DE1815192A1 - Improved polyxylylene adipamide fibers and methods of making them - Google Patents

Description

^PATe NTANWXlte -BOR6. DIPL.-INQ. GRAY DR. MANITZ. DR. DEUFEL

8 MUNICH 22, ROBERT-KOCH ^.

TELEPHONE 225110

lo / N - T Dec 17th, 196g

TOYO BOSEO EABUSHIKI Κ & Ι3Ή &

8, Dojima-Hamadori 2-chome, Kita-ku, Osaka, JAPM

Improved Polyxylylene Adipiziamidfaeern and Process bu their manufacture

PRIORII & q ?: Japan dated December 19, 1967 No. ₀ 81735/67

The invention relates to polyxylylene adipinamide fibers and their Manufacturing. "

The term "Polyxytylenadipinamide" used in the description and the claims refers to an aromatic polyamide, which consists essentially of a 3-condensation polymer of m-xylylenediamine or a mixture of m- / p «-xylyleadiamine with less than 30 % p- Xylylenediamine and adipic acid, which have a relative viscosity: 1 _β »1» 70 to 3 _e 60 ( ^{recovered at 25 0} O on a solution of 1 g in 100 ml of 96% dissolved polymer) _o

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Folyxylylene adipamide is a known polymer, and fibers made therefrom are commonly known as "MXB-6" fibers, however, it is well known that the thermal stability of polyxylylene adipamide in the molten state compared to other typical polyamides such as nylon-6 and Nylon-66 is so small that MXD-6 ^M fibers have not yet been made commercially.

Therefore, it is an object of the invention to overcome the problem of thermal vision Degradation of polyxylylene adylplnamide in the molten state to manage and thereby enable successful melt spinning of this substance «

Another object of the invention is to provide "MXB-6" fibers of excellent quality Establish uniformity by the thermal decomposition of the polymer in the melt spinning process caused problem is overcome and the spinning temperature and the Queuoh Uas volume are regulated *

Another object of the invention is to ^{produce excellent, novel W} MXD ~ 6 "fibers of high whiteness and without knots by melt-spinning the polymer in the presence of a small amount of a sydroxy compound."

Another object of the invention is to overcome the difficulty in drawing "ΜΧΰ-ο *" fibers.

Furthermore, it is an aim of the invention to provide ^H MXD-6 "fibers with a mechanical strength of more than 5 g / den and excellent

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recorded properties for various textile uses to manufacture.

The invention will be explained in detail in part with reference to the attached Drawings explained, these show:

1 - a diagram showing the relationship between birefringence and breaking strength of non-drawn ^M MXD-6 ⁿ fibers,

Figo 2 »a diagram which shows the whiteness of adipamide as a function of the size" r " _P, which will be defined later, and the relative viscosity of the polymer,

3 - a diagram which shows the course of the degree of whiteness as a function of the quantity ^H r "and the relative viscosity of the polymer.

Polyxylylene adipamide (referred to as ⁿ MXD-6 ⁿ polymers) was first discovered by Go Fmiston et al. In 1953 (US Pat. No. 2,766,221) and later various improvements were made to the production of the polymer and also to the production of 3-asers therefrom ("MXD -6 "fibers) (proposed US patents 2,987,506, 2 99? 463, 3,200,183, etc.). However, since the polymers have relatively poor thermal stability and are difficult to handle, in particular for the formation of satisfactory fibers, "MD-6" fibers have not previously been produced commercially.

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It has been found that, in order to obtain excellent "MXD-O * ¹ fibers, it is very important to select the correct birefringence for threads which can be melted and cooled, but not yet drawn (hereinafter referred to as non-drawn fibers). became· .

It is known to melt an "MXD-6 ^W polymer" and spin it through spinnerets to form fibers Molecular orientation stretched to improve the mechanical properties of the fibers ssu. Usually the non-stretched fiber is stretched in one or two stages on heated pins and / or hot plates. Non-stretched fiber proportional. "On the basis of this fact it has been found that with precise control of the strength and strength variation of the non-stretched fiber, stretched fibers of any desired strength and strength variation can be obtained *

It has also been found through experiments that the strength of a non-drawn fiber is related to its birefringence, as shown in FIG. The relationship between the birefringence and the breaking strength of a niolite-scattered ⁿ HXD-6 ⁿ fiber varies depending on the specific mol - ^ - content, X %, of p-xylylenediamine in the total xylylenedlamine, which is contained in the polymer »The curves A ₉ B and G apply to the respective cases: X = O Ji, X = 15 %

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and X = 27 # - It can be clearly seen from FIG. 1 that the breaking strength assumes a maximum value, regardless of the X value, when the birefringence (Δη) of the non-stretched fiber is approximately 4 × 10 -4, and in decreases substantially uniformly as the birefringence decreases. It can also be seen that with increasing birefringence (Δη) _{the breaking strength also decreases o} In this case, the greater the value of X, the greater the extent of the breaking strength decrease H, the range of birefringence of the non-verstreekten fiber is smaller in Fig x 1), jθ large the value of X is _o to satisfactorily fixed and practically usable ^M 6 ^Ü4XB-W to gain -Fasem, should the breaking strength of non-veratreckten Fibers larger than 4 g / den seln _o It has now been found that the birefringence (A ⁿ ) ^of undrawn fibers should satisfy the following equation:

2x1O " ³ i ^ n = (5? 6" iC

The breaking strength (g / den) of the "layer-drawn fiber is at a pulling rate (or draw rate) * 500% per minute in an atmosphere of 20 ⁰ G and a moisture content of 50 fa

The birefringence (^ n) of the undrawn fiber gives the Degree of molecular orientation and it varies depending on the viscosity of the polymer (ie the degree of polymerizate or the average molecular weight of the polylaeren), the spine ^ mpe ^ aturjanä the withdrawal speed bein

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Spinning time of the molten polymer. As a result of The following empirical formula was derived from various experiments and observations of these relationships:

Δη * / 0.085 x -J- + 0.25 x to "* ⁴ Mn + 70.3 - 0.25? 7 * ΙΟ *" ³ (1)

Here, Δη is the birefringence of undrawn easer, V is the spinning peeling speed (m / min), Q is the compression speed of the polymer melt (g / mm χ min), Mn is the mean molecular weight of the polymer and Φ is the spinning temperature ( ⁰ C). This formula has been obtained when the average molecular weight, Mn, is 15,000 to 30,000 and V / Q is 12 to 120. Usually Mn is within the above range, and V / Q, which determines the denier of undrawn fiber, also fits well within the above range Adjustment of the spinning temperature $ in any desired range ^ can be kept. As in the formula; is shown , the higher the spinning temperature Ϊ 1st ο, the lower Λ η With this in mind, it is understandable that if the spinning temperature becomes so high to degrade the polymer that - as shown in FIG. 1 - the Λτ. very

"becomes small regardless of X the breaking strength is uniformly decreased, as described above. Further, by increasing An au, can be made smaller. However, as shown in FIG Increase in front of «a as a function of Χ» If X is small, the upper limit value of Δη can be large, which means that the spinning temperature is low

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On the other hand, in the case of a large X, Ϊ must be to be mowed "

The key point of crystalline polymer is the temperature at which the crystal melts completely. At the melting point, the polymer is in a completely liquid state. In the real spinning process, however, the temperature of the molten polymer is set higher than the Sehmelspuiiktst '. The reason for this is that when the molten polymer is pressed through at the melt temperature or a temperature slightly above the melt, the viscosity will be so high that the thickness of the spun fiber will be uniform and, as a result, the strength will also be uneven " to this Ungleichmässigkelt liesmbauiainäem, the temperature © »» &"Iu the lower Cfrensse must be higher than the SchmelspunJrfe we put"the;! spin "temperature wis & änreih dae AnsiaaB dsa occurrence beet from * Ungleichmäasigkeiten the fiber ^ IBTS the Ergebsaies © of? Meeaung der DoppelbrechuBgsvaxiatiea (ί ^ ιι) Ewieelisn ßicht-stretched single fibers and the Bureliaesoer on? dui ^J eli SelMelzapion ?? » of ^M : .vDCD-6 ⁿ polymers (X = 27 MoI- ^) obtained, non-vera tr ect en Sinseliaser at different spinning temperatures I of 290, 280 rad 270 ⁰ G and quenching with cooling air of 0.5 ia / sec are the following:

Ϊ ( ⁰ C) variation of 4 »(CY

270 280 290

3 ^ 4

10.1 10.8

Variation of the Durclraeseere (CV £)

13.6 5.5

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Eb has been found that at a spinning temperature of 27O ⁰ C the variations of Δη and large diameter Bind. As the Kinsselfasern was found at temperatures from 270 to 280 ⁰ C by additional Einzeluntersuehungen the Ungleiehmässigkeit, the variation increases markedly below about 275 C. As a result of measurements of the same type as mentioned above? Δη and diameter for different polymers with different X values, it was found that when X = O the spinning temperature does not have to be below 265 ⁰ C »that the lower limit of the spinning temperature must be high as soon as X increases, and that at" one X should obey the following relationship below 30 %:

265 + O.33X £ T

From this it follows that with an X below 30 Mol- #, the spinning temperature T ( ⁰ G) to keep the birefringence of a non-drawn fiber and its unevenness within a desired range must be maintained as follows:

265 + O, 33X £ T ^ 290 ⁰ Co

. In the pail, however, where the molten polymer, like will be described later, spinning in the presence of a small amount of a hydroxyl compound, the spinning temperature may be to be humiliated a little.

The fibers freshly pressed through the spinning orifices are usually quenched or cooled with a stream of air. The smaller the difference between the temperature of the

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molten consequences when pressed through the spinning orifices and the temperature at which it is solidified, or In other words, the smaller the difference between the The faster the solidification of the fibers takes place, the faster the spinning temperature and the seheis point of the polymer is the probability of irregularities occurring in the coagulate. The higher the individual fibers, the larger

the speed of the cooling air flow for quenching the melted or semi-solidified fibers, "As described above, the upper limit of the spinning temperature is limited and its difference from the melting point of the polymer is not as great as in the case of nylon-6" Therefore, the unevenness occurs more likely in the undrawn fiber * The flow rate of the cooling air flow is an essential factor in reducing such irregularities. For example, an "MXD-6" polymer (average molecular weight 20,000, X ~ 27 $>) at a spinning temperature of 280 ⁰ G through a spinneret with 24 openings of a diameter of 0.25 mm with a melt Throughput of 14.5 g / min and a pull-off speed of 600 m / bin spun «. The speed of the KÜhlluftetrome (20 ° 0) was varied in this case and the variation of Δ η uftd determined from the diameter of the obtained monotonous fibers. The following results were obtained

Luftblasgesehwindiskelt variation of variation in diameter (m / sec) Δη (QY ^) diameter (CV <ß>)

10.1 5.5 2.0 2T, 5 14.3 4.0 50.2 27.1

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As a result of further and more detailed investigations of this kind, it was found that at a speed of the cooling air flow higher than 1.0 m / sec dLe variation increases sharply. As a result, the speed of the cooling air flow must be less than 1.0 m / sec to ^fl MXD ~ 6 "fibers with high quality, low Ungleichmassigkeit get au"

The above-mentioned conditions of the spinning (i.e. birefringence of the non-stretched fibers, spinning temperature, Q & a sh speed of the air stream) are particularly important for the invention. to use high-purity polymer produced with special care »

For example, it has been found äaß preferably a "MXD-6" -Polymeres ₉ is used which the following equations (2) and (3) gentigts

1 70 b

¹ ^ - »Ipei - 1_ o, 984r

where * denotes l _re i ei "6 relative viscosity which at 25 ° C on a solution of 1 g Poljrmeren dissolved in 100; ul 96 sulfuric acid ,, and r is a ratio of the number of moles of Hylonsalabeetaniiteilö (as in egg production of the polymer used would) on the sum of the molar number of said nylon salt constituents vüad of the viscosity stabilizers;

! share \ the / fcäts- /

Mo ^ number of the Ny lonsalzbestandt eile Molisahl of + Holsabl
Nylon salt stock * viscosity parts staliiliaatorea

* 0.70

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1811192

H *.

T one is the area below the transmission curve plotted against the wavelength from 340 to 80μm, which is in a Qiäarz-aellö (10 mm thickness) for ^SI MXD »6 ' ^s polymer solutions (concentration 20 g / 100 ml _for solvent: Formic acid) was measured. Cup. ^ q ₀ an area above this transmission curve iax. (see Figo 5) =

Xn of the Jofoen geBamaten equation (2) shows the right side

(111 - i iV> Pt * \ "

JLaLL -_Jj ^ ££ _) ate öaß -at Annäherimg the size "r" to 1 (where no stabilizer was Yerrrendet can be selected) \ _v * \ ^ · ^{η e} i ⁿ e ^m wider range "ground. If r = 1, the desired polymers are those with ¹ TL ₀ -J "= 1» 7 to 3 <> 6. If, on the other hand, r is smaller ^ the range becomes ^^ ¹ * ^ «!» which can be chosen for obtaining itcb preferred polymers, narrower, xind if τ is not greater than O _t 95, the left side, 1 1 ~ * ⁹ ^ ^{: er} Barael (2) cannot be satisfied ,,

Further, the relationship between relative viscosity ϊχ t -, ^- mxa the I € close the Bndgruppen -9On "MXD-6" -Polymeran ■ untersucat lani gefiaideiij that _s if the amount of PolymerisationsreaktioEs Substantially at 0.988 ^ + O OJ held ₅₁ becomes a. Polymer can be obtained, which approximately equation _K 2y. hefrfe & tgt «

Furthermore festgesteli / c _P was that sur obtaining a satisfactory polymer by adjusting this Hwi oäer de ^{"Rsaktloneav!} Is there a process in which the condensation polymer sation d-xreh heating the reaction? mixing in a high vacuum. (^ i 'usually with Ίβτ polymerisation of nylon> »66, tern · - ■ -ri? e: cwendei;)

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should be avoided. For example, the desired Ainet can RECOVERY, not with the conventional method but producing iron "MXD-6" polymers as described in US-AueiührungelDelspiölen PatentBoiiriften 2,766,221 and 2,997,463 heeohJ & just be effected _·:

It has been found that the desired adjustment can be effected in a process in which the polycondensation reaction is carried out in the presence of steam or water vapor in contact with the molten polymer. In this valley, there may be a pressure slightly above or below ataoephary pressure. This means that the extent of the polycondensation reaction can almost theoretically be determined from the water balance curve, such as the vapor phase and the giachmoleonic polymer in the reaction apparatus and kinetics of the polycondensation. reversible reaction (GV Schule: Z ₀ Physik, Ohem ₀ , A 182, 127t 1938) "

An aqueous lorning of adipic acid xylylandiamineala was placed in an autoclave. The balance was gradually refined while the inner bridge was kept below 4 to 10 kg / cm at 120 to 160 ⁰ O. laughing completion of the pressure rise, the autoclave was verschlössen and raising the temperature to 260 to 280 ⁰ O, and the reaction was conducted at an internal pressure of- 20 to 0 leg / cm ABG "echloe & s _o Ttae molecular weight of the resulting" MXD-6 "" Paly " eren (% _ΤΘ \ ** t> 7P) was about 10.00Oo.

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finding can be deformed *

to-adjust the values of r and ^ _rel. (d _o h _o substantially the extent of reaction) it is independent of the absolute value of η, particularly important to keep a substantial GKLeiehgewichtsmenge water in molten polymers "

If the polymerization reaction is continued until the extent of the reaction becomes higher than 0.992, side reactions of a complex nature would easily occur in the molten polymer, causing gelation and / or discoloration of the polymer. Such side reactions are also related to the melt viscosity of the molten primary Link. A local side reaction is more likely to occur, especially in the case of a high melt viscosity. Even if r \ - to achieve ■ ¹ *] ¹ J? o ^ efr brought above r = 1 - 0.997

therefore, it is possible that the whiteness of the polymer becomes _{0.7 to O 9 65o}

In this connection, FIG. 3 shows a diagram with a course of the degree of whiteness of the polymer as a function of H, _r £ i uad r._ The white grain is determined by equation (3) and it is used to determine the color of the polymer itself rate au. It is needless au noted that in FaIIe ₅ that an additive such as a pigment, the polymer was added, the color of the polymer should be evaluated even after removal of such an additive _0th

In Figo 2, the areas A and B associated poly-

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merieate suitable polymers according to the invention »and the The boundary line between areas B and 0 corresponds to empirical formula (2). Area A provides polymers with

a degree of whiteness> 0.72 _o Area B represents polymers with a degree of whiteness of 0.72 Ms 0.65, while area C represents polymers with a degree of whiteness of 0.65 to 0.40 «

Ss is therefore required to improve the whiteness of the polymer im Area B to improve whiteness> 0.7, a bleach zuugebeno It has been found that this improvement the whiteness by adding 10 to 1000 ppm of a beat the hypophosphorous acid (EypOg) can be achieved.

To further improve their whiteness-ea. Hypophosphorous acid, also polymers with a whiteness ^ Q ₅ , 7 can be added. ^:

It is surprising that many other, similar connections, for example phosphoric acids and phosphorous acids in comparison to the hypophosphorous acid, are not so effective.

The compounds of hypophosphorous acid which can be used according to the invention for the above purpose are hypophosphorous acid (BLPO ₂ ) and metal salts of hypophosphorous acid, for example sodium, potassium * calcium, zinc, aluminum, manganese or Cobalt Salse. The suitable amount of the hypophosphite compound to be contained in the polymer is 10 to 1000 ppm (calculated as hypophosphorous acid) _{or the like}

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Tues © HypophpspMt "compound is preferably present or added during the polycondensation to discoloration of the polymer during && r reaction, bu vantteidan atoä ensure gleiohmäasige distribution" However, it is also possible that Hypophospliit-Verblndung eum time of SohmelBens of the polymer before Shaping euzv ^ just.

In comparison, the degree of whiteness or the coloration of polymers how these are distinguished with the naked eye, the following:

Whiteness Färjjung when viewed

(ΐ / ΐ) with the naked eye

> 0.7 colorless

0.70 - 0.65 Slightly yellowish

0.65- - 0.60, slightly yellow

<0.6G yellow.

As is from ά & ν preceding MSasramg © rsiehtlieh it advantageous that a wesentlicfe © Ä @ Gl @ feg © © iffichtBm length ssumlndeet of water at the melting temperature of the polymer in this dee should be present. For shaping, such a polymer is melted again as such or in the form of chips, which is therefore carried out in the presence of Hasser. However, if the water in the polymer exceeds a certain amount (ie 0.5 mol / kg polymer), bubbles will appear In the polymer melt or in the fibers pressed through the spinning orifices, it was found that this difficulty was caused by at least one rope of water through a non-volatile one

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Hydroxyl compounds can be overcome. Amines can Not to be used as they prevent gel formation, however not the discoloration * Preferably the hydroxyl compound is present in the polymer at the spinning temperature in an amount of 0.05 to 0.7 mol per kg of polymer.

Examples of hydroxyl compounds ^ are: aliphatic ^ alcohols, for example propyl, butyl, octyl alcohol, ethylene glycol, Glycerin, pentaerythritol, neopentyiglycol, pyrogallol or cyclobexyl alcohol; Saccharides »for example glucose or Cellobiose and its mixtures «, it is common to use these compounds to be added as a carrier for antioxidants and pigments.

The concentration of the hydroxy compounds, which should be present in the polymer at the point of melt-spinning, should be such that they do not significantly change the equilibrium of the polycondensation at the spinning temperature.The equilibrium constant of the ⁿ MXD-6 ⁿ polymer at the spinning temperature is 5 .to 8 χ 10 · «Accordingly, the concentration of the hydroxyl compound should correspond to the water concentration which essentially maintains the equilibrium with the polymer which satisfies equation (t). The concentration of water or hydroxyl compound for maintaining a balance with the polymer varies somewhat depending on the equilibrium constant, \ ^ ι and the particular Viekositätsstabiiisator (especially if this is monofunctional or blfunktionell) "Usually, though, the amount of from 0.05 to 0.7 col / kg polymer is sufficient to prevent gel formation

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For example, the water concentration, holds the dps above equilibrium in the 'case of a polymer having dee Verepinnane rj ^ of about 2.0 at 275 ⁰ C 0.14 mol / kg poly-, Mereso

Subject to the above-mentioned conditions may be that '· ΜΧΒ-6 ~ ^η polymer extruded through the nozzle and cooled to nieht-exudes-stretched fibers in a conventional catfish herzu- »■ stellenp

The non-drawn fiber is verstreokt then to Figures 3 to 5 faohe length at 70 to 90 ⁰ C ', while the water content is kept below 4 $>, preferably desired in about 3 #> ,, Falls, the werstreckten fibers can in Conventionally, when the water content in the fibers exceeds 4% , undesirable superdrawing phenomena often occur. When the moisture absorption continues to increase, the fiber crystallizes and becomes difficult to draw. The thermal stretching and the heat setting can be carried out in a manner known per se (for example as in US Pat. No. 3,200,18; $) or the like

The quality of the polymer and the quality of the melt spinning can be rated by the number of knots in the drawn fiber and also by the ease of drawing, will". The most important factor is the absolute amount of in degraded polymer contained in the fiber o This can also be be judged by the amount of insoluble polymer, if the fiber is dissolved in formic acid. The relative measurement can be determined by measuring the fluorescence intensity of the polymer

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Solution (in formic acid) can be carried out on _{excitation with '3 o} 650 S. _o

As previously explained, the fraction "soluble in formic acid" eats a gel polymarisate, which is produced when a secondary or Nebon reaction has occurred to a certain extent.3 Even with polymers soluble in formic acid, fluorescence also occurs when an actual reaction has taken place Liato Eb is assumed that the fluorescence is caused by the presence of formed by the lifting reaction heterogeneous double bonds _o Sa has been found _s that daj3 polymer or its the rmt-arphoaphorigeii acid prepared I% ser by Addition.der compound is not only excellent in dea whiteness is but a gsriiige fluorescence! ^ enai did compared au polymers without the mentioned addition of the compound "aufweißt Therefore angenoicmen. that dieaa connection demonstration also a positive effect aur preventing occurred ans by Sekvjidärreaktionen t ₀

The knot observed in the stretched fiber represents a local, unusually thick tail with a diameter about 1.5 to 2 times that of the normal (Deil der S "aser and has a length of less than a few milliiaetars _o It is known that such knots occur in Uylon-6 and other synthetic fibers, but on the order of only 0 to 5 knots per 10 m It was common, -the conventional • 'MXD-6 "-Faern nodes in the order of magnitude of

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“Have a few hundred or a few thousand knots per 10 _m . In order to prevent the formation of pots, the presence and amount of the hydroxyl compound in the molten state is very important, as previously explained "If carefully selected polymer is used with the necessary caution" measures according to this invention, it is possible, ¹¹ MXIM! ! ¹¹ fibers with a number of knots below 15 per 10 m.

The invention is illustrated by the following examples

The final or thermally drawn polyxylylene adipamide fibers ("MXD-6 ¹¹ fibers) according to this invention have a strength which is about 1 to> g / den higher than that of undrawn fibers"

Example 1

A "ΚΚΒ-δ ¹¹ polymer! Aate with an average molecular weight of 21,000, prepared from a p- and rn'-XyIyIendiaiiin-Mischling with 15 mol $ p-xylylenediamine, was at a spinning temperature of 285 ° 0 and a peel rate of 600 m / min schmel2geBponnen "the Durchaata by the Spinnöffnungan was 14.5 g / mm 1 min _o the freshly spun fibers .wurden with air at a rate of 0.5 nt / sec chilled" water in an amount on the cooled fibers, of 2, f>f> applied by melting. The non-stretched fibers were then brought into direct contact with heated pins (at 80 ⁰ G) and a hot plate (at 180 ⁰ G) in order to apply them to the 3rd , 5-ftxche of the original length to ^ extend and finally

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181519T

at a speed of 210 m / win but derive from 'MXD-o'VPaeera.

Birefringence 3.0 * 10 "**

feetigfceit 397 g / den

d # a / 24 feiin » 6.1 g / d§o

The value of the mixture in the trek in the Faitm was 7.0 g / den and the BruohdAiiunÄ 23 Jt.

Beiablol 2

Sine illtehunf of 35 parts HylomAl · (auu »« OEyXf lendlemin and AdipinWlure), 0 _# 2 MoIHi (bejtoetn mat dti Vylonealis) Idiplnetor

and 65 fell · faiiwt · οΛ · η in a »

Antokl * T «an ebTftohi. The temperature of the temperature was increased, and since "Waeiar uneetihr Bfltunde" removed "" yourBd the internal pressure was below 4 ke / o · ² at ViO ⁰ o gtbelieto, and then the deep door «rf 26 <A> increased. The R * e4rtian "ttjrde one hour · continued while the internal pressure below 15 ke / o * nel of Inaentemyemtur tone AO ⁰ O cehalteB was. Then the pruok alleihlioh in 2 ötenden euf at "oeplAri" e "en Druok b" etM ^ e "etit. Denaoh became you Poljeerleat under iufulinine τοη ubermaintem Vempt entnoaaen · -.-. ■. ' ·. .. ■ r-. ■ "■ ^v -."

The properties of the etnaltenea Poljf »eriiilite wexen the following - 'Λ ·"''-' ■ ti ··; - - ■ ·;.

ι - ' ■ 'f ■■

) , 10 "" ³ mol / g 0.0916

\ 10 ~ ³ mol / g 0.0552

Extent of response 0.983

«Irel ² * ¹⁰

Degree of whiteness 0.80

Gel content (mg / kg) 0

Note: 1) Concentration of terminal carboxyl groups. 2) concentration of terminal amino groups

Example 3

The properties of different polymers, which by Repetition of essentially the same polymerization was obtained with the aid of the autoclave used in Example 2, are listed below:

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r / COOK / ß & J extent of whiteness 10-3 _{mol / g1} 0-3 _{mol / g} reaction H ₁ rel (T ₀ / ^T 1OO ⁾

1 0.0772 0.0583 0.984 2.26 0.79

"0.0604 O ₉ 0422 0.987 2.66 0.76

0.0471 0.0391 0.989 2.95 0.73

'V 0.0457 0.0299 0.991 3.20 0.69

+ »0.0368 0.0249 0.993 3.70 0.58

0.998. 0.0595 0.0373 0.989 2.72 0.78

ⁿ 0.0442 0.0315 0.992 3.20 0.72

+ ■ · 0.0301 0.0265 0.993 3.46 0.61

0.990 0.131 0.0410 0.984 2.10 0.79

+ "Oj0875 0.0070 0.993 2.75 0.59

+: The water of the aqueous solution of the nylon salt was removed, and then the pressure was gradually in about 1.5 h to 2 Torr reduced _o In dieBem pressure, the reaction was continued for 45 min.

It can be seen from this that the degree of whiteness of the polymer is influenced by the extent of the reaction, more than by the value from

Example 4

An aqueous solution "consisting of 30 parts of adipinear m-xylylenediamine and 100 parts of water was placed in an autoclave. At the same time was a phosphorus compound and 1 mol # (based on nylon salt) adipic acid (viscosity stabilizer) added. Then the temperature gradually rose

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180 C increased to remove the water «, the temperature became spell further increased to 265 ° C, practically everything

Drive out Waaser «. The pressure was reduced gradually ani 1 00 Torr, at this pressure, the heating was continued for 30 minutes, to the polycondensation absuechlieeeexu The resulting polyamide ( "MXD-ö" -polymerizates) was from the bottom dee autoclave removed and gequenaoht in a water bath and the usual Wise cut into schnitzel «The intrineiflea. The viscosity of the polymer differed somewhat depending on the phosphorus compound content, but was generally about 1.0. The polymer chips were melted again in a sticket off stream and heated for one hour. The relationship between whiteness and the type and content of

PhoBphor compound salary Whiteness of the Welflgrad naoh (PF '**) cutlet Wax treatment H ₃ PO ₄ 50 0.60 0.19 Ιΐ 100 0.57 0.20 η 50C » 0.55 0.20 It 1000 0.55 0.13 MnHPO ₄ 10 0.60 0.37 ti 20th 0.57 0.35 It 50 0.61 0.40 Il 100 0.57 0.33 CuHPO. 10 0.55 0, 28 π 20th 0.54 0.2β ti 50 0.54 0.25 Il 100 0.45 0.26

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SAD ORIGINAL

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KH ₂ PO ₄ 50 0.65 0.48 ■ Μ —ψ
Il 200
W. 0.68 0.50 NaHgPO ₄ 50
200 0.66
0.66 0.46
0.45 H ₃ PO ₃ 100 0.65 0.50 MnHPO- 10 * 0.45 0.20 Il 20th 0.53 0.26 Il 50 0.48 0.25 Il 100 0.52 0.27 It 200 0.53 0.30 H ₃ PO ₂
η 53
333 0.70
0.86 0.50
0.64 W. 500 0.85 0.70 η 1000 0.66 0.65 2000 0.82 0.56 Mo (H ₂ POg) ₂
η 80
160 0.76
0.80 0.52
0.60 η 270 0.81 0.62 η 540 0.84 0.70 NaHgPOg
η 37
360 0.77
0.87 0.54
0.68 η 720 0.89 0.77 η 1450 0.9? 0.84 Oa (H ₂ PO ₂ J ₂ 33 0.77 0.52 It 330 0.88 0.67 η 660 0.88 0.68 M. 1320 0.84 0.71 no additions B. - 0.60 0.30

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As is clear from this table, the whiteness of the polymer, even if phosphorous acids and phosphoric acids are added, is essentially the same as in the case without addition, and the whiteness is significantly reduced when heated. In contrast, "MXD-6 ^H polymers with a whiteness of more than 0.7 are obtained when hypophosphorous acids are added, and the decrease in whiteness on heating is slight.The retention of the various phosphorus compounds listed in this table was calculated as phosphoric acid (HJPO. ), phosphorous acid (HJPO ") and hypophosphorous acid (EUPQ ₂ ).

Example 5

The water content of the chips of each of the five types of polymer (X «0) listed in Table 1 was adjusted to 0.01 or 0.25% and the polymer was melt-spun under the following conditions

Spinning temperature 275 ⁰ C

Take-off speed 400 m / min

Air flow speed 0.5 m / sec

The undrawn fibers were to 3.5 faohe the original lengths over 80 ⁰ G heated pen "projecting stretches" The properties of the fibers thus obtained are shown in Table 2 below.

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\ el Indeed ell β 1 Carboxyl
end groups
Moles / 1 o ° κ • Whiteness No. 2.26 _r * Amlno-
end group a
Mol / Io ° a .. 0.0772 extent
the
reaction 0.78 1 2.72 1 0.0363 0.0595 0.984 0.75 2 2.10 0.998 0.0373 0.1310 0.989 0.79 3 3.20 0.990 0.0410 0.1442 0.984 0.70 4th 2 »75 0.998 0.0315 O ₃ 0875 O ₉ 992 0.63 5 0.990 0.0070 0.993 '

Yakosity stabilizer: adipic acid «

water
salary
in the
Schnitzel Table 2 Number of
Engten /
1o m
stretched
ter fibers D.
White
Degree 2)
Gel content
(mg / kg) 3)
Speci
fishes
Pluor
escent
i-nten-
sity ITr, '0.01 number of
Thread-
breaks
per kg
"at Ver
stretch SO 80 <0.1 0.02 ' 1 0.25 7th 0 84 <0.1 0.01 1 Qp01 0.1 10 -76 0.04 2 0.25 12.8 13th 81 <0.1 0.02 2 0.01 0.2. 7.5 82 <0.1 0.02 3 0.05 5 0 86 0.01 3 0.01 0.07 340 73 3.8 0.05 4th 0.02 24.0 11th 79 0.5 0.03 4th 0.01 0.3 4300 64 27 0.09 VJl 0.25 21 1200 73 22nd 0.05 5 6th

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₂₇ _ 1,815,191

Note: 1) Measured according to JI5 L-1073 (Judd method).

2) Amount (mg) of polymer which is insoluble in formic acid when dissolving 1 kg of solidified polymer Fibers.

3) A solution of the stretched Paser (1 g / 100 ml) dissolved in formic acid with light from

3650 pounds irradiated, and the fluorescence intensity compared with a standard solution (fluorescence intensity 1.00), which is a 100-fold dilution of a solution of 100 mg quinine sulfate, dissolved in 1 1 0.1 η H SO ^ is "

From Table 2 it can be seen that the number of "fawn broth" is included the extension and the number of enotons / 1 0 m in the manufactured Fibers have a relationship to the gel content (and thus for fluorescence intensity).

Example 6

The polymers 3 for «2 and [3 of Example 5 were prepared in the same way, but with the addition of Hatriunhypophosphit in such an amount that 100 ppm" based on the polymer, hypophosphite radical (HPOp) is present to 2 degree of whiteness (T / T _nn ) des The resulting polymer was 0.83 for No. ₀

3 ι OU

2, 0.70 for No. 5.

Example 7

A polycondensation (Γ (_ _β1 = 2.0) of mixed m- / p »-Xyl5rien-

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diamine (p ~ xylylenediamine content β 17fi) and adipic acid were dried to a water content below 0.05%. Ethylene glycol was added to this in amounts of 1, Of 0.6 »0.4 {0.1 and 0 wt .- ^ Then the polymer was eohmelsgeeponnen at the temperature given in the following table. 5 the length-to faone heated to 8O ⁰ G pins veratreckt to veratreekte fibers 70 of the au / 10 fibers obtained

The properties of the resulting pre-stretched fibers are shown in the following table: ,,

Bbyleh glycol

0.1 0.4 0.6 1.0

Whiteness ($) _t 66.: 75 78 83 82

spess. Fluorescence « _t

intensity 0.10 denier variation> 120 Gel content (mg / kg) 20

trel ² ' ²

Number of thread breaks (Anssahl / kg) 25.8

Melting Splnn Temperature ( ⁰ G) 275

Example 8

Polymetaxylylenadipinamid-Sohnitael (/ ^ ₆₁ «2,3) were spun in the same catfish as in Example 7 at 265 ⁰ C with the exception that the water content was varied.

0.06 0.04 0.03 - 0.02 70 15th 5 4th 75 0.6-0.5 <0.1 <0.1 2.1 2.5 1.9 1.9 8.3 0.1 0.06 0.05 275 270 268 268

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stretched fibers were made in the same manner as in Example 7 burned hot. The properties of the drawn fibers are listed in the following act el Ie:

Water content in the schnitzel
0.01 0.06 0.10 0.38 0.81 1.50

Degree of whiteness (fa) 65 68 76 5 83 83 Gel content 25th 13th ο, <0.1 <0.1

fluorescence impossible

intensity 0.08 0.05 Oj 04 0.02 0.02 borrowed

spin

2h the thread 28.9 6.8 0.16 0.05 0.04
Tarliche (number / kg)

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Claims (1)

PAIMa) REQUIREMENTS: 1 ο Process for the production of polyxylylene adlpinamide fibers by spinning out a molten Kondfinsationa " polymers of m-xylylenediamine or m- / p-xylylenediamine (p-xylylenediamine content less than 30 mol%) with; Adipic acid through spinning orifices, quenching the freshly spun fibers to obtain undrawn fibers, and Drawing of the undrawn fibers, characterized in that that the birefringence (Δη) of the not extended Fibers to a value "is set" as follows Equation is sufficient; 2.0 χ 10 ~ ³ it An S (5.6 + 0.16X) χ 10 "* ³ where X is the molar percentage of p-xylylenediamine in the diamine mixture means, 2. The method according to claim 1, characterized in that the Schmelaepinning temperature (press-through temperature) to one Value is set that satisfies the following equation: 265 + 0.33X = T ^ 290 where X is perpendicular as defined in claim 1, and T is measured in ° 0 will. 3. The method according to claim 1, characterized in that the freshly pressed, hot fibers through a cooling gas quenched at a speed less than 1 m / sec will. 909830/1334 4. The method according to claim t _f, characterized in that the birefringence (& n) is set in accordance with the following equation: To "/ 0.085 x V / Q * 0.25 x 10"^"4 Mn + 70.3 ■ - O, 25l7 ac 10 ^-5 where V is the withdrawal speed (m / min) of the non-calibrated fibers, Q is the throughput (g / mm τ min) when pressing the molten polymer, V / Q = 12 to 120, Mn is the average molecular weight (150,000 to 30,000) of the polymer and T are the temperature in C ". 5. The method according to claim 1, characterized in that the non-drawn fibers are drawn while the water content in the non-drawn fibers is kept less than 4 % . 6. The method according to claim 1, characterized in that the molten polymer to be spun at least one Compound of hypophosphorous. Acid in an amount of 10 to 1000 ppm (as hypophosphorous acid) contains 7o method according to claim 1, characterized in that at least the molten polymer to be spun a hydroxyl compound: contained in an amount of 0.05 to 0.7 mol per kg of polymer S ₀ method according to Aneprueh 1, characterized in that a polymer * is spun _t satisfies the following equation; 300830/13 70 ^ η 1.11 - 1.Q52r »70 - trel = .1" 0 "984r where "^ ₆ J _{1 is} the relative viscosity of the polymer; 1st, which was ^{measured at 25 0} O in comparison with a solution of 1 g of the polymer dissolved in 100 ml of 96% sulfuric acid, and r is the molar ratio of the nylon salt components in the polymer, and is defined as follows: MoXzeJbtl ^ jöl ey the nylon + the number of moles of the viscosity stabilizers 9 «, method according to claim 8, characterized in that a polymer is used which also satisfies the following equation where T and T. ^ _{0 have} the I> e £ inition given in the Beechreilnaig * 10e Thermally pre-stretched polysylylene adipamide fibers with less than 15 knots per 10 st. 11c Thermally drawn polyxylylene adipine amd fibers produced according to one of the processes of claims 1-9 « 909830/1334 ι 33 ·, Empty soap