DE1669518A1 - Crystalline, oriented threads - Google Patents

Description

December 29, 1967 RD-1233

BI m ΡΟΗΪ BE JJEMQtffiS AÄD COMPACT 10th and Market Streets »Wilmington, Delaware 19893, Y.

Crystalline, oriented threads

Polyamides made from bis (4-aminocyclohexyl) ethane (abbreviated here as PACH) and various aliphatic diacids are for example known from the ÜSA patent specification 2 512 606 (Bolton and Tfirk). These threads do not have the desired combination high strength and low shrinkage »which these days for technical yarns, especially if they are to be used for tire cord, are required.

It has now been found that threads attached to the polyamides »eraponnen are which from PACS! and aliphatic dissures pit 11 to 16 Carbon atoms have been formed, can be produced in such a way that they have a certain crystal structure; Yarns with this crystal structure are not the same as those listed earlier Flawed and are for all end-use purposes very desirable where high strength, high modulus and low shrinkage are required.

BATH ORIGINAL

109852/1772

SD-1233

This invention provides a high molecular weight, crystalline, oriented thread made from the polymer of bis- (4-aminocyolohezyl) -methane with a tranatrane-wtereoisonsren content of 70 to 100 (each and aliphatic diacids with 11 to 16 carbon atoms inclusive »Which thread has a crystal spacing in transverse direction from the crystal planes, or" d-value ⁿ from 4 »3 to 4.7 S,! Determined from the strongest equator reflections in a Bragg's x-ray diffraction & pattern * This crystal is for a Heine von Jaden characteristic "which, as will be explained below," change their X-ray center distance with increasing orientation.

These threads are mainly from the following »recurring Structural units built up:

- $ ~ / > -σ- / \ -ir-c- (ciH ₉ ) "-σ- (ι)

In this a9-14 "Torau way is η 1O ₉ ie the uic acid is dodecanedioic acid (according to the older lioiaenklatur ^fl See?:! NdicarbGnöS.ttr9") Depending on the precise working conditions used, ESden can be obtained "in which the polymer chains are extend up to at least 86 % or even 9% or very much of their thorei-ish "fully extended length * 3) he theoretically" _f completely extended length leaves cioli easily aue Stuart viiA

109152/177 2

BAD ORtGLNAU

ED-1233

Brieglet models based on working methods that are easy for the Pachmann to understand determine. In this respect, "International ! Cables For X-ray Crystallography ", Volume III» in particular page 276, Kynoch Press, Biraingham, England (1962).

it was found that each of the homo polyamides of formula (I) to lau 30 # ΈΛΟΚ- * "are piping Hisehpolymereneinheiten insofar" to -16 as Mischpolyiaerenbestandteile angenofflmen ¹ ·, ale λ. up to 30 6EW $ 5 of them, without serious loss of wünschene · priced properties form "on the ability of the HS-crystal βα or can be added to Polyraerenschmelzpunkt. Versmtlich the '' extended Polyaerenketten allow the addition of mixed polyraereneinheiten at nearly the same Einheitsl8nga _t so that the Kischpolymerefclr-est sndteil so "as if he were isomorphic This compatibility seigen not affect example Sylon 66 HiechpolyiBere" where the look repeating units exactly the same nuts (e.g. SS / ES mixed polymer, where f terephthalic acid

feEiv leomorphism occur '

Discussed Axisser at äeB above PACM-9 to ~ 16 mixed polymer units should Kischpolymörenbestandteile, regardless of whether the frencLo Eüstinidtoil Sac Jlmin, the acid or both ersetet, pre-a-af about 10 percent, will be limited ^ (calculated as the overall

Q O viöht 30 100 ff Polysicroe of PAoM-I, Y - / ^ C- (CH ₂ ) ^ -C _r / «der Z, where X eioli & τΐ ßie SUuregröas © in the free component, T sioi» nwf 2Z $ ^ Ni'iigSßse imd Z itself & m £ an AainsSureb constituent

1098 ^ 2/177

HIM 253

Diamines »which are suitable for the interpolymerization of all radicals T in the foreign constituents with (I)» bind dipri * 8re or disecondary diamines, in particular the aliphatic alpha-aaega * diamines with 2 and preferably 6 to 14 carbon atoms »such as hexamethylenediamine, 2 Ke thy! Hexamethylenediamine, tetramethylhexamethylenediamine, 2,5-dimethy! Hexamethylenediamine, di (aminopentyl) ether and di (aminopentyl) sulfide. Ring-containing diamines are, for example, Piperass _{substituted in T} Piperaaiue, such as Dieethylpiperasin, meta- or paara-xylylenediamine, diamine, para-phenylenediamine, ^ tß-Diaethyl 414 * -DiaainodioyclohexylpTopan-S , 1,4-DiaBinomethyloyolohöian, 1 _y 4 ** 2,3-dimetbylo7olohexatt, 1,4-Oycloheianaiamin vaaA Bie- (2-aulfo-4-amino-cyclohexyl) -methane. Diaoids which are suitable as PAOM-I constituents for Mieohpolymerieation ait (I) include aliphatic alpha-omega acids with 2 to 16 carbon atoms; Aromatic acids such as ferephthalic acid, leophthalic acid, sulfonated leophthalic acid, para-phenylene-diacid, bibtnmoic acid, S-methylterephthalic acid and 1,4-cyoloheian-dicarboxylic acid 5,5'-ThIOdIVaIerianstture;5,5'-OiydiTalerianB&ure; Di- (4-arboxyofclohexyl); Bis- (4-carboxyoyoloheiyl) -methane and BiB- (3Haethyl-4- * oarlioiycyclohexyl) -methane. Typical amino acids (or the corresponding lactams, if they exist) for Miechpolymerisation as Z components with (I) are, for example, alpha-omeea-amino acids with 2 to 12 carbon atoms, such as nitrogen and carbonyl carbon ι typical intermediates are pyrrole id cm, e ^ Aminohexanoic acid, - £ -Oaprolactam, H-aminoundecansfture

- 4 -109852/1772

BD-1233 ^

JT

and ^ -aminododecanoic acid. Also cyclieohe and / or aromatic amino acids, such as 4-Pipei ^t _{idincarbonsäure)} "- or p-Aainobeneeea & ure, 4 ~ A« lnocyolohexan ~ ee8ige & acid and 4 ^f ~ AsdiUH4-sie: eheByloarbonsäure, 4-Afflino ^ '- carboxy- (dicyclohexyl) -Methanf 4 ~ Asdns ~ eyolohexanoic acid or 3-aminocyclohexanafttire _> know to be used »

It is obvious that mixed polymer units, alters present all, can include those which have "white-valued organic constituents" about 4 l> generally about 20 carbon atoms, which by means of alino and / or carbonyl reactants as an integrating component "1" the linear Polyaerenkette be inserted * tteter "aweiwertiger organiaclier Beet ¹ * are awelwertige beds cause tanden," lad and mainly Xohlenwaaaeratoffa represent, but (1) duroh Betereatome "dl · TFTE * carbon at the amino or CarboBylreate bound as oxygen or sulfur, in The chain can be interrupted and / or (2) Subatltuenten for Vaaaeratoff carry kSnnaa, which such agents as sulfonate, sulfate, phosphate, phophinate, hydroxyl, acyl and the like. Although Torauga we have a "homopolyamide, we may also use a" homopolyamide for the invention rorhandeae Miechpolyaerenbeatandteile ▼ orsugawelae from organic hydrocarbon residues «·

Venn taden from the reaction product of PAOH and aliphatic DioarboneSuren “with 11 to 16 carbon atoms up to“ vasigen Streclcungsat ^ rhaititäten Terstreokt ”result in a boon.

109852/1772 -

BATH ORIGINAL

HD-1233

ray diffraction oyster, characterized on Xouator by a diffuse aura, indicating a remarkable pendulum of lateral order. Bb a single very sharp keridional reflexion occurs _r which indicates longitudinal θ order. These threads are essentially non-crystalline in the sense that "they show a three-dimensional order." Meridional- » reflection of the first and second and weak meridional reflection of the third order, the distinguishing feature of this crystal form is, daae their strongest Iquatorialreflexion a λ "d ^w _e rt -.w of about 5.1 his 5.2 S. corresponds. Kriatallform piping as ^{w n} ~ A KriBtallform!» is ezeiohnet the Zweekmössigfceit sake.

In contrast to the "A ⁿ crystal pattern described above, threads (" which have been rerstreokt according to the present invention, have an X-ray pattern in which the strongest equatorial reflection has a Bregg ^W d ^rt value of about 4.3 4 # 7 ^ anaeigt, and also show other characteristic differences, which indicate the presence of a new and different kind of polymorph, which is for the sake of convenience called "HS * -Eri8tallform" , which is characterized by a Bragg »e meridional reflection separated into two spots (" spots ") · The distance between these spots increases

9-8 5 2 "/ 177 2nd. _{BATH 0RIQ1NAL}

RD-1233

with increasing 3-thread orientation in the more strongly pre-stretched threads of higher strength. The crystal structure characterized by this Meridional Fleoken la Rojittfenray diagram is typical, but not essential, of the "high tension" or "HT ^B" crystal form called bo because it is produced by heating the filaments to a prescribed temperature under adequate tension At an even higher orientation nni ve au β, the heridional spots merge and reappear as a stripe (a stretched spot) and, as explained below, an ^{oil W} EO * crystal is known , new crystal shape formed.

The best known polyamides, polyhexamethylene adipamide, polyhexamethylene sebaeamide and polyeaprolactam (nylon 66 »610 and 6) have a crystal structure with a constant" ^W c "-Acheenab Ptand, which is directly proportional to the carbon atoms in the repeating structure of the polymer chain. have been generally opposed ssu these and most other polyamides, the terms {their crystal structure characterized, is with the PACM-11 -16-Polyaraiden the "o ^ Aehsenabstand shorter than the calculated from the Stuart and Brieglet-Hodellen. For example, the average growth is the chain length when adding two units to the CHG-acid does not, as might be expected would be 2.54 £ _r "but 1.96 S, which it is inferred that the chains in which ⁿ c ⁿ -Achsenriohtune not are fully stretched. In addition, the threads according to the invention also change

- 7 -109852/1772

HJM 233 _{or similar}

stall form of ^w o ^w ~ nit Aohsenabstand ierungsgrad Oriental of what these polymers gives store in such a way that "it increases this orientation also Rristalldimension" unimmt under the Polyaaiaen a unique position.

Bio HT-KriBtallfona ereoheint, if the polymer chainii in the crystal are stretched to at least »about 86 # of their theoretical length (that is, made longer} · If they are stretched to about 98 56 of their theoretical fingers * both the H3 ? ~ as well as the EG crystal form Tor; with increasing orientation - up to a chain extension τοη about 99 1 »the theoretical value - there are more crystals in the EC form · Such VSden have maximum pestibility ·

Ss should be emphasized "that aur distinguish the shapes careful and continuous into a one Köntgenstrahlenmethoden needed" The EC? Orm shows, as noted above * "o ⁿ -Achßenwiederholung, almost the slopes of the fully drawn models, ie 26.5% ■ for PAGM-12. A subdivision τοη other HS diffraction patterns is best made by observing the third layer line. This layer line spacing for the BO pora does not show the variability given above for the HT Fona. The EC ϊοηι shows a very strong one Xquatorial diffraction at 4 »3 £ in the Ctogensats to the 4.5 S distance which is typical for the HT pora.

109852/1772

BATH ORIGINAL

ED-1233

Similar to all thread-forming polyamides, PAOM-12 threads are spun and stretched to narrow an oriented yarn that is useful for textile purposes. Stretching is facilitated if heated by using a necked stretching pin (friction egg), a secret hat or holder elements in combination. A suitable arrangement is shown in US Pat. No. 2,533,013 (Hume). At Tadenverstrekkunge temperatures up to about 180 ° 0 dl * pre-stretched walls have practically no lateral order "but crystallization can be brought about by tempering at constant length and / or by a hot stress treatment, as explained above, with the production of the A-crystal form" Venn attempts are made, the strength of the threads nichtgeteoperten zv by using higher Teretreokungsrerhltltnisse. increase, the threads become dull and viscous due to the formation of transverse airways and are ecnit unsuitable for industrial use

A yarn which has the crystal structure according to the invention has better properties (e.g. strength, tension) than a non-crystalline yarn which has been produced with the same stretching ratio (see example Z). If the crude yarns are not annealed to form the "A ^ crystal structure, there is a loss of strength. Yarn with HT crystal form is superior to an OarK with an" A "crystal structure not only at low elongation ratios; there is also much that can be done better -rerstrekken, so arbv much higher VerBtreokungeTrekungeee are applied

1098S2 '/ 1772 bad omo.NAL

HD-1233

den can »whereby yarn © alt strength values of up to eu 9 or more grams per denier can be produced.

The correct stretching temperature is essential for the production of the threads according to the invention. It has been found empirically that the threads ^{should reach an "adentemperature in 0} O" which means that the expression (II)

t (° 0) »290 + 8 - 15m + 20 (-I) * (II)

should exceed the reproduced value. Here, m denotes the total number of carbon atoms in the main acid and S denotes the trane-trane ether isomer content of the PAOH in percentages (see the TJSA patent document 3,347,917 ^ Art., In which the production of FACH with varying tt content This formula serves as a guide in choosing the appropriate extension temperature, although in some cases it is found that small amounts of the HT crystal form slightly below the indicated temperature * Temperatures that are 10 to 20 ° G less than the * indicated by the? or * cl (II) are gate

eugsweiae at higher (a · B _t 6) extension rerhaltnieeeti applied"

An upper limit is that the scattering temperature is not should be so high that the thread, without resulting in a directly proportional orientation, »" is warped; d * h., "Verstreokung in vieooeen yiuss * (" rlecoue flow drawing ") suss ver

10985 2/1772

BATH ORIGINAL

RB-1233

"Stretching in vieooeen flues" occurs when the thread temperature is too close to the softening point of the polymer. The stretching is preferably carried out in two stages, the high temperature being used in the second stage. Bas in the ÜSA patent 3 091 015 is suitable, and any conventional heating means can be used, e.g. Beyond their elastic limit, stretched beyond their elastic limit, reach the prescribed temperatureThis high-temperature stretching usually forms a rope of a stretching process in which the threads achieve an orientation which is equivalent to that achieved with a stretching ratio of at least 3.5 will.

Oxidative degradation at melting temperatures should also be avoided "Bios are best achieved by spinning into an inert gas such as nitrogen or water vapor. The use of a heated inert gas is particularly desirable as this provides an environment in which the melted thread hinders with minimal orientation and maximal evenness of the cooling by the thread until the spinning titer or undrawn syrup are refined can. This method provides threads that can be drawn more than those with excessive spin orientation have been produced »

1 0 9 "8% ¹ 27 177 2

BATH ORIGINAL

BB-1233

A technical yarn with the most desirable properties is usually achieved by using τοη PACM-Diaain "it de" highest tt isomer content. Also, by using a polymer "it high molecular weight such properties are improved · Preferably, the molecular weight should be at least 18,000, and higher molecular weights are even more desirable," Practical considerations relating to Abt high Schmelzvisoosita't of polymers suggest the use τοη polymers Molekularge -) Weights τοη 25,000 to 35,000 close.

Within the general range τοη process conditions, which are suitable for generating the whisker crystal structure according to the invention, preference is given to those conditions according to which the? & Äen are exposed to the prescribed elevated temperatures while they are subjected to a tension τοη at least 5 $> or more. Even a very curative effect of the increased temperatures on the threads has proven to achieve the desired. The crystal structure proved to be suitable.

The threads according to the invention are used in such areas particularly useful where high strength, high modulus, and low shrinkage are desired. These areas of application include the reinforcement τοη mechanical rubber articles, soaps (especially for low pressure when standing (»flat spotting")),

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SAD

BD-1233

Belts, plastics, laminate, seat belts, tarpaulin, canvas, »rope, sewing thread, etc. Included are thread bits with a fiter of 1 feie 50 denier as well Higher titre honofilaments, for example those conofilaments whose diameter is 0.12 to 1.25 a (5 to 50 mils). The threads can also be used in flooken or staple fiber form will. Other threads or fibers ("fibers") can be combined with it for purposes of weaving.

When the threads are used as by-racks, the processing conditions used for ffylon 66 can usually be used. be drawn in. For example, a »standard cord construction (12 χ 12) is used for 840 denier gara such as in the case of clay polyhexaethylene adipamide. The Corel is immersed in an Eoroin-Formaldehyde-Iatex (EF1) adhesive and dried for 2 minutes with a tension of 0.9 kg at 150 °. The cord is then turned 5 to 13 pounds at 190 ° C to 220 ° 0 for 30 seconds to? Minute stretched. The soap is vulcanized under conventional conditions used for Sylon 66,

Test methods and standard working methods

The calculations of the lateral distance a (d-distance) and the "o" -axis dimension are carried out in the usual manner (see the Description of H * P, Klug and I ». E. Alexander in X-ray Diffraction Procedures, "John Wiley and Son, Inc." Few York, 1954 »

• 13 -109852/1772. _BAD original

BD-1233

in particular pages 88, 89, 333 »334» 335 »567 and 568)« of the Klug et al. Used in the work cited above or S is the vertical dimension of the unit sz eile.

If reference is made on the yarn module »is the« aftermarket module " ("initial modulus") turned off.

The "Breaking Strength * (T ^) (" Break ) tenacity *) is the one related to the fiter de · Qam »a» bite point strength; Ei "offers a useful * method of comparing the strength potential of yarns" which have different Yestlgkeiten and Dehmmgen, sn, throws you out of the picture

T ^ m T ( 1 + O _f O1 B)

calculates in which f the noreal »steadiness in g / den and B the Elongation at break of the yarn in Proaent are

The viscosities of the polyesters given here are relative viscosities (HV) as defined in US Pat. No. 2,385,890. Unless otherwise specified, a mixture of 50% formic acid and 50 % phenol is used.

strength and tendon and modulus are made using a Instron tensile strength testers at 60 pounds of tendon per minute beat inert. The yarn is kept at 24 ° 0 for 24 hours before the call day and 55 & ger relative humidity relaxed

,, _?; IO9V5V / I772 BADOR ₁ G ₁ NAL

RD-1233 _

example 1

A polymer is produced by adding a mixture of .beta., 2555 kg bis- (4-a "inoeyclane: xyl) -metfcÄn" with 70% trans-trans-ftereoieomer content, 9.0357 lbs dodecanedioic acid and 17.2 lbs Vaeeer is heated with stirring in an autoclave · The temperature is increased to 135 ° C, held for 30 minutes »and then 12.5 kg of distillate are removed under atmospheric pressure · Then 47 g of 25% acetic acid solution (stabilizer) and 39.6 g a solution of manganese (II) hypophosphite catalyst is added to the autoclave.The autoclave is then kept at 30 atmospheres at 285 ° C, and the pressure is reduced for 90 minutes, during which the temperature is increased to 300 ° C , lowered to atmospheric pressure. The autoclave is kept at a temperature of 300 ° C. for 90 minutes, after which the polymer is extruded, cooled and cut into blocks.

The polymer has a relative viscosity (K?) Of 115, measured in 93% Araissic acid (defined in US Pat. No. 2,385,890). The! Polymer is dried, aäengarn spun in a Sintragsschnek- ■ • 'ce nacbraalser "melted and at a temperature of 295 ° 0 za 34-I?. The yarn has an EV of 212. The (iarn is knitted over a stretching pin heated to 100 ° C on the 3.56foche. It then runs in a helical winding around a Kohr kit with a temperature gradient of 150 to 190 ° C (the in direction of the yarn run increases) until a total of 4.0 is reached.The Garatiter is 260 denier.

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10 9 8 5 2/1772

BD-1233

The yarn properties are given in Table I. For one If you try to increase the resistance to cooking, the total aspect ratio gradually increased to 5.24; the properties of these yarns are also listed in the table below.

Tabel

attempt Stretching
relationship strength Tendon, T _b gpd 1 4.0 4.8 15.9 5.6 2 4.25 5.2 14.9 6.0 3 4.5 5.5 14.2 6.3 4th 4.75 5.0 11.2 5.6 5 5.0 5.1 10.6 5.6 6th 5.24 5.1 10.5 5.6

It can be seen that the strength does not continue to increase with the stretching ratio. With the higher drawing ratios the yarn is hoisted by hoists, which peripheral taa the flocks walking around, increasingly dull, and streclningfibrückö Bind often

However, if the yarn of experiment 1 Over a hot spot at 150 ° C and an atif 200 and 210 ° C heated 2-zone plate is further stretched ^ i, 49 times), becomes a gan ?. with a strength of 6.4 g / de .; at 10.9 # Elongation preserved (T ^ - 7.1). With plate glass doors above about

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! € 9852/1772

BATH ORIGINAL

RD-1233

215 ° C falls the achievable yarn tenacity because of Verstreolomg 1 * viscoaen Flues and consequent low orientation "- effective from" The Gesamtverstrecimngsverh ltnis & for the 6.4 g / denier yarn is therefore 6? The Runtgen & radiation examination shows «that« the yarn has the ΗΦ crystal structure. The diffraction oyster shows that the crystal has a ^w d "distance of 4.6 £, an" o · axis dimension of 24.1 Å and two light spots at the first meridional reflection · The yarn has a Ϊ ^ value »of 13 $

is larger than that of the best yarn in Table I. Since the calculated ^w c "axis dimension for this polymer is 26.5 % , the warps in this yarn are fully stretched to 91 #.

Example 2

A polymer made from PACM-12 with a content of 90 # tt isomers "is melted and spun into a yarn." The yarn has a relative viscosity of 141 and a birefringence of 0.0153 · Da * 150 ° C heated pen to 3.0 times, and then while it is in a second Terstreckungsstufe with a series of three 10 cm long plates, which are heated to at 160, 170 and 180 ° C in the order of contact, on stretched i, 33 times · The total stretching ratio is 4.0; the speed of the gate push roller is 1.2 m per minute. The X-ray diagranea, which is typical for this yarn, shows practically no lateral order. If a hot plate is additionally arranged after the stretching stage

- 17 ^109852/1772

(total yarn contact about 0.8 a) to keep the yarn at constant Annealing length at 250 ° C results in yarn (2) »which has the" A "crystal shape.

If an attempt is made to increase the (total) draw ratio to (3) 4.25 and (4) 4.5, the yarn strength first and then down. Daa yarn (4) contains cross cracks, and many cracks occur when stretching Process conditions and yarn properties are given in Table II specified «

lot of contrast arises when the same supply thread over the pen heated to 150 ° 0 and the pen heated to 210, 230 and 240 ° C Plates stretched 4x and then tempered at 240.degree is, yarn (5), which is better in terms of strength and elongation as yarn (1) or (2), although the same draw ratio is applied. This yarn has the HT-Eristallform.

The stretching ratio series is, as shown in the table, continued until a yarn with a »fiter of 8 g per denier is produced at an aspect ratio of 5.2. This Yarn is mostly found in the EC crystal troal. The process conditions and yarn properties are listed in the table.

- 18 -

109852/1772

"BAD ORIGINAL

Ia "belle II

Try Mr.

Ge $ aa-tr er 3 tr e ckutisp-

relationship 4.0 4.0 4.25 4.50 4.0 5.0 5.2 160 160 160 160 210 210 210 Plate 2, ⁰ O 170 170 170 170 230 230 230 Plate 3, ⁰ O 180 180 180 180 240 240 240 - 19th
109852 Tenpeniag temperature,
OC
Birefringence after
drawing ("Drawn
Birefringence ") 0 , 0494 230
0.0461 0.0456 - 240
0.0495 240 240 _> SriStallfonß no A. no no HT ht / ec BC NJ Strength, gpd
Strain, # 5.9
10 5.8
13.3 5.8
12.4 5.7
11.0 6 * 8
13.2 7.6
9 * 4 8.2
9.0 Module, gpd. 44 38 40 40 41 58 58 to
6th
1

HB-1233

It is a yarn that has the HT crystal structure "lat, like" the Birefringence evident from drawn yarns from Hatur even with the same Yerstreokuitgeverh & ltnie and the same level of orientation more firmly (Versnob 5 compared to experiment 1).

Be i.8 vt ie , 1 3

PAC3M-12 yarns with different tt isomer content are used, as in Table III gaseous, mixed. The yarns have the ones in the table specified properties «ad structure ·. The Veretreokongabedinguages are chosen in such a way that in every »case the Hf crystal shape is created.

- 20 -

109852/1772

SAD

ED-1233

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- 21+ 109852/1772

SAD ORIGINAL

RB-1233 '22.

It is noted that as general strength and Anfangemodul dee yarn ait large expectant ^R e * ~ Aeh8enabstan & increase.

Example 4

From PAOM, since aliphatic dicarboxylic acids with 11 to 16 carbon atoms have been polymerized, a pure yarn is spun and stretched under various conditions. The procedural conditions. " Crystal shapes, * d * - ¥ erte (strong reflection) and "c" axis dimensions are compiled in Table IT. The yarns with a ⁿ A ⁿ crystal shape are tempered with constant lung to develop the steel structure. This stage is not required for yarns with an "Hf crystal structure" although the percentage crystallinity is increased by a tempering treatment when it is carried out on the yarn under stress.

- 22 - 109852/17 72. Bad om _G i _NAL

Table, IV

J) i3 acid

TT salary » $

Stretching ratio

Maximum elongation unteaporature, ° < Temperongs tea temperature, C.

Krietallfora d value, & c-AohsenabB ^ and, £ Garnelgeiiflcliafteui Feetigfceit elongation, i> modulus, gpd.

-11

90

5.0

225

B «

4.4

23.5

6.5 8.2

64

• -12

70

4.0

190

220

4.8

70

6.0

210

Bf

4.6

24 * 1

11

-12

90

4.0

180

230 A

5.8

13.3 38

90

4.0

240

240 Bf

6.8

41

• 13

* ♦ Best made of tempered polymer "iifloclc" i

97

3.1

200

fef
4.6

5.5

-14

3.1 200

Bf 4.6

24th, 9th

3.1

26th

-14 70
? 70 -16 70 70 "3 * ■ 4th 100 170 160 170 - 160 A. Bf A * Bf 5.0 4.6 5.0 4.7 25.2 * 9Λ 1.9 4 * 2 4.7 85 32 12.8
tm

Vi

cn σ> co cn

RD-1233

B β, 1 β ό iel 5

According to a similar Polymerisationsarbeiieweise as itt Example 1 was shown, a -Polymeres PACM-12 (90 $ tt) ax a relative viscosity of 182.4 prepared "The dried flakes are applied to a spinning unit having a SchneefcenschaelBer and at a Spinndiisentemperatur of 335 ° C extruded from threads. Bass yarn (HV 150) is stretched three times over a stretching pin heated to 155 ° C and then stretched again while it runs in a spiral shape around an ear, at the entrance end to 205 ° C, in the cement to 215 ° C and is heated to 245 ° G at the starting point.

is 5 »9. This yarn is next writing, as shown in animal patent geseigt of Hume, using a 160 ° ö erMtsten stretching pin _s on a heated plate at 240 ° C followed by _T susätzlich to the i, stretched 05fechö. The yarn has a tenacity of 9 _S 1 gwU. The ^w c "-AOhSWn ( ⁹ SW ^ TiSiOn is 26.4 ^, which corresponds to about 99 # of the theoretical distance ΗΪ- as well as the EC-Eristallf οπή.

Example β

A polymer made from PACM-12 (PACH with a tt isoicer content of 90% ) is poured in buckets of a feed screw melter at a temperature of 330 ° G and through a filter pack and a 17,000-liter inlet into its superheated water vapor atmosphere

109852/1772

BATH ORIGINAL

350 ° 0 extruded and then cooled in Lxift »Its sliding finish is applied to the threads, the middle of the feed B-tremi roll cabinet at a feed speed of 90 n / min. be sprung su a Yerstreckungseone. The yarn has a relative tittiness το »157.

The threads run around a 7 * 62 cm (3 in) stretching pin, which is heated to 150 ° C, then around a pair of daawiaohengeao-held, driven stretching rollers and from there in two helical turns in a bore that has sections "The aaf 210, 250 and 240 ° C are raised, with the tea temperature increasing in Rioht" ng des Garalattfe · The yarn next runs on a pair of long rolls, which are heated to 240 ° Q "The yarn Iftoft in 18 turns over these Hollen henm · Then the threads au a pair of conveyor rollers, the calibration »it the same speed as the Texperungerollen turn" and from there a au Spuleaechine. Yarns are produced at two different locations. The Terfahrena conditions »Yarn properties and crystal structure are listed in Table T»

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ED-1233

Tabel

Containing in the
system 4.0 Sristallfora HT 6aräfeetligkeit _r gpd » 7.4 13.6 BeginningFnsodule , gp <! · 41

4.8 HT / EC 7 * 9 12.7 48

Threads of the mixed polymer have, if they are veratreoct at the suitable temperature defined here, in any case the HT plastic structure. Biese & a »t üknmgefor» is sung in the following example.

Eb mixed polymers are produced and V & den are spun and under the conditions given in Table TI Teretreofct. The loos are examined for their crystal structure. They are results shown in the table

^109852/1772

BD-1233

labe lie YI

Verguche-Mr .

Main polymer bed component

Raised bed plate weight ratio never maximum stretching temperature, ⁰ O crystal form

PACH-I2 (70 tt) PAOM-12 (70 tt) PAOH-I ¹ ^ HDDP ² ^ «12 90/10 75/25 210 180 HT HT 4.6 4.6

1) I means isophthalic acid

2) HDDP means 4 # 4 ^t -DiamiTioaicyclohexylp2? Opane-2

- 27 109852/1772

Claims (1)

HS-1233 ag. DWWNr 196T Claims 1. Crystalline, oriented thread to the one »Polymers with high Molecular weight, characterized in that it is mainly consists of the following, recurring structural units / \ / X 44S (i) where η 9 - U means, reduced "70 Oew.-ji dee diamino components of the repeating units a tran" -transetereoiBoeere configuration and the load a KrI-etallabetand in the transverse direction of 4.3 to 4.7 f "beetieat" the strong Xquatorreflexionem in a Bragg * «open X-ray diffuser. 2 * thread according to claim 1, daisrok gekennaeiolmet, that he aas W at least 70 Öew, - ^ C recurring structural units of the forael I «aid Me en 50 eev.H ^ lliecÄpölyÄereebeetandteile ron PAOII-9 to PAOK-16 oeeteht. 3 * load "according to Aneparuch 1" thereby ffk ^ nnseiolmet, that "he eue sindeeteae 90 Oew.-Jt return leader ßtrmktureimheite" the - 2β - 109852/1772 bad AD-1233 4. Thread according to claim 3t, characterized in that η is 10 * 5 · thread according to claim 4 »geketmeeiohnet characterized in that the polymer chains his au least 86 ji its theoretical" τβΐΐ-st & constantly stretched LSnge gestreokt 6. Thread according to claim 5, characterized in that the poly sera chains are stretched to at least 98 pounds of their theoretical "roll" _Λ constantly stretched length · 7 * procedure mm preparing the 78 s according to claims 1 hie 6, characterized in that aan Widen composed mainly of recurring structural units of the forael I! 'Stand while the temperature of the filaments t (° 0) is equal to 290 + 8 * 15 * + 20 (~ 1) ^m is »distorted _t where s means the oil content of the carbon atoms in the diefture and S the trane-traniH-Stereoisoaerea · - content of the PAQH in present. - V) -109852/1772 bad