> with the substituents on the nitrogen atoms being n-butyl groups. The intrinsic viscosity was 0.8,

Doe polyamide was then erhitst to a temperature of 22O ⁰ C and the molten polymer in Sohmels spinning process in conventional manner through a spinneret (passage 1.6 g per minute) in • ine cooling atmosphere spun where the solidification of the thread took place. After this solidification, the threads were dusted with finely divided talc and then wound onto a bobbin at a speed of 70 m per minute.

The yarn produced in this way was sold according to the in Example 1 method used heat treated. The heat treated yarn had the following properties:

BATH ORIGINAL 009813/1637

Shrinkage in boiling water strength

Aiof engfisiodul Extensibility

elaatisohe recovery after. 50 % tendon

Work recovery after. 50 lbs stretch

3.1 * 1.082 g / denier 0.2422 g / denier 654.7 # 90 # 66 *.

Other files of the yarn were drawn to three times their original lungs under different drawing conditions, and the yarn thus produced was then heat-treated according to the procedures of Example 1. The drawing conditions and the associated Qarneigensohaftan are in the below Table listed)

Drawing conditions Shrinkage »
in boiling »
water Firm
speed A ^ ¹ Tf ¹ TiIgI Ti t *
bar
speed elast.
Bx & o ~
lung
after
50 pounds stretching. & work «»
relaxing
after
50 * gene 0.43 1.808 module
g / den. 417.3 91. 67 Cold pulling 1.67 1,589 0.4188 357.5 90 68 Warm pulling • 6O ⁰ G 2.67 0.9107 580.7 91 65 Waxing 0.2541 100 ⁰ C

Example 6

16.03 g (0.07 M) K-ethyl-omega-AininoundecaneäTJjre was added to 23.73 £ Co, 21 K) Spsilon-Caprolaotam to form a mixture, s was in der'das molar ratio of the components 0,333. 1 This mixture was then added to 0.02 wl of orthophorexic acid and 0.7 g

009813/1637

BATH ORIGINAL,

• ■> ". <■ -.

- 22 -

(Mege ^ Aainoundecaneäure ale catalysts for the following Polymerization of Aaino-Carboxylelure b * w · de «! ■ wottart; The polymerization took place in the same way as in Example 5.

In the case of the “substituted polyamides produced in this way 25% (approximately) of the lmidwaeeeretoffatome by ethyl groups. first. The internal quality of the polyamide was

Sa "Polyauid was! ■ Scheels-Spianrerfahren in the occasional way at a temperature tob 213 ⁰ " u filament, bath this as gladly wound up with a speed of 70a per minute. Bas yarn was in helseea state at 6Oi ⁰ C mxt three times its original length and then auegesogen sdtieie outlined in example 1 wäreebehandelt traversed. The extracted and water-treated gain has the following characteristics:

»Consistency 1.126 g / denier

Initial modulus 0.6108 g / denier Extensibility 263.3 t Reilrteaperatur 159 ⁰ O Hastische Irholung after 50 i "elongation 91% Work recovery after 50 f stretching 59 %

21.5 g. (0.1 H) Ir ^ e ^ l-Cawga ^ AadJioundecanBaure was given "u 33.9 g, (0.3 M) Epeiloo-Caprolaote" in order to create a sensation "with the aeol ratio of the cos ^ onents 0.333 ι 1 scam. These kiechnng were O ₉ O? «1 Qrthopjwephorsmure and f.0 g CeMga-OiainoQndecaneAare as latalyeators for the subsequent polymerization of the Jälno-Carbozylsiore b« w. de »Isatssi» give Mishuag was then obtained outer continental leash during a time τοη 48 hours at 265 ° 0. Bas

009813/1637

BATH ORIGINAL

semi-finished polymer was then completed by heating in an oil bath under a nitrogen atmosphere for one hour at a temperature of 265 ⁰ C and a anschlieesenden heating during the same time at a temperature of 300 ⁰ C. The fluttering was continued during these heating periods. The shorter polymerization cycle in this example in relation to that of the preceding examples is due to the faster polymerization rate of H-methyl-Ctoega-aminoundecanoic acid compared to ethyl- and butyl-substituted amino acids «

The yarn was made from the molten polyamide that the Degree of substitution was 25 #, processed in the melt-spinning process «The drawn and undrawn yarn had after Heat treatment according to Example 1 the properties given in the following table:

Drawing condition
gene Firm
speed
g / denier At first Stretchy Elaet.
recreation
after 509
strain Work
recreation
after 5O? 6
strain not sucked
but with valley
cumulatively pollinated 0.5281 module
g / denier speed eg 56 sucked cold
(15 ° CT on the
3 times the ur
initial
length 1.0621 0.1309 690.7 92 56 sucked hot
(60 ⁰ C) on the
3 times the ur
initial
length 1.1616 0.3346 337.3 92 55 0.3346 326.0

009813/1637

BATH ORIGINAL

Example 8

The production of the N-substituted polyamides according to Böiepiel 7 was repeated, except that the ingredients were chosen in the following amounts:

Component quantity ,

N-methyl-Qmega-aminoundecanoic acid 21.5 g (0.1 M)

Epsilon-Caprolactam 25.99 g (0.23 M) Omega aminoundecanoic acid 0.5 g

Orthophosphoric acid 0.03 ml

The N-substituted polyamide, "in which 30 f <> of the amide hydrogen atoms were replaced by methyl groups, had an intrinsic viscosity of 1.31 o It was processed in the melt-spinning process at a temperature of 270 ^° G to form elastic threads, which with a Speed of 70 m per minute were wound «,

Drawn and undrawn yarns were made from the threads, those according to the varnish treatment described in example 1 * procedure showed the values given in the following table «

Drawing conditions

Pestig-

speed

g / denier

At first-

module

g / denier

Extensibility

Elast · Recovery after $ 50 strain

Work recovery after $ 50 strain

not pulled

cold sucked (15 ⁰ C) to 3 times the original. length

hot drawn (60 ⁰ O) to the 3-fold of the ureprUngl »length

0.669 0.772

0.498

0.177 0.186

0.104

546 476.7

506

93 94

94

58 63

61

009813/1637

Examples 7 and 8 show the utility and utility of the invention, since they describe the preparation of !! - substituted polyamides in which the substituent is a methyl group represents, as well as the production of yarns with elastic properties of approximately the same size as those in N-substituted polyamides, in which the substituents form an ethyl or butyl group. This is in contrast to the previous expertise in connection with the · influence of Substituent groups affect the elastic properties of N-substituted polyamides since, in the prior art, methyl group substituents are abnormal with respect to other alkyl groups would have to be, since η-polyamides are not noticeably elastic Should have properties

Example 9 .

13.55 g (0.05 H) N-isobutyl-omega-aminodidecane acid was with 16.95 g of Bpsilon-Caprolactam mixed, with the Hol ratio of the components was 0.333 s 1. This mixture was 0.02 ml Orthophosphoric acid and 0.5 g of omega-jtainoundeoanoic acid added as catalysts for the subsequent polymerization of the amino-carboxylic acid or laotam

The mixture was then heated for 4 hours at 265 ^° C. with constant stirring. The semi-finished polymer was completed by heating in an oil bath under a nitrogen atmosphere for one hour at 285 ^° C. and further heating for 3 hours and 20 minutes at 300 ^° C. · The mixture was stirred during these heating periods.

The thus produced N-substituted polyamide had about a degree of substitution of 25 $> and an intrinsic viscosity of 0.98 "was the Sohmelz spinning process at 220 ⁰ C to threads comparable

009813/1637

that works at a rate of 35 β per minute a bobbin were wound up «Dae sponnene earn had the following major liability:

Strength 0.5679 g / denier Initial modulus O ₉ 1214 g / denier Elongation 480.8 lbs Elastic 'recovery after 50 pounds stretching 90 jL Work recovery after 50 pounds stretching 56 j6

SLn rope of the yarn was made according to the procedure τοη Example 1 heat-treated and then starred certain properties of the sany, which are listed below;

strength 0.6180 g / denier

Beginning of 8 * or 0.3045 f / denier Elongation 297.7 J * Elastic recovery after 50 J * stretch 95 lbs Work rest »after 50 i» stretching 59 i » Voltage drop after 30 minutes 43 pounds Voltage drop after 16 hours 50 i »

Sin other rope of the yarn of its original length was drained before the heat treatment was carried out in the above manner at a Teaperatur from 6O ⁰ C to three times. The heat treated and soaked yarn had the following properties:

strength 1.082 g / denier

Initial modulus 0.7759 g / denier Stretchability 180 % Tear temperature 17O ⁰ C Elastic recovery after 50 % stretch 93 lbs Work recovery after 50 % stretching S3%

009813/163?

BATH ORIGINAL

- 27 -

Voltage drop after 30 minutes $ 4315> Voltage drop after 16 hours 46.5 %

Example 10

25.7 g (0.1 M) N-isobutyl-omega-alinoundecanoic acid were added 36.1 g (0.3 M) enantholactam added to make a mixture form in which the molar ratio of the components 0.333 * 1 *> β-trugo This mixture was 0.04 ml of orthophosphoric acid and 1.2 g of omega-aminoundecanoic acid as catalysts for the subsequent Polymerization of the aminocarboxylic acid or «, the lactam added.

The mixture was then heated ^{at 265 °} C. for 4 hours with constant stirring. The polymerization was -during one hour at 285 ⁰ G and ansehliesseixdes heating for 3 1/2 hours at a Semperate, ¹ of 5Go ⁰ C & varYolXgtäE IGTE by heating in an oil bath under a nitrogen atmosphere, the mixture was continuously stirred during this heating period ©

In the H-substituted polyamides produced in this way, 25 # of the amide hydrogen atoms were replaced by isobutyl groups and the polyamides had an intrinsic viscosity of 1.02 °. The polyamide was processed into threads ^{in the melt-spinning process at a temperature of 240 ° C.,} which were wound onto a bobbin at a speed of 70 m per minute »The spun yarn had the following properties:

Tenacity 0.2516 g / denier

Initial modulus 0.1069 g / denier

Extensibility 440 pounds

Blastic recovery after 50 % stretch 90 #

Work recovery after $ 50> stretching $ 64.

009813/1637

Part of the yarn was heat treated according to Example 1 and certain properties of the same "are determined. Values are below listed:

Tenacity 0.9234 g / denier

Initial modulus 0.3860 g / D © nier

Elongation 406 %

Elastic recovery after 50 stretch 87 #

Work recovery after 50 % stretching 49 ##

Further sections of the yarn were drawn either cold or hot to three times the original length before being heat treated in the same catfish as described above were ο The drawn and heat-treated yarns had the following Characteristics:

cold drawn (15 ⁰ O)

strength 50 % elongation 1.999 g / denier Initial module ί stretching 1,798 g / denier Tear temperature 168 ⁰ C Extensibility 122 % Elastic recovery after 85 yr Work recovery after 50 s 47 * hot sezoÄen (6O ⁰ C) strength 50 i » elongation 1,967 g / den ± er Initial module £ elongation 1.945 g / denier Tear temperature 171 ⁰ C Extensibility 101 # Elastic recovery after 85 Ji Work recovery after 50? 45 %,

009813/1637

Example 11

A !! «- substituted polyamide was produced in the same Way as in Example 10, with the exception that the polymer! "· tied mixture 12.9 g (0.05 M) N-isobutyl-omega-aminoundecane acid, 2.7 g (0.1 M) enantholactam, 0.02 ml orthophosphoric acid and 1.0 g of Csnega ~ aminoundecanoic acid

In the polyamides produced therefrom, about 33 1/3 # of the amide water had only been replaced by isobutyl groups. The intrinsic viscosity was 0.82. The polyamide was ^{spun at a temperature of 204 °} C. in the Schmela spinning process to form threads which were wound up in the form of yarn at a speed of 70 m per minute. The yarn spun in this way had the following properties:

Tenacity 0.3644 g / denier

Starting modulus 0.1813 g / denier

Extensibility $ 337.3

Elastic recovery after 50 # stretch 86 %

Work recovery after $ 50> stretching 45 %

Example 12

77 g of N-isobutyl-omega-aminoundecanoic acid and 127 g of omega-caprylic lactam were added to form a mixture in which the molar ratio of the components was 0.333: 1. 0.2 g of phosphoric acid and 10 ml of water were added to this mixture as catalysts for the subsequent polymerization of the omega-aminocarboxylic acid or lactam.

The mixture was placed in a 1 1 large autoclave, the was provided with a stirrer, and the autoclave was then flushed with nitrogen and sealed. The ^ temperature of the

00 * 331 "* / 1 B 3.7

~ 30

Reaction mixture was raised mater a stickst of fUberdruok gradually to 285 ⁰ O. The mixture was stirred at the same temperature for 2 hours "During this time the pressure in the autoclave to atmospheric pressure was lowered and then the Reaktionemiechung · held for one hour under a Vakuua of 10 mm Hg at 285 ⁰ C It was then mix under a Nitrogen atmosphere cooled

The polyamide made from it, which is approximately 25 pounds of the Nitrogen atoms bearing isobutyl substituents had an internal one viscosity of 0.992 *

This N-Bubstituierte polyamide was processed la Schmelg-Spivta'-Cahren at a temperature of 248 ⁰ C in 5 filaments having a Gesamtdeniersahl of about 250 · The filaments were dusted with talc and then wound on a bobbin at a rate of 70 A per Out ·

The threads were then heat-treated by immersing the bobbin on which the threads were wound in water at 60 ^° C. and gradually increasing the temperature of the water to 1CO ⁰ O over 30 minutes. As a result of the heat treatment, the threads stretched by 1 , 3 pounds of their length. The heat-treated filaments had a Reißteeperatur of 142 ⁰ C ₉ an elastic recovery after 50 £ 87 £ elongation of work, and a recovery of 46 3 * ·

Example 15

An N-substituted polyamide was prepared in the manner described in Example 12, with the exception that the initial mixture contained 77 g of N-isobutylVOmega-aminoundecanoic acid and 99 g of Ctaega-capryllaotam, ie the monomers in a molar ratio of O ₉ 428: 1 were present.

009Π11 / 1Β37

Dae produced therefrom polyamide, wherein about 30 # of stickst off contributed atoms Isohutylsubstituenten had an intrinsic viscosity of 1.032, this N-substituted polyamide was processed in melt-spinning process "at a iemperatur of 235 ⁰ C au FSden, after the dusting et with talc at a rate of about 140 were wound per minute "The yarns of a similar heat treatment were then subjected as 5ο for example the threads thereafter showed a breaking temperature of 139 ⁰ C and after 50 fi stretching an elastic recovery of 90 # and a work recovery of 49 % o

Bine other amount of Η-substituted polyamides was processed in a similar manner but was extracted the filaments after extrusion on the Breifaclie their original length and then wämehefc ^ mdelt "The yarns shrank by 2.1 # their original läSigß after Wärmeöeh & ndl ^ ago The heat-treated threads had a breaking temperature iron 133 ⁰ G and after 50 $> stretching an elastic recovery of 87 $> and a workability recovery of 49 %.

Example 14

As an example of the stability of N-substituted polyamides according to the invention to a large number of chemical substances, their sensitivity to water and their resistance to bleaching, the properties of the threads are tabulated below after they have been subjected to a number of specific chemical treatments with the purpose of the threads to bleach, "to make a comparison, are the values obtained for the same properties at similar threads listed that ο varen however, been treated in any way, the threads were in all cases au 25 & K-substituted polyamides of same nature as the N-substituted ones

0 0 9813/1637

Pale pH 2.5 4th 10 Time ^ ernp « Vaschen Firm module Stretching J Blast tables 92 Recreation / work retention 5 $ stretching colour } White ι regulation Chlorite lead Min » C. speed at barko • $ 00 stretch. 1 g / 1 ITaClO ₂ I. g / Den, 100 fo 93 ÖC $ Dehn. 65 η 4 g / 1 lemons
acid j Dehnfj. 50 control I. 5.5 0.436 0.079 650 89 67 (unbleached) Chlorite bleach 51 modified 1 g / 1 Sodium hydro 30th 60 0.398 0.102 608 89 HaClO ₅
0.5 cfi3 / i phoephate TK Glacial acetic acid Addition reu then 3 cm Vl least «
water 96 η O ParesBig- O acid; Sodium hydroxide 7C CD 0.25 g / 1 10 g / 1 50 OO
Ca) Fatriumper » 45 85 η 0.438 0.100 699 94 89 η borate CD 70 uO 54 30th 85. H 0.443 0.119 625 96 94 π • 70 55 60 80 warm 0.419 0.097 628 91 Wasaer

Polyamides of Example 1 and 2 were also made in the same way

Example 15

To the relatively good stability of the elastic H-substituted Showing polyamide threads according to the invention to light is a must! different yarns according to the invention exposed to a xenon arc lamp for different times. The elastic properties before and after Exposures were then measured. »The results are in the listed in the following table. The yarns are identified in the notes to the table below:

yarn Exposure Elastic Work rest colour ■ . since (h) recreation after 50 # Deh after 50 # tion strain (O O 93 69 White 140 92 65 212 92 67 304 90 61 (2) 0 94 Sl White 140 92 61 212 91 60 304 90 58 (3) 0 93 59 White 161 92 59 198 93 57 296 93 57 (4) 0 90 66 White 101 92 63 200 92 63 296 92 62

009813/1637

«34 -

to the table

Yarn no »1 was a straight-spun (as-spun) yarn with a degree of H substitution of 25 %, produced by polymerization using the method according to Example 1 with N-leobutyl-Ctoega-aminoundecane acid and Epeilon-Caprolactaa in the HoI ratio clay 0.333 : U

Yarn No ₀ 2 was made of the same S- "ubstituierten vie polyamide yarn no. 1, but the yarn was drawn home at 60 ⁰ C and three times the original length stretched ·

Yarn Kr, 3 var made from the same H-substituted poly * amide like the torch-going yarns, but the yarn was heat-treated by a method according to Example 1.

Yarn Hr ₀ 4 var aas the melt spun from an H-substituted polyamide with a degree of H-substitution of about 25 ^, which by polymerization according to the method of Example 9 of H ^ isobutyl '^ lmega-aminoundecanoic acid and Bpsilon-caprolactam in a molar ratio of 0.333 sec. 1 · Bas yarn was heat treated according to the procedure of Example 1.

It can be seen from the table that even after exposure times within 300 hours the yarns were not yellowed and were still elastic «

009813/1637

Claims (1)

Claim 1 «Process for the production of H-substituted polyamides, which can be charged from the melt, characterized in that heat is applied and, in the presence of a polymerization catalyst, the lactam and an araino-garlic acid and an H-substituted carbonic acid with at least 7 carbon atoms are brought about, The itea & tion partners are brought together in such quantities that the ratio of the omega-oxylsiloxylsilurel component to the xactam component is 0.177: 1 xmä 0.50 s 1 ". Method siaeli claim 1 _s that the Iiactam is caprolactam, Enaiithoiae'fcaa _e Caprolactam or a mixture of swai or more of these lactams J «The method according to claim 1, characterized in -gekesmz @ ichn @ t ₉ claS an N-substituted aminocarlioxylic acid of the general Poxmel t is _s in which χ a great saw! which is greater than 6, and R represents a hydrocarbon or substituted hydrocarbon group * 4o method according to claim 3, characterized in that a carbon group is used as the carbon group. 5ο method according to claim 4 »characterized in that as N-substituted omega-aminoarboxylic acid an IT-alkyl-omega-amino-decanoic acid is used, such as H-M © thyl-, ethyl-, 009813/1637 BATH ORIGINAL η-Butyl "or Isobutyl-Omega-AndnoiirMiecansäure" 60 Procedures according to Address 4 'can be characterized by the fact that as Η-substituted omega-aminoarboxylic acid an N-AUiyI * omega-aminododecanoic acid is used »for example N-methyl, ethyl», n-butyl or isobutyl-omega-alainodidecanoic acid 7. The method according to claims 1 to 6, characterized in that the method for producing the base material of spun threads is carried out in such a way that the degree of H substitution is 15 here 34 #, and that the strength is at least 0.2 g / denier, preferably 0 , 4 g / denier, the elastic recovery after 50 # stretching is at least 85 % and the work recovery after 50 # stretching is at least 40% «, PATENTANWtttf (Ä.-ίΝβ H. riNCKE, DIPI.-IN & H. BOOI WPL-IHG. S. SlABQOt 009813/1637