DE1494692A1 - Process for the production of shaped articles from solutions of completely aromatic polyamides - Google Patents

Description

from solutions of completely aroaatic folysaiden

The invention relates to a method for the production of shaped and stretched (attenuated) objects that are resistant to high temperatures, for example of fibers, pilms or foils, threads, yarns or the like. In particular, the invention relates to a method ' for the production of "araebestündisen fibers, threads, oils and other high strength molded articles made from wholly aromatic polyaida compositions.

cj

J Since kurxea there has been a need for molded articles of improved high temperature resistance · This need has been partially met by the creation of

Pol ^ axidaassen covered. This completely BAD OWGINAL

909944/1724

Arcaatiscnen polyamides know ins ^ esaat in general in the series described in the Vi »i ^ e, that? they do not have any aliphatic fertilizers or abscesses in aren’t reliable, recurring structural units. These include all r & nans-stabilized jiinc systems, both benzolaromatic and heteroaromatic. Examples of such

include:

FoIy- (si-p)

H H

• <r

PoIj-N ₁ Ii'-D-phen ^ lenbie-iE-beaz ζ aiid) -tere J

HC

Il

H C

H C

909844/1724

BATH O ^ GINAL

rc:.

l-i / r is- ^ -t er.r. nid) - *, * ■ '-I Ipi.erv If ic »: t or.-

C H

HO

KO

HO

^ ₀

P0I7-2,5-bisa; oid

-1,3,4-cxaiiazcliscphthale .ure-

- - ^l o

Poly-3, 4'-diaminobenzanilide-isoplitaalsiureaaid "H OH HC 0

OH

BAD Of ¹ UGINAL

and poly-4,4'-diaaiinobenzan H.idterephthalic acid amide

-K -

Because of the peculiar chemical structure of these fully aromatic olefin / amide moles, they have been found to be very difficult to process into shaped counterparts. Any real or true melting point prevents satisfactory melt expulsion or extrusion. Their low solubility in most common solvents polyamide leads to difficulty in dry and Naßextrudieren or -auestoßen, falls no state lösliehmachenden means ι eg Balze of alkali or alkaline earth metals, the solutions' ground added. This, in turn, requires precise and extensive and expensive post-treatments to remove the stumps from the molded objects and requires severe conditions of heat and elongation or attenuation in order to obtain a satisfactory fine structure in the final objects.

Accordingly, it is a purpose of the invention to provide molded articles made from wholly aromatic Polyamides.

• 01144/1724

Another purpose of the invention is to provide dense, stretched shapes or structures of the unusual high crystallinity, orientation and thermal stability »

Another object of the invention is to provide an improved modified wet ejection or extrusion process for the production of filaments, fibers, films and other molded objects made of completely aromatic polyamides "

Another purpose of the invention is to provide a dry jet wet pinning process for the production of Fully aromatic polyamides with improved zero strength temperatures, high birefringence, thermal stability and strength

Another purpose of the invention is to provide a process for the spinning of fully aromatic particles Polyamides, which allow an improved extraction of solvents and inorganic SAAs from the polymer solution permitted·

Other purposes and advantages of the invention will be apparent from the description below.

According to the invention, there will be particularly valuable improvements in molding or extruding complete aromatic polyamides created by the use of a Troekenstraol Har.spinnververfahren, with the polymerizat-

• 01144/1714

solution immediately after injection or extrusion for a course stretch from about 3.17 to 38.1 mm (1/8 to 1.5 inohes) and preferably from about 6.35 to 25 »* ■» _ (V * hi · 1 1Mb) through a gaefgrmiges medium passed me · »before it is passed into the coagulation or precipitation bath · 9a · gaseous medium allows an instant skin kerm formation before the fiber enters the coagulation bath · The B · * · drawing" dry jet .l wet spinning "refers to the fact that in the process according to the invention the spinneret or the nozzle or spray surface is suspended or arranged above the Koegulierbadfluäsigkeit. After the coagulation, the fiber or thread depends on the type of merisate used either washed or passed on to the next stage of the process. The remaining successive stages are the stages of orientation, milling, if necessary the application of a finish or finish, drying and an additional stage reokstuff by means of heat, which is hereinafter referred to as "hot stretch ⁿ * -8tufe" Surprisingly, the use of this method of operation leads to a significantly improved extraction of inorganic salts from polymeric acid solution, improved structural properties of the molded objects and excellent heat stability.

90SI44 / 1724

BATH ORIGINAL

There are methods for making the wholly aromatic polyamides according to the invention in patents and US Pat Patent applications already described. In general, the fully aromatic polyamides according to the invention can be used can be prepared in a customary and convenient manner; they are preferably grounded by combining an aromatic Dicarboxylic acid chloride and an aromatic diamine in a lower alkplamide as a solvent to form the desired polyamide and produced by hydrogen chloride as a by-product · The hydrogen chloride must be neutralized or be removed in order to reduce its harmful influence on dl «BlVh prevent resulting objects. The neutralization dee Hydrogen chloride can expediently be achieved by adding an alkali or alkaline earth base to form a salt and water.

As a result of this neutralization reaction, the polymers are further dissolved in the lower dialkyl amide, which contains an amount of salt and water which is the same is proportional to the hydrogen chloride formed during the polymerization. This amount of salt is in the range of about 1 to 8%, based on the solution weighted, of alkali or Erdalkolichlorid · These solutions can also be prepared by adding a salt-free washed polymer to a solvent made from a lower dialkyl amide and 1 to 8% of alkali or alkaline earth, chloride or bromide

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at a temperature of 60 to 90 ⁰ O is stirred. Although not. is absolutely important, the addition of up to 4 % water in total to these spinning liquids is preferred to improve the stability

It is desirable and appropriate to use the same solvent for the polymerization and the spinning. For this purpose, lower alkylamides, for example dimethylformamide and diethyl acetamide, with a content of up to 10% by weight of dissolved ketallic salts, for example Lithium chloride, lithium bromide, calcium chloride, potassium chloride, tin chloride and the like. Balzt ₉ particularly useful. Calcium chloride and idthium chloride are preferred -pyrrolidone and hexamethylphosphonic acid triamide. The dissolving power of these solvents is usually increased by the addition of the aforementioned salts to the spinning solution. Other solvents can be obtained by using mixtures of two or more of these solvents. Concentrated sulfuric acid can also be used.

The polymer solution can at temperatures of 30.degree up to 120 0 can be injected or extruded. The Polj Sat concentration can be within preferred limits

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BATH

-Q-

Increase or decrease from 10 to 30% to provide a suitable solution viscosity. Conversely, the Diversity of a given concentration through kurses Xrhit ~ zen or cool the solution at one point immediately before adjusted the injection openings; will. Die, spinneret Urt preferably with the surface of the coagulating bath fixture, which is substantially parallel to the surface, so that the dia The sprouted solution goes through a course of gaseous construction before entering the coagulating bath. Si is norma It's easy to adjust the nozzle! dafi the AJtafcand is obtained and this distance depends on sound

• ■

Filtration, viscosity, temperature and other dope conditions - ^: Usually this distance is about <3 * 17 am to 38.1 stm (1/8 to 1.5 inches) and preferably ί about 12.7 an (1/2 inch). However, this spacing can be increased by taking precautions so that neighboring polyesters do not come into contact with one another and adhere to one another before they enter the coagulating bath.

The heat-resistant wholly aromatic polyamides are advantageously from solutions with about 10% bia 30%, preferably 12% to 20 wt -.% Of the wholly aromatic polyamides having inherent viscosities of about 0.6 to 3.0 or above, and above about 1 voraugsweise , 2, measured at 30 ⁰ O in the form, a r · 0.5% solution " iv. Diaethylacetaaiict with .a ... content t. ^ -, - icstea LitLium ^ iU <·! <!, geeponne»

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BATH ORIGINAL

-1C-

To achieve ν. η should achieve optimal results the spinnable variables are brought into relation with one another in such a way that less than 1%, if anything is lost, des Solvent, based on the weight of the solution, into the gaseous medium from the sprayed or extruded Electricity is evaporated

Se has been found that wholly aromatic PoIjamide with inherent viscosities of about 0.6 to 3.0 _t or more and preferably immediately anocnlieQenden above about 2,0'nach the method according to the invention by changes in the coagulation bath and in which the Koaguli-rung Level can be spun. If the manufacture of fibers or threads for clothing and similar end uses is desired, these fibers or threads should have a denier in the range of about 1.C to 3.0 denier per thread (dpf) and strengths of about 2.5 bib 5, 0 g / den · In order to produce fibers or feathers within this titer and strength range · the inherent viscosity should preferably be approximately 1.2 to 2.0. When a polymer with an inherent viscosity within this range is spun into fibers or threads using a solvent and water as a coagulating bath, a backdiiJ-fusion of water into the fibers or threads often occurs in which solutions :: t. fcelsystem existing salinity an excessive samphire U · \

9098U / 172-- '

BA OPHGINAL

laser. The product obtained in this jail is a matted brown yarn which has poor tensile strength, large voids and a granular structure increase, a better approximation is achieved by changing the composition of the eoagulating bath towards a solution of water and a polyalkylene glycol. We; . " On the other hand, the production of fibers or thread for tire cord and other heavy, industrial applications week is desirable, which has a strength of about 5" 5 to 8.5 g / den usd a liter of "6 to 8 days" aj · Ta4 «n upwards», 41 · ligwar viscosity la range from «vwa 2.0 to 2.4% above, fibers or threads« with higher titer values (9 to 15 denier per thread) can conveniently and appropriately from polymers At this level of intrinsic viscosity, the polyalkylene glycol coagulating bath is less effective and leads to the threads sticking or fusing. In these cases, an aqueous coagulating bath is preferred.

The polyalkylene glycol coagulating bath comprises a mixture from about 70% to 95 # water by weight and of about 30% to 5% of a polyalkylene glycol. The one used here

909644/1724

The term "polyalkylene glycol" refers to polyethers, which can be derived from alkylene oxides or glycols and are represented by the formula HO (RO) * in which B is a methylene, ethylene, propylene and butylene, and η is an integer of at least 4 means · Bai polyglycol can have inert components »such as methoxy polyethylene glycol, and can consist of a mixture of polyalkylene glycols. These glycols have molecular weights of about 2CO to 6000, preferably from 600 to 2000. Although large changes in the Spinnbodteiapera are permissible, a temperature in the range of about 5 ° 0 to 60 ⁰ C, preferably from about 10 ⁰ C to 30 ⁰ C, preferred «

The coagulating bath for polymers with an inherent viscosity of about 2.0 or more, which is made from a mixture from 0 to 4-0%, preferably 0 to 10%, of a dialkyl amide in Water is very effective even after there is a significant concentration of metal salt in the coagulating bath has formed itself · It is advisable to use the coagulating bath to continuously supply fresh solvent-water mixture « while a portion of the Bados containing solvent, metal salt concentrations is continuously withdrawn, whereby a substantially constant environment for coagulation or precipitation is maintained. To be constant in the bathroom

909844/1724

fi

Coagulation ensure the solution is circulated and, by the continuous addition ▼ on fresh solution or water, while continuously withdrawing a having equivalent proportion of the spent solution is removed »bsi a preferred Konsentration be kept · The temperature of Kotgulierbads can 10 ° 0 to 50 ⁰ C, voreugaweise 15 ° 0 to 25 * 0, during the coagulation amount · If the coagulation is auegeführt in the above-described spinning bath, the wholly aromatic polyamide fibers have characteristics in accordance with the invention, its conversion by further treatment or processing into useful fibers or allow threads with unique and novel eggshells.

In the method according to the invention, the coagulation stage is followed by an orientation stage in which the fiber or thread material relaxes or from less than about simple to about four times its length in a conventional bath of hot water or in a drawing bath of boiling water a temperature of about 50 ⁰ C to 100 ° C can be stretched · The orientation of the fiber can be washing the fiber on the take-up roller or the first roller (godet), which pulls the fiber from the Eoagulierbad and it to the Streokbad with hot water supplies, include. This special water washing is desirable when very high salt concentrate ions are present, which occur, for example, when particularly insoluble polymers from solvents containing sale are spun.

909844/1724 bad opmqinal

149 * 892

After orientation, the fiber or thread material is washed with water at a temperature of 15 ° to 65 ° 0 , with higher washing temperatures being used when shorter washing times are required and lower washing temperatures being used when longer washing times are required, essentially remove all traces of solvents and salts. The washed, oriented fibrous or filamentary material is then passed through an optionally aqueous AuarÜBtungsbad where common Scumiermittwl and respectively "or anti-static agents can be applied. Of the applicable finishes or finishes, an agent of an antistatic type for regulating static charge or electricity has proven particularly valuable. Without an antistatic agent, the dried fibers or threads tend to repel one another and are difficult to handle in further treatment or processing stages .

The fiber or thread material is dried in a customary manner on cylindrical rollers heated by means of steam or by any other suitable drying device. The temperature is preferably maintained at about 120 to 160 ⁰ G ⁰ C.

After the drying process, the fiber or fiber product can be preheated by placing eo over a srhiteten Straightening pin or by a heated container, e.g.

909944/1724 bad original

Heizanlag · or a hot block slot passes, wherein the fiber or thread material continuously to about 300 ⁰ C, bit 500 ⁰ C, preferably _t 400 ⁰ C to 450 ⁰ O is conditioned. ! The Paser- or FadenproÄukt is then 1 to 4 times over a heated surface, beisfielsweise a heater or heat Heißschuh- the shoe type, at about 300 ° to 45O ⁰ C!

drawn. On the other hand, after drying, the fiber or thread material can be moved immediately to the heated surface if a continuous spider jet is used is desired at 350 ° to 50 ° 0 # _f, j, the facer after the hot stretching _# can be several times over a / heated '■ surface by application of small roller guides are directed. The stretched (or stretched and warmth sta- j bilized) fiber is finally made using a;

• ί

common mounting devices collected on spools

When spinning fibers or threads from polymers _; the general formula: _mmmm

f ^ jj J ^ \ ⁰ Y ^ ° f ^ \ °

BH 1 J — O-HH — l · | —SH-C — I- J — NH-C — l · J — 0- -

9098 * _{4/1724 BAD} ormH M

for example poly-K.N'-a-phenyienbis-Oa-beneaiiid ^ terephthalic acid amide

and Poly-N ₁ N'-a-phenylenbie-fa-benaamid ^ leophtlwlelttr ·· »! *

I found the inclusion of an immersion bath with the created orphan ntfca desgulierbad desired, which contains a solvent extraction agent to improve the glans and other shafts of the fiber or thread material. Suitable extraction agents that can be used include monohydroxy and Polyhydroxy compounds such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, ethylene glycol, propylene glycol, butylene glycol, glycerine and mixtures of these compounds with up to 50% water. Other extractants are polyalkylene glycols with molecular weights of 600 to 2,000, see for example Polyethylene glycol has a molecular weight of 100% amides, for example dimethyl aetaaid, dimethylformamide and urea, mixed together with a mixture of 40 bits. »He, can, also be used.

909844/1724

BATH ORIGINAL

sen acetonitrile (ΟΗ, ΟΉ) The extractive agents are preferred if the inherent viscosity of the polymer is below about 1.90 and the desired titer 6 den per thread or above is "

The invention is explained in more detail below with reference to the drawing.

Fig. 1 is a side view, partly in section, schematically showing a device of a type γ / which can be used in carrying out the method according to the invention.

Fig. 2 shows a drawing of a jriiotomicrograph Cross-sectional view of fibers produced by the dry-jet wet spinning process have been received

Fig. 3 shows a drawing of a photomicrograph Cross-sectional view of fibers obtained from a conventional NaS spinning procedure.

Referring to Fig. 1, reference numeral 1 denotes the polymer solution holding tank. The Irolymerisatlösung is via a jumper 2 through a filter 3, which consists of two Consists of layers of polyamide (Kylon) and a layer of flanjaell, a nozzle holder 4 and pumped out of the Soinndüse 5. The Spinneret is by means of a circulating warm medium through the nozzle holder to the er> vüns., uttj temperature regulated. Di. · ΐ Ι> · "Ϊ3β has ί ciiaalfra'ds« 10 to 100 holes,

^S "'■ *'" * ^J BAD OSGINAL

76. $ where each hole has a diameter of about? £ φ to

(> up to 20 mils) The nozzle surface is arranged toraugswelse parallel to the surface of the coagulation bath 7 The polymer solution is sprayed out in the downward direction and enters the coagulation bath, whereby sk 6 »which is arranged under the bath surface immediately below the nozzle | is forwarded. The partially coagulated thread or fiber material moves further in the bath _t emerges * and goes over to the first take-up or guide rollers 8 (godet rolls) can be equipped with an immersion bath e «£ a ₉ which contains a solvent extraction agent by means of which the freshly coagulated yarn is further extracted before drawing The fiber material is then passed through a finishing bath 11 and onto drying rollers 12 · After a thorough drying * has been obtained, the fiber material is passed immediately over the hot pin 13 and stretched by rollers 15 over a shoe 14 · The pin is normally brought to a temperature of about 50 ° C above the shoe temperature in order to allow adequate preheating of the yarn make sure · If ei τ Of «α use as preheating egg :; we;!, ä-ioll the temperature innorhilb des ·: ι * Sh

A09844 / 17H

BATH ORIGINAL

T494892

«19 -

Be 10Ö ° G above shoe temperature «On the other hand, they can Ground the yarns preheated with the drying rollers alone. The drawn yarn is then collected on a bobbin 16 using a conventional take-up device.

The difference in the fiber cross-sections in FIGS. 2 and 3 clearly shows the gate part of the process according to FIG of the invention. The after de «Jroekenstrahl-NaßapinnYerfah ·· ren spun laverns from? ig * 2 have a well-iced clear internal structure, while those from fig »3, weleae Wet-accumulated fibers show sahra-rich cavities on the outside.

/ \ Here preferred and optisalvn spinning conditions »for elA fiber or thread material old a filter of 6 dene> 4 • iod in the following Xe & elle I» usaauae

Table I.

Spinning condition preferred · work- optimal range

Polymer properties 1.70-2.50 2.20 Polymer solids, % 15-22 20 ^;

Temperature of the spinning liquid at the nozzle, ° C 40 - 130 70>

Distance from the surface area '

to the Spinnbadobepf pool, cm 0 635 - 3.81 1 * 2?

Cinches) (0.25 - 1.50) (0.50):

Spinning bath coagulation,

based on volume \

% Water 90 - 100 99}

% Solvent 10-0 1

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Table I (continued)

• Spinning condition

Spin bath temperature, ° 0

first wave speed m / mim (fpa)

Orientation stretch washer temperature, ⁰ C equipment

Reduced concentration

Preferred work area

10-30

3,657 - 4-5.72 (12-15O5

optimal

0.88 - 2.80 times 15 - 65

25th

/ 10.3 (34)

2.10-faeh 60

an antistatic an antietatied

taking part in making means *

and / or lubricants and or

medium 'lubricant

0.5 - 10.0 2 _t 0 0.95-1.00-fold 1.0-fold 120 - 160 150

3.96 - 128 (13 - 420)

300-500 300-450 1.0-4.0 times

4.97 - 217.6 (16.3-714)

The maximum hot stretching that can be carried out is gon de » Orientation extension depends on the total spread from the spinneret or nozzle face to the end take-up roll varies from about 2.0 to 12.0 times

Stretching between washing and drying equipment Temperature of drying ■ -walte, ⁰ C

Drying drum speed, m / min (fpm)

Preheater oven temperature, ⁰ C shoe temperature, ⁰ C HeistreekauemaS final speed, m / min 450

375

1.70 times

36.88

809844/1724

ORlStNAL INSPECTED

The invention is illustrated below with reference to the examples, in which the percentages given are based on the Total solution weight, unless * otherwise stated. In the examples five different fully * » constantly aromatic polymers for use »wdfrel three different 8pider systems are compared

example 1

Poly-N, N ¹ -m-phenylenebis (m-benzamide) -2,6-naphthylenedicarboxamide was polymerized according to the manner described in US patent application 8er.Hb 222 930, with a solution containing 20% polymer, 3% lithium chloride, 1% lasser and 76 % dimetbylacetamide with a viscosity of 17,260 poise at 23.5 ° 0 was obtained. The solution was on

102 ⁰ O heated and in hot air in a 4.57 m (15

Spun using a 127ft (5 mil) A) UBe 'with -14 holes

A bit KinlaBlufttemperatur of 215 ⁰ C ₁ a spinning speed of about 228.6 n / ain (750 fpn) and a You-j senstreekung of the 7 _t 82 times the dry-spun. The paper material was collected on a spool and then leached for 2 days with four changes of deionized water at room temperature at intervals of about 12 hours. The fiber material dried at this point in the process contained about 4.5 % dimethyl acetamide. The fibers

BAD OWSINAL

909844/1724

or threads were then unwound from the bobbin on feed rollers and fed at about 42.7 m per minute (141 fpm) over a hot shoe about 30.48 cn (12 inch) long " ^{regulated at 300 °} C." the 1 _t 7 faobcgestretkt "ad _a uf coils collected · This thread" or R & SCRM * tcri9l bes ** in Table II below, which is given in example 9, listed properties.

Belaiiel 2

The polymer-solvent system used in Example 1 was heated to 85.degree. C. and used with a 12 fb (5 mil) spinneret with 10 holes for wet spinning in an aqueous spinning bath at 55.degree. After a distance of about 58.4 cm (23 inches) immersion in the spinning bath, the filament was advanced through draw rollers which stretched the vasers or filaments 1.13 times in the spinning bath. From the spinning bath, the fibers or filaments were subjected to orientation stretching of 2.25 times in a boiling water bath. The fiber material was then advanced to a set of washing rollers and washed with 55 ° O water. After this. For washing, an antistatic finish dispersion at a level of 3% was applied from an aqueous finish bath. After the finish was applied, the fiber material was advanced over heated drying rollers at a temperature of 135 ° C, where it was further stretched 1.16 times and g

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BATH

149 * 192

was dried early. After drying, the fiber material was passed over a stretching shoe about 30.48 cm (12 inches) at 290 ° 0 and fed by feed rollers by additional dejf 1, 5 times' stretched. The paser or thread material was then collected on bobbins at a final spinning speed of about 26.6 m per minute (87.3 fpm) · The properties of this fiber material are given in Table TI below.

Example 3

The polymer-solvent system used in Example 1 was according to the manner indicated in Fig. 1 under the conditions prescribed in Table I above. The oil properties of the fiber material obtained are compiled below in Table II.

Example 4

The conditions used in Example S were followed in this example with the modification that the polymer used was poly-N, N ¹ -a-phenylenebis- (a-bensamide) -4,4 * -blflp & enyldiearboxamide. The preparation of this polymer is in the above-mentioned US patent application Ser. N. 222 930 described. The Sigenscha! th of the fiber material obtained are listed in Table II below.

BAD OfiiQiNAL

909144/1724

U94692

Example 5

The conditions used in Example 3 were followed in this example using poly-N, N ¹ -mphenylene-bis- (m-benzamide) -terephthalic acid amide as the polymer. The preparation of this polymer is described in US patent application SN 222,932. The properties of the fiber material obtained are shown in Table II below.

Example 6

The conditions used in Example 1 were followed in this example with the following modifications. The polymer, poly (m-phenylene isophthalic acid amide) was prepared according to the procedure described in US Pat. No. 3,006,899, a dimethylacetamide solution containing 20 # polymer and 3% lithium chloride with a viscosity of 5,760 poise at 25 ⁰ C was obtained. The solution was heated to 110 ° C. It. was a 152 / H (6 mil) spinneret with 14 orifices or holes and

909844/1724

an inlet air temperature of 175 ° C was used. the Spinning speed was about 40.2 m / min (132 fpm), the die stretch was 4.58 and the pasers were to 5.62 times over one regulated at 325 ° C hot shoe stretched. The properties of these fibers are listed in Table II below.

/ Example 7

The spinning solution used in Example 6 was used in this example, the solution being spun under the conditions used in Example 3 became. The properties of the fiber material obtained are shown in Table II below.

Example 8

A solution with a content of 18 % poly-3,4 ¹ - diaminobenzanilidisophthalic acid amide in dimethylacetamide, which contained 3 % of dissolved lithium chloride, was produced. The solution was ^{heated to 63 0} C and in a spinning tower of about 4:> 7 in (i. ^C : fx- \ wounding a 127. (,, {/ ' nri ij-luct., Ult ;', öffnurx-

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gen dry spun. A nozzle extension of the 3.7-fold, a spinning speed of about 68.5 m per minute (225 fpm), an inlet air temperature of 190 ° C and an outlet air temperature of I65 ⁰ C were applied. The fiber material was wound onto a perforated bobbin and continuously leached with water at room temperature for 24 hours. After leaching, the fiber material was air dried at room temperature. The dried fiber or filament was then unwound from the spool on feed rollers and passed through an oven at about 12 inches (30.48 cm) maintained at 425 ° G at a speed of about 123 fpm was performed and then immediately stretched to 1.7 times over a shoe of about 30.48 cm (12 inches), which was adjusted to 425 ⁰ C. After drawing, the fiber material was collected on bobbins. The properties of this fiber material are listed in Table II below.

BATH ORIGINAL 909844/1724

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■ - 27 -

Example 9

A solution containing 18 # poly-3,4 ¹ -diaminobenzanilide terephthalic acid amide in dimethylacetamide containing 3% dissolved lithium chloride was prepared and spun according to the manner shown in FIG. 1 under the conditions described in Table I. The properties of the fiber material obtained are summarized in Table II below.

BAD ORiSINAL

909844/1724

example 1 2 Table II 4th of threads 2.9 * 7th 8th Q 1
IV)
no % Titer, den / thread 2.1 5.0 8.30 5 6.0 1.7 2.5 2.6 I. Strength, g / den 3.2 2.9 £ L £ »n * owed 6.10 23.3 6th 4.0 a 4.0 Strain, % 19.7 16.5 3 20.8 1,843 1.5 16.7 a 29 Refractive index
(parallel) 1,785 b 10.4 1,855 0.134 6.50 1,812 1,820 - Birefringence 0.100 b 6.10 0.222 500 33.0 0.154 0.165 250 Zero strengths
temperature, C 302 320 15.1 500 38.3 1,792 515
- *? © 325 5CC M content (parts
per million parts) 85 1.930 3.4 0.139 0.24 2.4 - . 0.274 470 515 15.8 0.5

a bundle bend, elongation

fepMhuBgsindex- (uni DoppeH> reohungs-) values are due to the presence of γη large cavities dL of a granular structure not reproducible. . - *

co **. cn co

U94692

The birefringence awertβ given in the table above were obtained by comparing the parallel and vertical breadth indices in planar transversely polarized a folane oroae-polarized) light using the bevel line work white determined «· The birefringence is calculated from the Breohungsindices. The zero strength temperature test was determined by heating a yarn at a load of 0.1 g each in a nitrogen atmosphere. The temperature increased to the extent of 5 ° 0 de minute increased until the sample broke. The temperature at which the sample broke was taken as the zero strength temperature taken.

The superiority of the dry jet wet spinning process versus dry spinning is based on the ease and completeness of salt removal, the superior orientation and crystallinity in the stretched lasers or threads visible *. In the glimpse of the Hatred spinning method compared to trooken jet wet spinning work ·! «· another distinction can easily be demonstrated The same polymer as described in Example 3, was after the Trookenatrahl-Najeplnarbeitweise with the modification spun that the nozzle extension to the 1.3i-f adie was restricted. After collecting the fibers or threads, among other things under stable trooken-jet wet spinning conditions, the spinneret is lowered into the spinning bath and the sample remains unchanged any condition other than immersion of the

909844/1724 _BAD

Spinneret wet spun. The thread cross-section obtained in the dry steel wet spinning operation is shown in FIG. The cross-section obtained during the wet planning process is shown in FIG. The dry-jet wet-spun fiber was void-free and is very preferred over the heavily voided structures shown in FIG. During the dry-jet wet spinning was the distance from the face of the spinneret to the point in the longitudinal direction of the F _a abels thinking, in which the coagulated fiber or mat appeared about 17 | 78 "m (7 inches). This same location was observed when the fiber was wet spun at a distance of only about 1.27 cm (0.5 inches) from the spinning surface.

Example 10

The spinning conditions used in Example 9 were repeated with the modification that the maximum nozzle extension both for the Trockenstranl-Naßspinnarbeitsweiee as was also determined for the wet spinning mode of operation .. The maximum nozzle stretch is referred to as the maximum stretch., which can be used between the spinneret face and the first feed rollers without breaking the threads to cause. The maximum nozzle stretch for the hatred » epinnarbeitaweise was 1.18-faoh. For the Trookenatray hatred spinning process was a nozzle extension of 7-3 times

BAD OPHGINAL

909844/1724

obtainable. The opportunity with this greater leeway Spinning in the nozzle extension is what the dry jet Uaßspinn Vorfr.iren does more flexible and versatile and more convenient to use than the wet spinning system a higher degree of orientation and crystallinity in that "^ ndfaeer- or end thread material facilitated and a comfortable Spinning a much larger range of denier values enables

Example 11 '

The spinning conditions used in Example 9 were repeated with the modification that the maximum orientation e-j stretching of the sample was determined according to the Tiockenstraul wet spinning procedure and of the sample according to the Saß pinning process, the nozzle extension again being 1.5 for both systems was established. When using the boiling water bath for both gleiehenj Spinney star a maximum elongation of orientation \ was added to the 1.27-fold for the ji j wet spun sample and for the dry-jet BTafepinn sample

to the
observed by / 2.80 times * These results again show; the desired flexibility and versatility and greater ■ lightness of the dry-jet-wet-spinning bysteaas compared to the wet-spinning method «

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Example 12

The shrinkage under dry heat of samples was determined for the samples according to the troiken jet wet spinning method of Examples 3, 4, 5 and 7 in comparison with a dry-spun sample according to Example 6. The heat loss caused by the low shrinkage at 4-0O ⁰ G is displayed "is greatly increased in the samples according to the TrockenstrahlnaJggeiMfeftiPbeiteweise · dor In Table III below, the shrinkage values are listed in comparatively dry Wäxm · t

Table III Example ^ Trooktnhitze-Sohrumpung at 400 ⁰ O

} 7.7 *

4 10.7 * '

5 7.0 %

6 81.0 %

7th 10.5 %

The dry-heat shrinkage was obtained by decreasing at a 20 cm. long yarn was measured after 3 minutes of contact with a heated metal surface. The percentage shrinkage was calculated from the change in length.

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Example 13

A solution with a content of 20% poly-N, N'-m-pheny-Ienbis- (m-benzamide) -tereph.thalsäureami4. (with an inherent viscosity of 1.92), 3 % lithium chloride, 1 % water and 76 % dimethyl acetamide was produced. More lithium caloride was added to increase the concentration to 650 lithium chloride. The solution A 'was heated to 20 ⁰ O and spun as in Example i with the changes indicated below. The coagulating bath was formed vcn 80 # water and 20% Folyäthylenglykol having an average molecular weight of $ 1000 at a temperature of 20 ⁰ C · The fiber was subjected to a preceding wash on the first guide roller after leaving the coagulation bath and prior to orientation stretching. The spinning stability w _p r good and there would be a fiber with a titer of 5 | 1 to each filament having a strength of 5.0 g / d, an elongation of 29.1%, a modulus of 82 g / denier and a Nullfestigkeitsteipperatur of 511 ⁰ C obtained. . .

example

A solution of poly-NjN'-m-paenylenbis-Cm-benzamid) - ^ ■, A -'- biphenyldicarbansäureamid was prepared and as in Example 13 spun “A fiber with a titer of 8.3 denier per thread and a strength of 6.1 g / denier was obtained Elongation of 20.8% and a modulus of 82 g / den

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Example 15

A solution of poly-N, ^N-1 -m phenylentis- (m-benzamide) -2,6-naphthylendiearbonsäureamid was prepared and spun according to the procedure set forth in Bei _t iel. 13 A fiber with a titer of 2.2 denier per thread, with a tenacity of 7.0 g / denier, an elongation of 16.6%, a modulus of 118 g / denier and a zero strength temperature of 506 ⁰ O was obtained.

An examination of these samples shows that the method according to the invention resulted in fibers or filaments with significantly improved properties compared to those of the previous technology. obtained by other methods and is mainly in the range of 50 ° C to about 525 ° C. The wholly aromatic fibers described previously in the art possess stigkeitsteaiperaturen all Nullfe- which lie well below 50O ⁰ and G

in most cases below 4-5O ⁰ G · The shrinkage under dry heat and the occurrence of voids are substantially improved · The shrinkage under dry heat at 40O ⁰ C Q, which is given in Table III is particularly

o »remarkable as they are an improvement for the same F ** »» ■ ■ ".

* - · ser in Examples 6 and 7 from about 80 to about 10% shrinkage

^ * shows · The birefringence values are also at all ^ Fibers made by the method according to the invention are, greatly improved, which have a birefringence of above 0.150.

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Example 16

A solution of 20% poly-S, N ¹ -m-phenylenebis (o-benaaaid) -2,6-naphthalenedicar1> oneäureaeid% with an intrinsic viscosity of 2.38 l of the ethyl acetate with a content% * 5% dissolved lithium chloride was under the conditions indicated in Table X · the spun fiber was a Düeenstreckung to the 3.14-fold, a Orientierungsβtreckung to 2.55 times and a final hot stretching the ν, I ₄ 27 times at 35O ° C issued · the train - and elongation properties of the fiber were 11 * 6 den / thread, 5 »86 g / den strength, 14.10 # elongation and a modulus of 134.0 g / den.

Example 17

This example explains different drainage »· or solvent extractants useful in improving the spinning of polymers of the formula below *

(KT ^ J — S-N3— ^ J — HH »G— \ I— BH-G— F ^ JC-

Froben of oly-N _f H ¹ -a-phenylenebi3- (m-benzaaiid) -terephthalic acid amide with an egg viscosity of 1.9 were spun under the conditions prescribed in Table I, with the modification that the orientation baths

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- 56 -

ρeratür to about 50 ⁰ O was lowered with the addition of an immersion bath at the first guide or take-up roller ₉ and the following solvent extractant for use reached · A: alcohols

1. Ethanol

2. Isopropanol 3 · ethylene glycol

4 · 70% ethylene glycol (based on volume) in waeeer 5 · glycerin

6. Fo Iyethylene glycol with a molecular weight of 1CX) O B: amides

1. 50% dimethyl aetamide (based on volume) in water

2 37% harm (based on volume) in water

In any case, the use of the Extraktionemittel yielded · a uniform collapse of the fiber, the elimination gläossad any tendency of Fmser rar bonding, an improved "Oarntrocknung8ausmaB the Troeknung8w $ ASEM _v higher · yarns and a wider range in the 8pinnvariablen _t which allwirkung without Grensf could be used

The advantages of following the procedure according to the Effinduag manufactured ve fibers from completely aromatic polyamide compared to such fibers, -4ie after the dry or lafieplfife · » are made by working, are obviously · Dal Ver—

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faaren is particularly valuable and unique and unusual in terms of simplicity, ease of execution, and economically and technically attractive and advantageous Use of conventional fiber spinning equipment. The process avoids the risk of explosion and fire and in some cases dangerous and ineffective leaching operations that are common to the previously known working methods were characteristic. The available range of Fiber orientation "un'03koi" bin> \ t; ions is another advantageous feature ^ character of the process ^ -as ^ ernai: the invention · the after fibers made by the method according to the invention have an excellent strength, a particularly good one v Thermal stability and high gloss.

Fibers or threads with such properties are particular useful in molded articles intended for purposes involving exposure to elevated temperatures is required to find application · In the form of fibers, threads and other shaped objects Dun ^ s areas ^ e.g. for electrical insulation, industrial filters or technical filters, conveyor belts, Heifencord, heat-resistant parachutes, protective clothing or the like, usable.

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Claims (1)

Claims 1 · Method of making molded articles from Solutions of fully aromatic polyamides, thereby characterized by spraying or extruding the solution downwardly into a stream by mixing the solution presses through a shaped opening into a gaseous medium in which only a small amount of the solvent is evaporated from the stream, the stream is passed through the medium for a short distance and into a coagulating bath leads, which contains a liquid consisting of a precipitant for the polymer and an extractant for the solvent, the object formed in this way is withdrawn from the coagulating bath, the object through eir.e Conducts washing liquid, where it is stretched to orient the polymerisation molecules, washes the object, dries and passed through a heated environment under tension to produce the molded article. 2, method according to claim 1, characterized in that a polyamide solution with a content of $ 10 to $ 30 Polyamide, based on the solution weight, for a Temperaco ° door from about 25 ° C to 10O ⁰ C over a stretch! of about 3.17 mm ^ 38.1 mm (1/8 to 1.5 inches) through the gaseous medium. ** "there is a traction agent for the solvent and is kept at space \, t ^» 3P »rat; only _{% is} the polymer material thereafter < J ** - W '4 ^L < ^f ' BAD OWGlNAL ^ ¹¹ V - <■ j. performs boiling water as a washing liquid, wherein an aspect ratio of entertaining "is applied to the 1 to 4-facheto, the fiber material is formed with water at a temperature of 40 ° to 8O ⁰ C is washed at a temperature of 120 ° to 160 ⁰ C. dries and passes through a preheated environment at a temperature of 400 to 480 ⁰ C under sufficient tension to stretch the fiber material by 1 to 4 times its length 3. The method according to claim 1 or 2, characterized in that a solution of polyamide in ein.niederen -Pialkylamid with a content of 1 £ to 8j £ of an alkali or alkaline earth metal halide in a solution β * empera door from 40 ° to 100 ° C passes a distance of about 6.35 mm to 25.4 mm (1/4 to 1 inch) through the gaseous medium into the coagulating bath which contains about 1 to 10 / »of a lower dialkyl amide and 90 to 99 % water and maintained at room temperature and withdrawing the fiber from the coagulating bath at a rate sufficient to provide a nozzle elongation of about 2 to 7 times its length. 4. Method according to one of Claims 1 to 3, characterized in that that the lower Dilakylamid ^ imethylacetamid or dimethylformamide used 5. The method according to any one of claims 1 to 3, characterized in, that lithium chloride, calcium chloride or lithium bromide are used as alkali or alkaline earth halide. 909844/1724 6 · A method according to any one of claims 1 to 5, characterized in that a polymer solution with a Eige '- viscosity of from about 1.2 to 2.0 in the held at a temperature of about 10 ° to 30 ⁰ C coagulating bath which containing a mixture of about 70 to 95 percent water by weight and about 30 to 5 percent of a polyalkylene glycol passes the paser through a first wash liquid of water and a temperature of about 15 to 60 C i "häf% _T by a second washing liquid from V / ater out at a temperature of about 50 ° to 65 ⁰ C. 7. The method according to any one of claims 1 to 5, characterized in that a polymer! Sat solution with a content of 10 to 22 # polyamide, based on the solution weight, and with an inherent viscosity of about 2.0 to 3.0 in the Coagulating bath made of about 1 to 10 # of the solvent and 90 to 99 $> water at room temperature and the Paser washes with water at a temperature of about 15 ° to 65 C. § · Process according to one of claims 1 to 7 »characterized in that a solution with a content of 15 to 22 #, based on the weight of the solution, of N, N ^f -m-phenylenebis- (m-benzamide) -2, 6-naphthylenedicarboxamide, EoIy-H, N ¹ -m-phenylenebis (m-benzamide) -terephthalic acid amide, poly- (m-phenylene isophthalic acid amide), poly-3,4'-diaminobenzanilidisophthalic acid amide or poly-N, N ¹ -ra-phenylene - (m-benzamide) -4,4 * -biphenyldicarboxamide, 85 to 98 i ° _s fe 909844/1724 U94692 ^ imethylacetamide, 1 to 10 # lithium chloride and 1 to 55 * water are used, with an extension of 0.88 to 2.80 times the length of the paser being applied during the passage through the hot wash liquid and the paser being applied by a preheated one environment results from a Vorerhitzerofen at a temperature of 200 ° to 45O ⁰ C and heated to a temperature of 200 ⁰ C to 450 ⁰ C shoe · 909844/1724 Blank ite