DE1810426A1 - Mass and fibers or threads made from it - Google Patents

Description

The invention is based on compositions of matter or masses (dopes) Directed by carbocyclic aromatic polyamides in Liquid media corresponding to the purpose are formed, which optically are anisotropic (in the masses in different directions different light permeability and characteristic beiges). These Masses and related isotropic masses are used in the manufacture of l®r threads with an exceptionally high initial modulus and <ienti <az ° angle used

Di® invention relates to new, optically anisotropic masses made by essentially linear, stiff-chain, carbocyclic, aromatic

Polyamides formed in appropriate, liquid media · = ο With these masses and with related isotropic masses

Fibers ... and threads, foils, fibrids and coatings. In particular, fibers are od © 2? Threads of exceptionally high height i ^ odül and a small orientation angle received.

9 0 9887/1693 ' ^l '

ί 1810428

Di © masses gepäss the 'invention, the optically anisotropic sisid (determined by late-described methods) ·, are constituents from d®r group carbocyclic _a aromatic polyamide whose emanating from each © romatiaishen core, chain verls η straight bonds substantially coaxial or opposite directed parallel j are formed in sweclcent speaking ₉ liquid media. The liquid media for the formation of the masses according to the invention include, in particular, amide and urea, for which example is given later, alone for a _{combination of Ir 1} , with certain salsa (see B "LiCl) ; concentrated sulfuric acid, the frsies SG, oäes? Ifesses, may contain ^1; MP alone for si © h © der in connection snife susat means such as water © der Salsen Cs = B. NaF) 5 HSO ₇ Pj and HSO ₃ Cl.

The above ₃ optissh anisotropic masssn © d @ r aiaa related © n, isotropic mass- »di © bestinsnt © aroraatic folyamides contain, manufactured®! ^ Threads and fibers according to the invention have unique® properties in the spun state ■ {like later b®- s <slwi @ bsgjra) wi © aü © h after heat treatment (like later bösehriebsn) = These faesra or threads have instoösonder® an initial weight of about 200 g / the ₃ forsugöweiee about © fcwa 300 g / oen. Si @ s @ n waiter an orientation angle ©!. From untez · @twa HS and weis® under © twa 35 »■ Sesondsr ©, preferred fibers or threads according to the invention have farnex = ¹ a strength of over

Di © E & finamng is also described in more detail below, in which

Fig. X a Fh & sendlssgräsnm one (water = and lii

according to d ^ r K finding explained,

Pig «Il a © typical Bessi@hur.ig swis®h @ n Yis © 3Bität uetS. Po! L3? M3 k © ns © ntration bsi ä®o Mass © ^ gsmäss tlsr Srfir; duTig ₅ wsbsi d ^ v tieohe Konsentratiorispunkt su sshan is ₉ Fig. ΪΣΙ © ine t ^ piseh © Kurv © eisuss R6ntg®nfeeugMK.gsdiagrä ^ tore ües

Fig _o IV and γ w © ifeer @ Phasendisigrasüai® of masses according to ö @ 2 ^s invention and ■ -

; -. 909887/1693 - 2 -.

Fig. VI and VII critical concentration points of particular masses according to the invention as a function of the inherent Viscosi ity.

To the carbocyclic, aromatic polyamides for the purposes of the invention (of which the preferred, anisotropic masses according to of the invention are formed and / or from which the fibers and threads are made according to the invention know) belong to those in which the chain-lengthening bonds in the toilet are coaxial or in opposite directions and run parallel. These preferred polyamides are characterized by repeating units the formula

(I)

OOHH
-i " ⁿ tt _
^ CHCNR ° -N_7,

where R and R * (if the chain extending bonds are essentially run coaxially) of the group

Ι, Ί-phenylene, ^ • -biphenylene, / |, l | ⁿ -terphenylene and 2,7 -phenanthrylene

or R and R · (if the chain- extending bonds are essentially parallel) of the group

1,5-naphthylene, 2,6-naphthylene, 1,5-anthrylene, 2,6-anthrylene and

- 3

16 93

ή 1810428

2,6-anthraquinonylene

belong. R and R * can be the same or different and often have substituents on the aromatic nuclei (e.g. chlorine, meter » yl or methoxy).

Further polyamides according to the invention can be identified by repeating units of the formula

H (II) * rjl-R "-N Ψ

denote where R "of the group * ^xv - i, * i-phenylene and

listened to. Similarly, R ″ can be found on the aromatic nuclei Have substituents (e.g. methyl).

Copolymers, the recurring® units of the formula I as well as of the formula XI are also suitable for anisotropic masses of random (statistically disordered) copolymers of the same are preferred in the manufacture of fibers and filaments from anisotropic or isotropic masses. Under "irregular" is here too ▼ arise that the interpolymer consists of molecules that Containing units of one or more different kinds in irregular succession in large numbers. With the proviso that the stoichiometric requirements for the high * polymer formation is sufficient, the units can be of type AB (e.g. from p-aminoben & oylchloridhydrochlorid), AA (β. B. from ρ-phenylenediaroin or 2,6-dichloF-p-phenylenediamine) or BB («. B. from Terephthaloyl or isophthaloyle chloride) or mixtures thereof belong. It is not necessary that the relativ® Ansah! the different types of entity in different molecules or the same even in different parts of the same molecule is.

. "S0S887 / 1693 '" * "■

Although the polymer chains described above are mainly formed by Araid members (-CONH-5 and aromatic ring cores as described above), the polymers for the preparation of the Hassen according to the invention can also be up to about 10 % (on a molar basis) of the description above corresponding elements, e.g. units forming aromatic polyamide, the chain-extending bonds of which have no coaxial or parallel and oppositely directed course, e.g. are meta-oriented, or members that do not represent amides, e.g. urea or ester groups.

The aromatic polyamides for the purposes of the invention include poly (p-benzamide), poly-Cp-phenylene terephthalaramide), poly (2-chloro-p-phenylene cerephthalamide), poly (2,6-dichloro-p-phenylene- 2,6-naphthalamide) ₃ poly (p-phenylene p, p * -biphenyldicarboxamid), poly (p., p'-phenylenbenzamid), poly- (I _S 5 ~ naphthylenterephthalanid), parent aromatic © mixed polyamides such as z. B. the <p, p'-Diamin®b @ n§sanilid / t ^f erephthalajaid) -Mis © hp © lyamid, and random

like s. B. the (95/5) - (p-Bensaraid / m-Benzamid) -

Di @ positionnmg ^ indications for Bubstituentengruiippen on the aromatic nuclei of the polymers for the purposes of the invention relate to the packingCen) d © @ or ά®τ substituents on the diamine, the diacid or the other reaction participants from which the Polymer © is produced. So is-g. B. one won to end Ende'regellos © V © ^ fe @ £ lung polymer-forming "units in the chain, if si © m6gli © h ists from the Harn®η _s with any given polymers hi @ s? B © s @ i © hoet Wi ^ d ₉ with includes.

F®lyamid @ ₃ wi © öi @ © b © nb @ sehri @ b @ n @ n, with an inherent vision (wi © later b®s®te> i®b®n5 ^ on at least about 0, 7 "and vorsnag @ i? @ IB® TOn over about i _s 0 are fiber or thread-forming and particularly suitable for di® 2week © d @ r invention.

A Sj @ ^ ®pg) ügt @ s polyamide according to the invention, which is essentially homopolymer P © ly-Cp-b © nsamid), which essentially consists of like

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HO

exists is. slightly according to certain corresponding sweok, dissolved in special solvents kidneys are borrowed, if desired »LitfciiHWhlarid and may contain terminators *.

Suitable monomers include p ~ AminobenTOylhElog © «ii§ali © der formula

O (IV) Xj * ^

where Xj belongs to the group Jkvylsulfonafc-, Alkylsulfonafc-, ate-. and Halogenr @ ate, preferably §? ob! ^ qüqv ~ € fal®rmmt® and X ₂ ® & s © n halogen radical, to put it bluntly © ■ Brosi - © denotes. That. b © v @ 7 £ iigte Midsioiqsi * © “forms the pH hydrochloride. Other gceigsi ^% @ Honom @ r @ are p hydrobromide, p-

sulfonate and p «Assinoben8oyl @ hlL @ pidhydrogen8ulfatB Change, not in the tap» ü © w Formula W li @ g © »ä © Μ © μ © μ®2 ⁸ @, _ ζ« Β «p-Aaiino chloriässslffat, are © benfalis g © ®igo © t »The fee ^ orsiigte p-

Solution foss p-53 »i © nylamini
n © n Arbeifesweiee ^ © n Ovaf sirö Langes · ,. J ₀ pvakt. Chen. 148, (293?) With anhydrous B®silngraag © s2 get iferö® «» The massive and anhydrous® La ^ ®i ° iasig dl®s @ ® monomers © 2 »f © lg © in

ren Teüspemturen sur

To the solvents for 'di © Pel ^ erisatiensreaktion the one »äea?

N, N ₉ N *, N ^B

909887/1893

W-methylpiperidone-2

1,3-Dieethyli * ida «elidinon-2 (i.e. H, N« -Dis »thyiathylenur-

material)

N-methyloaprolaotaa N-aoetyipyrrolidine N ^ -diithylacetamide N-ethylpyrrolidone-2 N, H-Di "ethylpropione" id Η, Ν-Dinethylisobutyraaid Ν, Ν-Dieethylbutyraaid

T * traiiydro-1, 3-dinethyl-2 (1H) -pyrieidinone (i.e. N, N'-di «ethyl-

propylene hydrocarbon)

As a precaution, the FolfasrisatlonsMisehting nit salt η, such as lithium chloride, rereetxt; Such an addition can support the maintenance of a fluid mixture.

As mentioned above, chain terminators can be used in these polytechnics The ease with which the subsequent processing of the polyamide takes place and increases the stability of the polyamide for use in the polymerisation-spinning composite process described later. To the Xettensbbreehem for this purpose belong Bonofunctional compounds which react with the sulfur chloride end groups of these polyamides, such as aianonia, monoaaine (see B. methylaln, dinethylaine, ethylamine, butylanine, dibutylanine, cyolohexylaain, aniline, etc.) contain an asdd-forming group, such as, Ν-diethylethyleneditunine, hydroxylic compounds such as methyl alcohol, ethyl alcohol, propylene alcohol, phenol, water, etc., and nonofunctional compounds which are capable of reacting with the terminal groups of the polyamides, like other fluorides (see e.g. acetyl chloride), Acetic anhydrides (e.g. acetic anhydride, phthalic anhydride etc.) and isocyanates Cs. B. Phenylieocyanat, m-Tolylieocyanat, Ethyl isooyanate, etc.). To bifunctional chain breakers for the ▼ underlying purpose include terephthaloylchloride, Ieophthaloylchlorid, Sebacylchlorid, ^, ^ »- Biphenyldieulfcmylchlorid, Pyrotnellit- 909887/1693 " ⁷ "

acid dianhydride, p-phenylenediisoey & nat, BensidindÜsoeyanat, bis- <ti-leoeyanatopheny1 ) -methane, p-Phenylenediamine »mrPhenyiendiamine, Bensidin, Bi8- (4-aninophenyl) -8ther» Ν, Ν'-Eiaininopl rephthäle8uredihydz>& 2id and Xso-

To carry out the polymerization, you can use the desired © (ra) monomers (ni (as, when used, "den-chain terminator and Isithiumehterid}) in d © m gewtaschfeen Amid-- © der Ureaflus @ n ^ n vigorously stir the resulting solution from

cool until ®in® vimvse solution oder'eine Dieke, gel Wet present "One the other hand & m desired Monossere first in a small! tag® @ @ r in anhydrous, inert, © ^ ga ™" nieehen liquid as Teurahydrofursn, Dioacan "Bensol or Aeetonijbril, aiafsehlämraeii, before the amide drone agent is sugesetet" Vsrasugswoi®® is the resulting mix of monomer and organic liquid'at increased speed stirred unu rae <sh a sustnieniäesig .--- large® Haimraeng © des: by means of gugeeets ^. After a different method of working , the amidizing agent is frozen and mixed in the frozen state with the desired monomer. The solvent is allowed to thaw and the resulting mixture is stirred until a viscous solution or gel-like mass is formed.

In each of the above techniques which Polymerieatlonereaktion at low temperatures, i.e., ₀ h. kept below 60 ° C and preferably in the range from -15 to «30 ° C, for which purpose, if necessary, cooling is carried out from the outside. The reaction mixture is continuously stirred until it gradually changes into a viscous solution or thick, gel-like mass. The reaction is generally allowed to proceed for about 1 to 48 hours, preferably about 2 to 24 hours.

To achieve the highest molecular weights, these polymerizations are carried out under strictly anhydrous conditions. Reaction vessel and auxiliary equipment, solvents, and Reaktionsteilnehmer- be carefully dried before dero Einsatts, and the reaction vessel is continuously purged wfihrond the polymerization with a stream of dry inert es.ses _s "ss _e B * ₉ nitrogen. ■ '■ ·. .. · "■ -

387/1693

The polymerization reaction produces an acidic by-product (e.g. HCl or HBr), which is preferably neutralized. Neutralization is particularly preferred in those described below Procedures in which the reaction mixture is prepared for direct use in the production of shaped structures from the polymer will. In such a case, a base from the group is preferably used to neutralize the reaction mixture Lithium carbonate, oxide, hydroxide, hydroxide monohydrate and hydride and calcium oxide, hydroxide, hydride and carbonate and mixtures thereof. The use of a neutralizing agent is im In view of the fact that the acid causes serious corrosion problems in the processing equipment (e.g. the spinneret). Neutralization may also be necessary in order to obtain more fluid compositions, which facilitates the formation of shaped structures. When using a stoichiometric Amount of neutralizing agent can be an insoluble excess left behind, its removal before the creation of a shaped Form Cs. B. by spinning) may be necessary. Depending on the inherent viscosity desired, the neutralizing agent before, shortly after or long after the monomer feed can be added to the reaction medium. The addition of neutralizing agent can cause a sharp increase in molecular weight of the polymer (determined by measuring the inherent viscosity of the from an aliquot of the reaction mixture polymers isolated before and after neutralization).

The masses can also use excess neutralizing agents contain other insoluble material which is preferably removed by conventional means prior to the formation of a shaped article shall be. Z. Bo can with an acidic polymerization system, the bromine ion supplies, and use of lithium hydroxide as a neutralizing agent 'the accumulating lithium bromide in certain Masses must be insoluble, and the bromide should be removed prior to spinning or casting the mass.

Di® composition can be used to form a fluid of the for the spinning or casting of the desired solids content and / or od @ r viscosity under the conditions discussed later - in a vacuum © be narrowed.

909887/1693 " ⁹ "

E. ϊ. du Pont de Nemours and Company Q-I031

To isolate the poly (phenenzamide), the polymerisation solution is combined with a softener for the polymer, e.g. water, on a suitable mixer and in this way converted into a powder. Bas powdered® Polymer® is processed with water as well as alcohol over Naehfe in a Vacuurofew: ' ^{dried at, about 60 to 90 0} C' before it is stored or treated for the following processing & aoe

The essentially lioüiop @ lyni @ re poly "(p" benzamide) " obtained in the above Mais® mist © in PeakteShenvörhalteals (Feal £ Height" Ratio, abbreviated PER) from below 0 * 86 "to" and dwüteertinatts in Sedimentationsprüfimg of the polymer in the tube k min Bmäimmt determine (the tests are later tmechriebera} ® It is understood that for a Prob® "this Polpieresi * the bet ®tkä $ titen temperatures spun © _of; been © rfeitet iS _1, um F & ®lzhMh% n ^r f®F- ■ relation OgBS tlbeFSQhr © it @ si Immm the SediMHta & iwseigeffiSuSften can © benfalis aater © © eia « äw & h © la Poly« {p ^ bensaB) id) ratt PHR of over 0.86 © leases itself for the purposes of the invention. ζ «, Β <. for anisotFopt- mass »@us dies ©« Polyraere ^ in HF oäer deurn-.

Polyamides for di © 2w @ eke der Ipfindimg köime »© henden Coreaktiöiistöiljffiel» © »ash low temperature I & solution polymerisation« methodeii (ie at below 6 © ⁰ C and as a precaution at »10 to +30 ⁰ C) Mtolieh ü @ n tu dep HSA »Pat @ nfcseteift 3'063 966 for the production of iroa Poly« {p ~ p! & ^e nyl ^e nteirepht & ai & inid) besehPi® levels are obtained »Ζ · Β * such Polyamid® can be hextest, indeBi mam p "PteByl © NCTI & raif? t odor ^ -ChloF-p-pheiiyleiiciiaraiw with polyamidbiläeEflen derivatives of terephthalic acid to the reaction brings is convenient eingaeetat in" form your OiIaIoge ° halides, di © after vertxmAeir methods leieht 8isids "This BieaÄonelnr®. gewlStolicli id. rd- the © islttyecilil © i * i <ä isevoFzugW these Niedert @ siperatuF-L ^ ungspolysii @ FlsatiORen are fttot, as nan siy ^ Siitet © isie gßMkXt® JLisimg d®s Bianisis lsi a solution smifctei © öei »eiSietaF sniitteia aos of the group HexajBethylpSwsphornsiiäj, N-ffelfchylpyrrölidoK-S wsid "'

usiter stirrer ?, and -nihlea * da · BIsitapeefeloFM hi ^ siigegeteis «. Frequently 9 0 9.8

1310426 Ai

the polymer will fill out within a few minutes, and in other cases gelation of the reaction mixture can cause * step. In various cases it may be desirable to stir the reaction mixture for 30 minutes to several hours or longer or let it stand. To isolate the polymer, you can quench the reaction with a non-lots for the polymer, e.g. B. water, move on an appropriate mixer. Before storage or subsequent processing to bulk, the polymer is collected, washed and dried.

The production of other valuable polymers and copolymers is explained in the following examples. These representations can also be “in-situ synthesis” directly extrudable, anisotropic Include masses (e.g. as shown in Example 4 **).

The liquid media for the formation of the anisotropic masses according to the invention include

1. Certain amides, ureas or mixtures thereof, including Ν, Ν-Diaethylaeetamid, Ν, Ν-Dlmethylpropionamid, Ν, Ν-Dioethylbutyramld, Ν, Ν-Dlmethylisobutyraaid, Ν, Ν-Dimethylmethoxyaoetaldidfhyyl -2, N-methyl-. piperidon-2, N-Methylcaprolaotarn, N-XtI ^ 2pyrrolidon-2, N-Acetylpyrrolidon, N-Acetylpiperldin, N.N'-Dikudthyläthylenurea, N, ti'-methylene propyleneurea, hexamethylphosphoramide and N, N, N ¹ , N * -Tetramethylurea, which can be used alone or in combination with lithium chloride and / or calcium chloride,.

2. Concentrated sulfuric acid with a concentration of about 90% by weight ₉ usually> 98 to 100 _{% by weight of H 2} SOj or oleum (e.g. sulfuric acid with a content of free SO of up to 20 % or more ), which may contain salt (z. B. NaHPOj, Na ₂ SO ,,, Kaliumaeetat, which can be present in an amount of 2 to 3 % of the total weight of the mass), the choice of the most favorable for a production of a given mass Sulfuric acid concentration is partly based on the inherent viscosity of the polymer used,

3 «Hydrogen fluoride (acid) alone or in combination with additives such as water (1 to 2 % of the total weight of the mass

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se), NaP or KF (i to 2 JE of the total weight of the mass), in © rter chlorinated carbon (e.g. CHgCIg) or mixtures thereof (in an amount of up to 5 % of the total weight of the mass), ή. Chloro- or fluo-eialfanoic acids.

Making the mass:

Polymers and mixed polymer®, which have been produced according to the methods described above and isolated after their formation, can be combined with an appropriate liquid medium to form the compositions or masses (execution forms of this type are hereinafter referred to as insulating polymer masses). In certain other embodiments, such compositions or masses are formed in a polymerization spinning machine. The polymerisation process utilizes the polymerisation process (such embodiments are hereinafter referred to as n-situ polymer mass). The mass can also contain other substances, such as small amounts of inert, organic liquids (see e.g. tetrahydrofuran , Oioxane, benzene or acetonitrile), which are used to disperse the monomer, other amide or base substances (e.g. hexanethyl phosphoraoid or N, N _f H ', N'-T «trÄa» fchyl ~ urea), water ( that was intentionally introduced or is present incidentally) and the acidic by-product of the polymerization reaction (see e.g. when working with a lower ionetric amount of a neutralizing agent Is).

* The usual additives, such as dyes, fillers, matting agents, UV stabilizers, antioxidants, etc., can be introduced to achieve their respective puncture with the polymer or misoh polymer or in the compositions according to the invention before the Production of shaped structures from these being dispersed *

The anisotropic masses according to the invention can consist of an anisotropic unit phase or an emulsion of anisotropic and isotropic phases in any ratio or of any dispersion degrees are formed. ! The also sw l @ p @ t elimination of Fm @ ern and Threads according to the invention are isotropic!% Eeen have a

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909887/1693 '. . - ^: - "-. ^l ~

isotropic single phase. X in these phases or in the emulsion can also, especially in the preparation of the mass by dissolving isolated polymer, very small amounts of undissolved Polymers are present. Below the mass there is a shaped structure providing Cz. B. thread- or fiber-forming, film-forming or to understand fibrid-forming) polymer-solvent system, which can also contain more than one of the above phases.

Anisotropic masses:

If the constituents forming the mass are combined in particular concentration ranges according to the invention, optically anisotropic masses result, i.e. microscopic regions of a given mass are birefringentj a larger sample of the mass depolarized, linearly polarized light (described below, also referred to here simply as light or polarized light ), as the light permeability properties of the microscopic areas of the mass vary with direction. This characteristic is related to the presence of at least part of the Hasse in the liquid crystalline or mescmorphic state. Liquid crystals are as described by GH _Brown's Industrial Research, May 1966, S "53 to 57", with many of their properties swisehen the liquid and solid states. They thus have peculiar structural arrangements, which partly give them the order of crystals and the fluidity of liquids *

The present in the anisotropic masses genass the invention steifkattigen, aromatic polymers are likely to constitute substantially rod-like structure in the liquid medium · The rod-like configuration shows a study dilute solutions in which the exponent C ° PZJ 4 the relationship ° KM <t by Mark and Houwink (£ yj * intrinsic viscosity, M * molecular weight, K a constant so that <* can be easily determined) is relatively high. The vast majority of polymers for which this relationship has been determined? are described in the literature and have given values below 0.9. Of the polymers used in the compositions according to the invention, see oc determined by poly (p-benzamide) su 1.6, this being based on non-fractionated polymers

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certain value is based on an inherent viscosity in the range of 0.1 to 2 and weight average molecular weight determinations in sulfuric acid (95 to 98 Cfew.g). If a given exceeds a certain critical concentration point, an anisotropic phase _{0 is} formed which has the characteristics · ■ of anisotropic masses according to the invention ·

A given polyamide / liquid medium mass exists underneath a certain polyamide con ^ entration © ine tropie of the cash register. Hit sunetüaarääep Polyasaidkoneeistration climb ¹ ! Viscosity of the mass at "an" * hereinafter "la" cryptic centering point "designated psistkfe. however, results in ®i © h in dar

the curve of the vieeosifcät as a function of the ion concentration a® strong discontinuity when 'the mass from deip isotropic in the par * » "tially anisotropic state goes down" £ in further? Polyiraidxiisats

leads to ainem Absinkem of "¥ iseoiitä% of the mass _s while the masses more anitotFop» »Sii% ® exemplified © Tdww® become the Viseosität as a function of ion © nte & ^ I © n is beechri®-- ben in Bfiapiel 73 and in XX explains <>

A given measure of enjoyment of the findang is as stated above. _e to "isotropic" mim the components of Hasse in particular tionsbers-iohen vorliegesi. Ztdeeten the Konsentration äea or Miaühp © ly "@ y @ si und seineip inhS?" Nten Viseosity and the perature di © aUgen®in the BeMniebo. baetiiiit $ in requested a given polymer / or 'Mieehpolyoer / FIÜBeigfBediuiii-N gsi "anisötrcp let" b "st®ht eitii) venfietolte Bagieteimg" BeiepieUtefte ÄaeeiabeBiehim "·" gen utsiü i »* Example 6 and Figure" I and .in Äispiel 7k and Pig · Vi

and V shown ο Ede Bastinsiiisig · solehei »Eazielittiagea fir« ader «masses according to the d®p invention spawns Yes Metitiifievep

critieeh «consensus point

gen polyamide wi © aueii'fieisen 0 © wiehtsprozentaüt Viscosiiätj, desi Jewtliigea FlflesieBsillwa nmi'äes ³ f @ mp © ratnr “The effect of the © swichtsproaentsatsss of the PolpieBia oai.der T @ mpeiäF © tiarfl on laesess sni two νerseh ii "« «iges - Example 75« Di® toswlrkwsig de? isÄirwtea ¥ iseo @ ifeät 'on sw @ i -different »Polyamides are in Enlspiel 7k w & a ü®n Fig. 1 and VI

909887/1893

According to the invention, anisotropic dimensions can be produced which contain polymers and copolymers of the type described above with a content of up to about 10 units of aromatic units, the chain-extending bonds of which are not essentially coaxial or parallel and oppositely directed. For example, a random, high molecular weight mixed polyamide in the form of 95/5 mixed poly (p-benBamide / m-benzamide) can be produced from p-aminobenzoylchloride hydrochloride and m-aminobenzoylchloride hydrochloride using the low-temperature polymerisation techniques described above. One of such a mixed polyanide in z. B. Ν, Ν-Dimethylacetamld and Llthlumehlcrid produced Hasse seigt the optical anisotropy.

t-

Anisotropic masses made from aromatic mixed polyamides !!, in which all chain-extending bonds are in the p-position, are also within the scope of the invention. For example, an ordered ^{misohpolyanide made from 4,4 f} -dia * inobensanilid and terephthaloylchloride or 2,6-naphthaloylchloride can be incorporated into an anisotropic mixture, which 1. the mixed polymer, an amide solution and LithiumBohlorld or 2. the mixed polymer, a suitable sulphuric acid or Contains oleum.

A good spinnable group of anisotropic wet contains about 6 to 15% by weight of poly (p-phenylene terephthalamide) with an inherent viscosity in the range of about 0.7 to 2.1, 0.5 to 5% by weight of lithium chloride, the remainder being one Amide mixture of Hexamethylphosphoramid and H-Kethylpyrrolidon-2 with a content of over k $ VoIJi of Hexamethylphosphoramid. The relative amounts of these Beatand parts, especially hexamethylphosphoraide and K-methylpyrrolidone-2, contribute to the ease with which these spinning masses are obtained certain Amidmisehung is used. If, on the other hand, a different amide solution containing more hexamethylphosphoramide is used using the same amounts of polymer and string, the combined constituents must be heated to at least about 35 ° C to achieve a liquid, anisotropic layer, the birefringence of which is observable . The making of the wet

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precaution takes place by vigorous misoing of the ingredients and at low temperatures, 8. B. such low temperatures as O to -10 ° C.

Another well-spinnable group of anisotropic masses contains about 5 to 25 Qew. % Poly (2-chloro * -p-phenylene terephthalamide) with an inherent viscosity in the range from about 0.7 to 3 0.5 to 8% by weight of lithium chloride, the remainder being H, N-dimethyl acetamide. In addition, anisotropic masses can be produced * the 1. poly- (2-chloro-p-phenylene terephthalamide), calcium chloride and N, N, N ^B , N «-tetramethylurea (abbreviated TMU) and 2. the same polymer together with N, N- Contains dimethyl acetamide and calcium chloride ». An anisotropic mass is obtained by adding 2.5 g of poly (2-chlos ⁱ -p-phenylene terephthalamide) C ^ £ _nh «1.27) with 25 ml of an aue 3» 5 g of thium chloride and 100 ml of TMU prepared mixture combined. This mass gives, under the polarizing microscope - «in brightfield and, determined in the manner described here, a permeability value (T) of 8i,

Between the amount of poly (2-®hlor «p'-phenylent @ Fephthalssiid © s) and its inherent viscosity, the amount of Salt® and the toew. The amount (s) of amide (s) which determine whether a given composition is optically anisotropic under otherwise constant conditions or not, is an intricate relationship. For example, an isotropic mass can be achieved by changing the. Polfner consistency can be converted into an anisotropic one. A clear mass 8. B. do 10 g of Pöly ^ Tz ^ cblor-p-phenyleneterephthalamld) ^ * ^ ^ _n J ₁ * * * * 3 in 100 Bd of a mixture of 100 al Ν, Ν-dimethjlacetamide and H, 3 g lithium chloride is isotropic, but becomes cloudy and, like Liehtdepolarisationsuntersuchungen Beigen, anisotropic if you add another 10 g of the polymer. The observation that a mass of 20 g of poly- (2-ehior-p-phenylent @ repht! Ialasdd) BIt ^ _n J ₁ «1.13 and 100 ml of a mixture of 100 ml H _f N * Diaethylaeetaiiid and 7 g Lithlurachlorid is isotropic.

P € »ly- (2-9hlor-p-phenyleneterephthalami« Sl deflated cash registers let you see in two layers »laid out, · iti% ter @ isotropic volumes inside · more dense and anisotropic. This. Separation can see B ₈ achieved

- 16 - ■ - ■ - -

90988 7/1693 ..

1810428

be made by making a spinning mass a corresponding time Cx ^ B. a week) or by spinning. Corresponding to the convertibility of an isotropic poly (2-chloro-p-phenylene terephthalamide) mass into an anisotropic mass by changing the polymer carbonate with constant inherent viscosity of the polymer, one can change the volume of a given anisotropic phase in an i-layer dimension. Achieve the system by incorporating a polymer of higher inherent viscosity into the mass. For example, a mass separates the 10 g poly (2-chloro-p-phenylenterephthalamld) with ^e * ^nem 3Z-i _nn ^s * »* ■ * in 100 ml of a by combining 100 ml of N, N-Dimethy! Acetamide and 3.12 g of the lithium chloride mixture obtained, on long standing in two layers, of which the bottom layer makes up 20% of the total volume. If the mass is made with 10 g of this polymer with an inherent viscosity of 1.85, the anisotropic bottom layer forms 33 % of the total volume.

It has been shown that the maximum amount of salt that can be put into a anisotropic mass of this polymer can be present, with increasing inherent viscosity of the material used to produce the mass Polymer increases.

The combinations of the above-mentioned components are chosen so that an anisotropic cash arises; With certain constituent combinations, the case “that” this result is not obtained, for example, “forms” was oleua with all polymers according to the invention, but all these “possible masses not bosses” are usually anisotropic (cf., for example, Example 39 ). Similarly, poly- (p-phenylene-p, p'-biphenyldicarboxamide) and poly (p, p ¹ -phenylenbenzamide) in oleum form anisotropic masses, but not in HF or in the amides and ureas, which are the case with other polymers according to of the invention are suitable. The methods described below allow easy determination of whether a given mass is anisotropic.

Determination of the optical anisotropy: In the following examples is the anisotropic character of the masses according to the invention Hand see B. 1. a visual determination of the "RfihropaleBzens", 2. An observation of the bright field with a polarizing microscope

- 17 -909887/1693

or 3 · of numerical values of the Liehtdurshllasskelt by crossed polarizers, designated as "T" © of the "DDA",

To determine the T-value, one can use arais®t? Ope Amid · » hü @ r urea mass to find a solution which is produced in the manner described here.« And is partially suspended »holds solid matter« wiping a polarizer and an analyzer feiwgan _: are in a cross position. The arrangement of the! & 8 »piP © b © ι 80 u thick layer allows comfortable work«. You give one from inside a Kasseprob® according to the ». Evt indung cleared drops on a "dry" glass slide, presses a square on a part of a liquid on <ä @ n Tfc'opfesi under aweb / läing ^ ie » ⁸⁸ BaAe ^{8 of a part of the liquid}
Open the glass that rests on a ilaei ter dioke (@in Dwchnasser ¥ oe 1 ^ 3 en is sin ten) at Einöii Ma »d and enriches the l & teter
the binder Cu. B * ⁸⁹ BHeO * - (I) -Iifef ^ ®in transpas ^ ntes ³ ^ fiexib-IeBp ₉ waeaerfester adhesive stiff d®i »Äsaas-idesdn) _β where a diF®kt @ e can help the Masg © tendedeH, and Oils Keilsehsi © id © with surplus Itessej, the * igeiiepspeeefe wlrt »WSteend - des ^ Äs · - working so.ll © n with ά @ τ ilbiielien care Abdarapftog-i" Feuehmigkeita- «uftialinej» i ^ increased, So-äjnege and SAerfWgfege ■■ j egliehe suspended Peeftsfeofftellshen vef-mie € eii "earth"

The wedge is on a stage

The wedge is so Bisn ^ WüöäaBBä
shines through "© lohe" top sight beam

Man raiast di® intensity b®i geStreüste® Polarieafe © ^ top (I® _a where da® bo @ hg @ sfesllfe © s iae? Opli © g © n des » fx> © b®

r @ ne Ϊ® - if. The hindMF © fety®t®Rä © Li @ ht can rain poss? & Iüiilich © fi

Selen- 'or CEdmim ^ra Li @ ibttii @ asg®pIfe @ n _s Bolometes "» ν.) Are cleared. The same MeesMngesi S2? F © Igen in © laera © appropriately structured »air enfetealf £ © iii © fi

909887 / 1S93

determined. Bring the amide or urea compounds into the wedge gemflea of the invention, then the quantity (I * - xj) - (zf - 1 °) an Ifert greater than zero, which is also greater than with the application of appropriate care and precise technical equipment Experimental error can be explained. This value gives the gain of the Light obstructions through the analyzer due to the presence of c the rehearsal again. The order of magnitude of (if - zj) - (1 ° - zj) changes with the solvent used, the polymer concentration, the concentration of the salt and the unit in which the light intensity is measured.

The device used in the examples to determine the anisotropic character or T value of the amide or urea fmassen consists essentially of a light source of the type "A. O. Spencer Orthosoope Illuminator * with a tungsten overvoltage - mlkoskoplasp · (color temperature 3800 ° K), an optical wedge that the sample, an optical wedge containing air, one Bausch and Loeb polarization microscope with a 1Ox Leits objective and "ines 1Ox Leit" Periplan eyepiece (g), a Kaaera of the type "Polaroid MP3 Industrial Land Camera" and an Ooesen light meter of the type "Slnarsix *. The one containing the sample Wedge is formed in the manner described above and on the Objekttiioh <d. H. swisehjm polarizer and. analyzer) arranged in such a way that the path of every light that passes through the analyzer and the

ht, «a sample thickness of 80 u is available. Polari sator and toilyiiraa ^^ asfg'agiLj ^

Planes of polarization are obtained · That the analyzer must des The laser light is directed into the camera and the light meter is in the image plane (on the frosted glass height) sat (ij). The "B" solution is immediately followed with the analyzer removed (I?). By repeating the determination of the air control wedge at a thickness of 80 μm, ij and if. Are obtained. DIo τοπ dos exposure meter indicated values dl · are expressed in logarithmic units on the basis of 2, can be passed through Multiplication slt 0.501 (i.e. Ig 2) to "Ine logarithmically" leveled out for base 10, whereupon the Nuserus (base 10) of these products -, expression

- 19 -

909887/1693

Bftsx · zo usreennon, where the nuserus (base ΙΌ) is a \ kte as ij ', X *', ij 'and if'. The ij '/ l ·' is equal to the ratio of the intensities of the

bath

through «ti © d®s? Ifaesse subject to tfefeeffSttöhung hindtsrehfejpe & eiideiri Lichtes-υ- and the ratio IJ / ij gives the corresponding throw for the control wedge. The difference (ij '/ l * ¹ ) - (I?' / I ⁰ ') reflects the increase in the intensity dee due to the light passing through the wedge of the mass subjected to the investigation.

-Because for a depolarisiersndo sample the maximum value vera xj / X? ™ ij IT ^ L ttieopetiseh equals O _s § 'is al »Ipdex for ύί® increase in yLchtdurclilfieeigkeit (T) the Qrösee 2 CXj / Σ * - Χψ / 1. ) »100 BiMeknäß» da -awf Äieee quietly ier maximum value equals 100 depth »In the case of the ieeeuhg close to the above» As »fair wise, masses get old Meyten von.ttoesp Hiev els enleots» © p artet be & niebieto °.

Endare Meeeungs, the ®iu9 anieotropic ψοη isotropa

i dieee a «tf den Depolaslsationsanieotiropee ^ edl

Dep © l «risÄfeion Inleofcropy _t abgekiret DDl) directed is here with" ianieotropen Amid- wad OlewrasiÄeeen aßgewaMfe ". You here © famed öpöeee represents a wet ftf the Bepol» piee% iim by a fr ^ bm faindtvattretarentatj, i is polarized üureh the formula

\ " In imäetep " mm & imm ^^ i mn «iner) dl« isotrop) "leads n £ ttüMm ^ iiiiteltefelior in - Aüa Sitia · that a gtg # lwn« r absorber double mete a gleiiii ife Zirefachen desjepigen at © infaifcer Diek · shows vmu ^ - "üÄ-e ^ 'B ··» stiBRBungen in parallel bm ^ nenkmQht arranged polarizer analyzer beeeiotinen® with this formula in-fact' is nine Present <■ differen "gl0i @ taung represented in the ftmxie the 'intensity of the incident Liehtoe "always eingeetellt so that wn old par & l Lelen Polmrieatoren eowohl b # ii; d®.p blank as iueh 2. the eigentlishen fmbe eisi" ter unit © ra & apreohenite (de ti a aneeige of 10 © Si.) Meieuag v © n ^ Cuni £ ^.) What for 1 »a velisfe & ndig © Abwa @ ®nli> oit ¥ cm oepolarisation and

- 20 -

909887/1693

BAD ORlQJNAL

far 2. a complete depolarization for the observed PeId means. In this case, the equation is simplified as follows:

DDA s

egg - 1

The range is from 0 to 100, with the former being complete isotropy and the latter® being complete anisotropy for the observed field.

A polarization microscope of the Bausch and Lomb type (rotatable polarizer, fixed analyzer) is used as the apparatus for the DDA determinations and a "Silge and Kühne Ortho-Illuminator B" type device with a 100- "GE BMY" type W lamp. The change in light intensity to regulate% - (and '& ^) takes place by means of the neutral density filter and the iris diaphragm of the light source. The light passing through is picked up by a light-sensitive resistor (type "GE B-1036") operated at 22 1/2 V, while the relative intensity is displayed with a 50 mA milliammeter. The light passes through the parts as follows: light source, polarizer, condenser, sample, microscope objective (2Ox Leitz, NA 0.33 »FL long), analyzer, eyepiece (1Ox, compensating) and photoresistor.

All determinations are made in the red light obtained with the red filters of the light source. The photoresist is calibrated with a series of Konpensatorfilterfarbfilmen (Kodak Color Compensating filter film CC50R) to obtain a single film a Opasität 1 (Durehläesigkeitsanseige de "exposure meter 100%) _t swel films of 2 assigns etc. During calibration, the films on the Abandoned stage while the microscope is focused approximately on the center of the filter film stack (vertically). The working conditions provided for the photoresistor are designed to produce a linear Eioh curve with the logarithmic Bjiachem measured values plotted against the opacity. The opacity values of the sample are then read directly from the calibration curve. In this way a relative "rotopasity" value for the sample is obtained.

To prepare the samples for the determination one takes one Drip on the mass from the interior of a larger volume

- 21 - ' 90 3 887/16 93

Pointing sample and puts it on a sheet of glass made of resistant glass ("Pyrex"), puts an annular spacer 51 µm thick made of fluorocarbon resin C "Teflon" (R)) on the sheet and then closes the cell as a second sheet of glass. This structure is used in a very special arrangement, which brings the Qlas sw system to the evening ring while ensuring a constant test disk of 51 ρ. These samples are then 1 to 1 S / 2 hours. Leave to relax before taking measurements. Blind specimens are prepared in the same way with pure solvent.

On visual observations (under the microscope with crossed polarizers) of the masses for which the DDA value is determined, r any positive value of the DDA indicates the "presence of anisotropic phase. Apart from the extreme cases in which less than about 5 % of a Phase present "is the amount of anisotropic phase present in the mass, the greater the higher the DDA value, with the sensitivity of the device playing a role in extreme cases in the case of non-uniform distribution or dispersion, a choice of small fields of view possible, the anisotropic phase in a below-average amount or not at all. A wet of £ 00% anisotropy does not always give a DDA value of 100, which is probably due to irregularities in the texture.

'With the "RQhropalesseni" a property of anisotropic mas * sen, the type of which is determined by visual observation with the naked eye.

Many masses according to the invention appear upon observation cloudy or not in bulk in a clear container very clear and yet contain no or practically no undissolved solid. If the mass is viewed in the reflected, Usually lies by tilting or rolling the container or also only disturbed by slow to moderate stirring, 1st a uharakteristissher, slightly observable, satin-like shimmer or to determine the appearance after the failure has ceased to exist in his Intensity. Slowly wears off. An observation of various

- 22 -909887 / 1693

Masses convey no color sensation, while others can show a bluish tone or even a degree of colourfulness, which the viewer describes as pearl-like or opalescent. Foreign color in the mass, such as yellow discolouration due to smaller amounts of impurities or as the intrinsic color of some polymers, codify the color observation resulting from shear effects. Masses subjected to interference in the above manner often appear to be streaky and / or grainy on the surface. All of these visual effects are believed to be due to the birefringent or anisotropic nature of at least some of the dimensions and the inconsistent alignment of a large number of small, ordered areas. In the interest of the courses, the visual observation of all the variations in the above statement is referred to in the examples as the appearance of the "ROhropalessenz". A description of the cash registers as anisotropic can mean that they have enabled this effect or that they have been shown to de-clarify qualitatively or quantitatively as birefringent and linearly polarized light when observed according to methods described elsewhere between light-polarizing elements, such as under the microscope to have.

The use of the masses and their suitability as well as the manufacture of threads and fibers are described below.

The above-described compositions or masses according to the invention can easily be used for the production of fibers and filaments, films, fibrids, and tops.

The masses are ejected according to conventional wet and dry planning techniques using conventional devices, see thread. During wet spinning, a mass containing the polymer, prepared in a corresponding manner and at a temperature of from 0 to about 100 ° C., is poured into the mass produced during the manufacture of the mass Solvent-matched precipitation bath used, ζ. B. a water bath held at 0 to 90 ° C, expelled. Other fillers or coagulants for the purposes of the invention include ethylene glycol, glycerine, mixtures of water, methanol and an amide or humic solvent, mixtures of water and alcohols and aqueous salsa baths, these being ζ. B. at a temperature x-

- 23 -

30 9087/1093

«20 to * 90 C With the invention
see a

Naoh their education leads and on

a «eh the PiSdoss © itosp <Sqo

opltas

i © ss

ice »5? istolaca

often 200

The so
see ίη Β

in ®in®r on one

0.1 So for 5 min. _F vei'ewgsa'eiee 0, i treatment lsi; explained later. , - ■

9 0 3 Γ ¹ B 7/1 R Π "

1810428

Pieces obtained from the masses according to the invention, threads and fibers such as Qarne have excellent chemical and thermal properties. They retain their tensile strength when they are heated for half an hour and then boiled in aqueous salic acid and alkali metal solution. They turn to look "earnestly soaking in commercially used Trockenrelnigungs-Lösungsmltteln as perchlorethylene and trichlorethylene, at 60 ° C as essentially unaffected. They do not maintain the combustion when they are removed from an open flame. Due to their excellent tensile strength properties, they are particularly suitable as reinforcement for plastic ©.

The masses according to the invention are based on the conventional one Wet extrusion technology films can be produced, whereby such films usually under one during subsequent drying and washing Holding power. The masses produced in the above way can also be used according to Schorfällteohniken (e.g. * as in the USA patent = · 2 999 788) can be shaped into fillets; she can also be applied in liquid form as a coating on a variety of substrates, which take the form of surface material, paper, Wire, netting, fibers and threads, fabrics and the like, foams, Postetoff bodies or microporous bodies, etc. have and of glass, ceramics, bricks, concrete, metal (see e.g. copper, steel, Aluminum and brass), wood and other cellulosic materials, wool, polyamides, polyesters, polyacrylonitrile, polyolefins, Polyvinyl halides !!, cured epoxy resins, cured aldehyde-urea resins, etc. can be formed.

In general, a fiber can be obtained from an anisotropic mass, whose properties in the spun state match those of one otherwise similar mass that is isotropic or less anisotropic Cd. h, its emulsion of isotropic and anisotropic phases, In which the isotropic phase predominates), obtained are superior. Comparisons of the properties of a fiber made from a hemisotropic mass and those made from a slightly anisotropic or isefcropsn mass can be found in the examples.

Di® inhäv% nte ¥ isoo & i £ ät is given by the equation

- 25 -

9 0 9 8 Ö 7/1 6 9 3

defines “worlsi ^ _{p @} 2 di © relative viscosity and C © ine concentration iron 0.5 g mean the polymer / 100 al solvent. The relativ® Yispogifcät (? _Re i> ^w & ^riä bestifasjtj, by di® Duvehfluee since © iner v®rdö »Kt @ it Mawng de» Polymers through the capillary vises © · sin & ter through those © of the pure solvent difidierfe '» The ¥ © r-Löawngesi used here to determine the relative ¥ is © oaifcäfe, ¥ © r-Löawngesi have the Iensents? Atiöns mentioned above for C®

turn b © i 30 ^ö C under '¥ © rw © ndung (95- to »98J» iges ») 38teef © lsSure determined as MsusigamitteX»

δβη F®otigk © it, elongation and initial asodule are expressed with dsr iiimg T / B / Mi specified and their common units, ie g / d®n, % and g / d®n, di © Faseyprofcssi are not boiled off iaiaegsiraselien) ₈ but in general mind @ efc®ns 16 hours at 2i ° G and- 65 $ Talative Fewcht © conditioned, (hereinafter referred to as "Eigümrait & iid ¹ "'b @ s8 @ iehn®t), unless stated.

Heat treatment of the ⁹ fibers; As far as it is stated otherwise in the Baiapielcm ₉ b © @ the Wimeb® trade is based on the Spimian, who the "its the fiitidan Ziiemaera ^ & tongue ?! and Mas'üon ggraäsE dor invention threads obtained with Qarrra i & ntarworn $ in WaaehQn or soaking the in. "R" p © mi "ii © ii Sratand present thread materiala. or oaraa in water until © a im. borrowed from dan Spinraaedia «and bsw. or Sal "-frei -ist, Trookr" n WIi then Erhitmn in one of the following provisions 1 to D:

A) This device consists of a © »InKesrnrote made of rostfraism steel of 8t, 3 'era length © wid l _g 9 $ on the Xnnend'vruhmeeser, the kon ~ ira @ iK®m wide H®hr ' Ψοη 2 » 69 cm outside diameter

is, where the entire structure is arranged in the middle Ib sinsm 30, ft8 »egg» -El9ktr @ furnace »Dursh sswei Hipp © l in the outer tube, which is at a distance of 25 s ¹ * era from eta? Röh ^ mitts baid · »esitIg this arranged SiM ₉ is stiekst © ffgaa so © ing® *», that ae the annulus is seen through the pipes through the flow. The nitrogen? flows out of the Hingratum through ®in <2 small, 909887/169 3 -2δ -

P 18 20 426.2 ** April 9

E. X. du Pont de Nemour-ε and Compasiv Ql5 &

in the to! mir ear wall aRgebrdtoeta öffawHß Xn di- .; Middle of the inner tube and further out of the tube ends with such a speed to the outside that the atim: & - jJiiirc ir ?, the heated 30 "^ 8-era zone of the inner tube at least once every minute te is displaced. The exterior of the device protruding from the oven is up to e & wa 5.08 em yojj. each end made of asbestos-tape beviickell-. IIIe O.feiitomperatur is directed by a Jhernropr.ar, in the Shut Aussenwatid of the outer tubes by Hartietntng befee% <n <; l « ¹ - tiTid with a controller of the type" Minneapol? s Honßywolx ^ i-rvrme ' ^{111 stands} in Verkäme dmig. In the heated tube there is a temperature profile with a maximum temperature in the middle range vt-.r · The heat treatment -Kennteinperatur will of iron fortified by lies ^ l ^ Uv >>% to represent Auesenmittelfläche of Innenrnhrs ^ iiormopaar determined · oils threads are wltoden pipe at IJuJ ¹ QhIauffsii dös Hohre voa FtUirun "gen lakes trated and before a Berülbiisiiß rci ^ ä * n held.

B) This device is identical to device A in terms of pipe dimensions, furnace type, etc. and we «? 5 *? operated in the same general manner and "nteroheJdo"; si oh from dor Vorrich « tion A in the amount of insulation applied to the ends and the arrangement of the nitrogen inlets on the same Auesenrohvseite - instead of on gegenlieger.deK · Pages like at device A. Between these two devices can make difference! in nitrogen flow rates result.

C) This device consists of a lunen tube. made of stainless Steel 89 cm long and 1.27 cm inside diameter, which is concentric in a second 2.5 cm stainless steel tube Diameter and 45.7 om length, v / obei the entire Set up in the middle of a 50.48 cm electric furnace

is. Through a butt attached to each end of the floodpipe! Stlokstoffgas occurs so that Q ^ v ainströmende nitrogen flows through the annular space between the two. From the annulus the nitrogen flows two small ones, ibj the inner tube wall in the middle 909887/1 R g 3

'1810428

^ 9 * April I9t> 9

Openings in the inner tube wad further from the Xim © nr © hr © nd @ n rait such a speed near the outside that the atmosphere in the heated 20.48 ~ em »zone of the inner tube is changed at least once a minute» © i © off The outer ends of the device protruding from the furnace are wrapped with glass wool over a distance of about 5ίθ8 cm from each end. The furnace temperature is controlled by means of a Hegler of the type "Minneapolis <= Honeywell * fyrovan ©" ^M via a pair of thermals in contact with the center of the outer surface of the tube, and there is a temperature profile in the heated tube in the Mlftelf "rich maximum" temperature before. Until the heat treatment® »memx temperature is determined by a second, with the outer center surface of the inner tube in B @ rraopa®r © held «

Ό) CIa device ventilates from a stainless steel drill with an inner diameter of 7 # 26 mm and a length of 81.3 cm. In the Hohrmitt® a Helesetlotetoffstrom is introduced via a pipeline "of" emerges with such speed from-piercing that the atmosphere in the tube eix & times in a minute is changed. Bas tube is located in a concentric steel pipe of the nitrogen prior to entry through flows into the yarn treatment "zone. The entire structure is arranged in a small incinerator of 0.3 ta length®. By means of a thermocouple, which is attached to the outer surface of the steel pipe by brazing and is arranged close to the furnace elements, and a Hegler of the type "Minneapolis" Honeywell 'Fyrovane "connected to it, the furnace" and pipe temperature are regulated to such a value "that a thermocouple is controlled by brazing Thermocouple attached to the outer surface of the inner heat treatment tube indicates the temperature in this area. The part of the heat treatment tube protruding from the incineration furnace is wrapped with additional heating elements. An image obtained by changing the position of a Frtiftherinopaars, typical temperature profile in the tube (for a center "or" Neen "temperature of 536 ⁰ C) lists the following table.

- New friction side 28 909887/1693

W. Temperature profile of the Distance from entry Wftrneb «action ear sans, em χ 2.54 O 6th OK 12th Ii? 15th 16 £ 7 18th 20th 22nd zn 28 32 tempera tur, ⁰ C 135 179 336 152 515 532 537 • 536 527 W. 368 270 213 184

The sinsats of devices A, B, C and D are in the examples each with this code letter together with the nominal heat treatment temperature observed in the middle section (approx. 2.5 to 5.1 cm) of the respective inner tube.

The peak height ratio represents a hatred for the relative intensity of the two equatorial main diffraction peaks in poly ~ (p-beniamide) PER) is achieved using a reflection technique the intensity curve of the X-ray diffraction image is possible with an X-ray diffractometer.

The determination is performed using isolated poly (p-ben "- amide) performed as follows: Combine the Polymerisatioaemisehung slowly with a large excess of non-Clear for the polymer ₉ e. B. V & sser, stirs vigorously on a suitable mixer and thereby leads to a powdery or fine-grained form, washes the powdered polymer by repeated stirring on the mixer and then thoroughly filtered with water, if desired, also with ethanol, and dried in a vacuum oven at 6 * 0

- 29 -

9 0 9887/16 93

up to 90 C, b © v®r> da © material stored ed®p fir al® following and® processing treated

Exposure to pressure V © n 219 _a 8 kg / esa w <swd®n approx. 0.5 g water and © mid- odea? JisrnsfcofffffreiefS PolyKares pressed in Px »®b <shalfc © r. Unfcas? V © 3re © ralrag τοη CuK <t ° -StFshiung Use of 0.5 ^{0 <} ° slots is drawn at a scanning speed of 1 °, 2 @, ps · © minute, © ines »recording sheet speed of ZjS ^ cm / min, nmd @ ira © r Zeitkensfeante vo »2 ein »ätskMTVQ vosi β to HO®, " 2®, aiaf (2 ©
dem snishtgebougtsn nn & aem gefoiSMgfean BOr _ä d © l) _s where the blow of the Hegist? iergerät @ 8 s &. is set that the @ r Feak m & xira & lei? Intensity at least 50% d @% Clinesr ^ ü) Masestabes

To? Achievement of the? HH ~ W @ ict®8 wiM fcel d @ F'Dlffraksunäehst © in® QsnaniSlissi © won, "irad®m man die lur" measuring points b © i 8 and 38 °, 2S ₁₁ , with "iner © © rMea vertiiüdlet »lan then falls from the peaks in the nine toh 20.3« nd 23,% ® »20,« Vertical Cb®i constant 2 @ widths) to the GriiMXisde Äid, »with ¹ -telt di® peak height (in Worm d®r ^ gistriarblattimteTteilung) over the Qrundlirai®. Dor fHH ~ ¥ ert is then sias the Sleieli ^ ing PHH ■ A / B determined, where A the hat »de» sang @ for bai 20,3®, 20, böfindliehen P @ ak® over a®r Grimd line in units and B the ntspreehende Höte at the lower end of 23 peaks

A typical! Teve '· one of ®i »© ra gepnliwrteBst - from preparations in amide or urine of ftedien genSss - $ ®τ EFfinSösg isolated poiy- (l, l» -beißsamiä) «Han © polyin © reB seigt FIg. VI. Ia drawing from the su ersehenden way w®n MIVD ZWM lnsgle £ © b * effects one Annlhenmgsgerad® g © isg © ii s, made at the gen.

Sedimentation spray; "Hatred is solidified © iss® tSsniis wa 1.0

new lithium chloride in 30 ml tr © eim @ m-il- _s li- <BiMetfefl.a © stamM with 0 * 5 g troekneia polymer powder, * .®rkjeia®rt & ut ® £ n @ 'iseileliengress v © n about 20 u © the d-axtinter, 'verechliesslr- da «! © te» aife ein® stopper isradl subjects the on ßO ^: up to 8 © ° .C »rhitsSisis yard contents with a mechanical' Binri-cöi & ung ΊΘ min ..«, up to sn% rock 3 stirring. "Remain" ielsfcbsra
909887 / 1δ93 - 3 ©

Contents cooled to -70 ° (£ · B. by immersion in a bath of solid carbon dioxide and acetone), then allowed to warm up until the stirring can be enjoyed again, and heated as above. The F.chr is then allowed to stand upright without stirring for an additional 24 hours. After this period of time, no deposited poly-residue sisde ^ in the tube sheet can be determined.

Orientation eidtikel: The orientation angle of the fiber is determined according to the general method of nadi Irina and Tobolsk ?, Textile Research Journal, Vol. 21, p. 805, ie 822 C195D. Using Kinsats τοη Cu & GrS & Fahlung * with a fiber sample thickness of 0.05 on, a sample-FilÄ distance of 5 ca and an exposure time of 45 minutes, a Veitwinkel X-ray diffraction diagram (Durehlichtdiagranm) of the fiber and blast by emitting the Orientation angle of the sample is the arc length (in Orad) at half the aaxial intensity of an equatorial main diffraction point (which in poly (p-benzamide) is 20.3 °, 2Θ}. Since the XntensitStskurve is essentially a Gaussian curve ^{9 and} If the measurement is carried out at half the Haxlaal intensity, the physical statement of the orientation angle obtained by the determination is that approximately 77 Ji of the crystallites are oriented around the Faeeraohse within this angle.

The sur Bestiaaung des Orientleruegsvinkel on in the examples The celebrations described (according to the following sequence) are drawn in, spemical arcs are shaking in the following positions, 2Θ, result:

Pai IOt after Qrad (2Θ) Fiber after (A) Qrad (28) at Lgame example (H) 1 CA-i) 22.56 4th (A) 24.3? 1 CH-i) 22, ^ p 4th (A) 15.59 1 (A-2> 22.56 6th (H) 22.73 1 (Η-2Ϊ 22.52 7th 22, HH 2 <A> 22, * 9 7th 21.45

90 9 8 87/1893

BAD ORfQlNAl,

8 CA) 22 ₉ W. o | HJ
9 CA) 21.30 9 CH) 22.00 10 Ci) 22, 32 10 CHI 11 CA) 21 * 55 11 CH) ZIj) T ¹ O 13 CA) 22.39 SJ CH) \ ' 22.22 i * CA) 22.3 * i * cw 22 _f i2 15 CD 22, ** 15 CH) 22, * 6 16 (A) 22, ** 16 Ci) 22.52 1? CA) - 22.93 IT CW 22.59 18 CA) 22 _e 51

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1810428

Fiber after (A) Degree (2Θ5 Fiber naoh Degree (29) example CH) example 45 (A) 23.51 54 (A) 25.69 45 (H) 22.59 54 (H) 19.97 46 (A) 23.46 55 (A-I) 26.08 46 (H) 22.51 55 (H) 18.47 47 CH) 22.39 55 (H) 18.47 47 (A) .22.05 55 (A-2!) 26.06 48 CH) 22.78 56 (A-I) 22.98 51 (A) 22.29 56 (A-2) 22.93 51 (H) 20.20 57 (A) 23.07 52 (A) 22.69 57 (H) 22.44 52 (H) 22.07 67A (A) 22.64 53 23.22 67D (A) 22.56 53 22.34 68 (H) 22.12

Here, the course oaks have the following meaning: A «Spun fiber H s wftrsebehandeite fiber

A-1 * first fiber in the example as spun A-2 * solid fiber in the example in the spun state H- £ * first heat-treated fiber in the example H-2 «» wide heat treated fiber in the example

Fibers, fibers or yarns according to the invention "in the as-spun state" are defined as those which are formed in normal spinning processes (i.e. the formation, shaping or finishing stages), but which have not yet been stretched. ) or have undergone heat treatment which changes the molecular order or arrangement of the Folynersolelcfile. The material may, however, have been subjected to cheese and troekim work after removal of solvents or impurities. Other work that can be carried out without changing the basic character of the material includes übereügen o4er adhesives, 2. the physical treatment by turning, crimping, cutting uf stack and 3 · Einsat ζ the fiber at de? Substantially shaped structures, of fabrics and the like, paper, resin "^ of rubber composites, etc. 909807/16 93 - 33 -

The following examples serve to explain the practice of the invention ₉ without referring to it.

Be i s ρ i e 1 1

This example explains Io äi® manufacture of tepephthBlamiäJj, '2. the production with anisotropic and isotropic components of the same and 3> ° 3? aes from the same "

', ι 71 »ig CO _s 35 mol) powdered terephth & loyl»

ehlorid su be at once a solution of 37 ton "8 gp" Phenylendisunin CO ₃ 35 Hol) in a Hieehung w®n ^l L2Q ml Hexamefchylphosphor-5iMd 210 ml of 'N ~ methyl-2' pswö! id n © in a with one, liaftgetri © ⁸

Stirrer and one-sai Sal @ iusß8hl © rid ~ Tro © k @ nr © hr equipped i ~ l-Harsherstellungskessel Added, The temperature of the Re & kfcionßiaisishung is a "water bath at room temperature Nuode ™ rierfe" That within minutes ^ © rli @ g @ nd ©, solid material is allowed to stand at RaumfcesispeFatw ₉ dsnn combined with water and raseh on e.inem 3.785 ™ l ^m Mi @ @ r eh stirred j dae Deduce ■ with stirring on © inesa mixer three times with water gewas @ h © n and . by filtration on a coarse-pored
isolated lind dasm über @ ma © hfc in Valcuussofen up to about 7Ü ^W -0 nefc. Di © inherent © Vi®e © sity ₉ determined on a solution of 125 hjj polymers! » in 25 ml _S Q 95 "to 98g © ^ ₀ liger Sehwsfelsäure is,

He ^ atstellung d @ s ° anisotropic mass ©: A © mixture "/ © n 36 _s ü gc! @E © big @ n polymers and 2β * ^Λ Ι g rau @ hens3 © r SshwefelsMur © 15 ^ frsies S0_) is under Cooling takes place in an ice-water bath in a 505 ml "'Harsh © r8tellungslk @ ®®sl wasssffi ¹ ®! with © insm lüftestrisben & n Kühr ©; S © h @ ifo @ nbauart gemi® @ ht _e One stirs overasht and leaves äis · Mi '

15 day® b @ £ RaumtesspeFattir stand © «» Di © waste «seigfe di @ Rtihr @ psil @ s & @ ns unü d @ p © larisi © rt linear

.diareh hate spiders .. the aßisö ^ ropen Masses Eir «part of the above Weis® manufactured © n Spännraase® is ■ suw E: ^ tfer ™

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ke Edelrostallspinndüae with 20 holes of 0.076 mm diameter, an aqueous precipitation bath of about 5.1 cm in width and about 2,5Ί cm "depth ejected" having a temperature v © n Ht ° C. After passing through a distance of about O _s 6l m In the bath, the thread * = well out of the water at an angle of about H5 ° and on an electrically driven winder and collected on a perforated bobbin at 19.8 m / min Water washes and dries in air at RauffitGEiperatttF. The threads have a low crystallinity and an orientationGWink®! Of 3 ^ ° (determined on the wide-angle X-ray diagram); T / E / M ^ 5 * 3 / 10.4 / 171 / 5.0 the"

Heat treating the fiber from the anisotropic mass; The above Fadsngut is at 7.63 m / min, through the heated to 600 ° 0 tube U9T device A and at 8 _a 3 ^f * »/ min. collected. The resulting fibers show a high crystallinity and an orientation angle of 15 °, T / E / M ^ / den 12.8 / a, 9 / 8l7 / it, 8i _o

Production of an isotropic mass egg A mixture of 9.0 g of the above polymers and 111.0 g of fuming sulfuric acid (2 % free SO,) is water-free with βίικ ^ τ while cooling with an ice-water bath in one 500 »ml ^{CT Haraherstellungskessol} . air-driven stirrers of the disk type, mixed. The mixture is stirred above or until a clear, viscous mixture is obtained, during which time the cooling bath is allowed to warm to room temperature.

Fiber production by wet spinning of the isotropic M? P «« e; A portion of the clear SpSnnmftiiSfj obtained as above wü ^ ß z & r Entf'CET / i ^ g singeschlose air gssöhleudert and d-mii ralft «inßi? mechanically ftr.setriebcnen Xnjektioiißspritze dureh tvXne Eds ^ mc ^ ^ allspiendues "ori 0.025 J ¹ cm thickness mii 20 holes of O, ö? b mm" Durshmesser in ice about 3 _t l cm wide and about 2.5 * 1 cm deep, aqueous precipitation bath * # on Ratsm-

outgostosoen · A b & d segment ^ν ίση about 0.63 passes through. m fuh? fc to thE Vorfßdengufc unt @ r einsm angle of about 55 ^f from the WaoBerbad out and asu eissai. "ßlekferisch angetr5.eböasn Ati coiler and sammelfc it on einsr perforated spool 11.3 m / Hin", followed by 3 StcL. In Iceifeem, running water and in air at Rp.umfeempsratur fcrosknci. The Päüen soigen

909887/1693 " ^{? 5} "

a low crystallinity and an orientation angle ψοη @ about 50 ° (determined on the wide-angle diagram); T / E / M ^ / den 3.1 / 20.8 / 106 / 7.0.

Heat treatment of the fiber from the isotropic mass The above thread material is passed through the heated to 550 ° C. cabbage ^{8 of} the device .A at 7.63 m / min and "- collected" at 8.1 "" / min. Di © Paser shows a high crystallinity near an orientation angle of 19 ° J T / E / Mj / den 5,3 / 1,4 / 40i /!?, 7. "

- φ

This example explains I ₀ diö Heretellimg won terephthalamid) a "2. an anisotropic olai

high modulus .. Pae.er ame

dieuain in a marriage of
300 ml of N-methyl-2-pyrrolidone

on a Mischerι due within

rial is about 20 min

to one- 3.785-1

is under- IGhren on a © «Miioties ⁵

Alcohol and etfilleaelieh '

on ®i "m Bu" lmertidet "r

Vakuuraofen at about iOO ^ö C

(9795 I of theory) ι

solution of 125 mg. Polyjeerwa in 25 »0 el

H®rstellusig der- anisotropic. Mass: A mixture of 50 "0 g ä @ s obi · = genes polymers and * 50 _{,. 0 g fuming sulfuric acid CO 8} S $ free SO-) is under KQhlwng" it-a-KIs-looser-B "! i «eifs # m 5Ο0« »αΙ-Harzh» rat®lliing8k®asel anhydrous with an air-blown mixer of the Seheibenbauart gemisülit «The Sfieehung is Qbemaetet stirred, during which one takes a cooling bath while warming the» «© Zeiteraaä to room temperature leaves. The resulting © mass shows oil® RühropaloesEens \ and depolarized linear-polarized light »your.

_909887/1693 .- ■ '■■

Solution viscosity at room temperature as determined with a Brookfield Viscometer (Model FlVF) using a # 7 spindle a spindle speed of 2 rpm, is 5000 P; at a speed of 20 rpm, the compound has a solution viscosity of only 1660 P.

Paeer Production by Wet Spinning: The spinning wet prepared in the above manner is centrifuged to remove entrapped air and then at about 0.8 ml / min, at a pressure of 26 kg / cm through a noble metal spinning nozzle 0.064 cm thick with 20 holes of 0.0051 cm in diameter into an aqueous precipitation bath maintained at 43 ° C, about 40 cm wide, 14 cm deep and 94 cm long, which has stainless steel rollers at a distance of about 0.61 m from one another. The roving material is drawn through the bath and around the rollers so that it passes through the water bath three times, and then out of the bath at an angle of about 45 ° and to an electrically driven winder and on a perforated spool with 8.24 n / Min, collected while "" on the bobbin is wetted by passing through a water container located on the lower part of the bobbin. The thread is then washed overnight in cold running water, whereupon a part is removed for the heat treatment and the rest is dried on the bobbin in air at room temperature. The dry threads show a slight crystallinity and an orientation angle of 31 ° (determined on wide-angle X-ray diagrams) j TZEZM ₁ / den 7, OZ9, iZ173Zi, 93.

Heat treatment of the wet fiber: The wet (washed) thread material produced in the above manner is passed through at 7.63 a / min to 500 ° C heated tube of the device B out and collected at 8.09 m / min. The resulting threads show a high crystallinity and an orientation angle of 11 ° (determined on wide-angle X-ray diagramsaaa); TZEZK ^ den 13.7 / 1.6 / 888 / 3.23.

Eg 1 3

This example illustrates the preparation of poly (2-methyl-pphenyl & n-2,6-n8iphthalamide) and an anisotropic mass thereof.

Polymar preparation: Han gives 12.65 g CO, 05 mol) 2 ", 6 ~ naphthaloyl-

Vi.

Chloride at once to a slurry of 2-methyl-p-phenylene-. diamine-dihydrochloipid (9.75 g, 0.05 mol) in N »N -'Dinethylacetamide (120 ml, from CaH, overdistilled at reduced pressure and stored over 5A" molecular sieve) in <ain®m with one room driven stirrer and. © Ines »Calolunchlorid-Troekonrohr. equipped 500 ~ ml» HarEherstellungskssBel ssu The temperature d © i> Beakuionsmlsejiung is a · room temperature water bath · moderated Within minutes there is a paitenarfeigen material before, ÖAI wtn üb & wn & QHb at Haumtesnpa'ratur Atehanllsst, the fast going into a hard, stiff material, whereupon ₉ Og (0.1 mol) of lithium oxide is mixed in with a spatula and the resulting mixture is combined with water and stirred at a high speed on a 5.785-1 mixer öta »Polymers is washed three times with water under tubes on a mixer and t! yj? sh filtering on one at p ^ obporigon

isolated and in the ¥ akuumofeii b®i about

70 ° C dried over. Polymer yield 13.9 g (92.2 % of theory); Irrihä ^ nes fis ^ osity, determined on ®ϊη®τ solution of 125 polymers * in 2 *>, Q ml 95- bi® 98'gow.jtiger S © hw®f @ lsäur ©, 2.08.

Preparation of the anisotropic Masses Bine mixture wüu 7 * 5 g of the above polymer UNU l§, 0 g of 99 "^ g @ wJ {ig @ Sefumfbisäure is waiseerfrei under cooling with ice-© isseai-Waeser 'Bad in a 200 ml flask Dog with a ssQ «? lmniseh nagetrtebetien 'scrambled eggs * ü®w Paiäoluauart mixed Di® mixture wiTa Obemasht gerthrt, whereby mm the XOhlbad during, this Söitrauffl» see on Haumtoraperätur © noise. The incurred, fluid cash register seeps Rühropalsseris and depolarizes linearly polarized Li @ ht »

BQ ₁₁₁ J ₁₁ S ρ ie 1 H

This example shows the production of poly-C2,6-dJLohlor-pphenylen-2,6 ~ naphthalaroici) and the direct 'fiber production from the anisotropic N, H-dimethylauetamide / lithium chloride reaction mixture *

Polymer and Spinnir.asse production: 12.65 g (Ο · ₈ Ο5 MoJ.) 2.6- “MaphthaIöylohl © rid on 'oirana! a solution of 8.85 S 2,6-dichloro-p-phenylenediaiKiin {0.05 mol »sublimed) in N, N» dimethyl acetamide (120 ml, _{distilled from CaM 2} with reduced pressure 309887/1693 - 38 -

BAD OBIQfKJAL

and via 5A molecular sieve) In one with an air gear benert stirrer and a calcium chloride drying tube equipped 50 ml brewing kettle, stir vigorously and moderate the temperature with a cold (i.e. have a temperature of 20 ° C the} water bath. After about 35 minutes of stirring, a stiff material lies before, that you let stand at room temperature, what with 1.50 g (0.053 mol) of lithium oxide can be mixed in with a spatula. The fluid mass obtained within a few minutes shows agitation and depolarized linearly polarized light. A small part of the mass is combined with water and stirred at high speed on an O, $ ir6-1 mixer. The polymer is under Stir on a mixer three times old water and washed through Filtration on a coarse-pored sintered glass Buchner filter, whereupon it is dried overnight in a vacuum oven at about 70 ° C. The inherent viscosity, determined on a solution of 125 μg of polya in 25.0 ml of 95 to 98% by weight of sulfuric acid, is 1.99%

Fiber preparation by wet spinning: The above mass is removed by a closed Qa * · g * ech * rd * rt and then only about 3.5 »l / min. b * l · 1η · Β pressure of 3.52 kg / ea ² through an Ed «laetall ~ spinndQse of 0.0254 approx. Dieke old 100 holes of 0.076 mm diameter into an aqueous precipitation bath of approx approx. width, 14 approx. depth and 94 cm. length, which has orphans made of stainless steel at a distance of approx. 0.61 a from each other. so-called, that the water bath runs through three times, and then at an angle of about 45 ° out of the “bath and eu” into the electrically driven winding device and on a perforated reel at 11.9 a / min , whereupon it was washed in cold running water for 3 hours and dried in room temperature air. The threads have a low crystal length and an orientation angle of about 50 ° (determined aa Wttltwinkel-Roentgendlagram) j TZEZH ₁ ZdOn 8.7 / 8.6 / 222 / 3.75.

Heat treatment of fiber: That made in the above manner Fadengtit is 7.63 a / min, through the tube heated to 500 ° of device B and collects 8.49 m / min

- 39 -

909887/1693

Orientation angle of 10 ° ■ tin *) »T / E ^ / den 10.5 / 2,

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909887/1693

The mixture is stirred overnight, keeping the cooling bath during

this period can be warmed to room temperature. The resulting, fluid mass shows Rühropaleszenz and depolarizes linearly polarized® light.

Fiber production by wet spinning: The Splnnmasee produced in the above manner is thrown euf the removal of enclosed oasis and then by means of a mechanically driven injection syringe through a noble metal spinning nozzle 0.064 cm thick with 20 holes 0.076 mm in diameter into an aqueous precipitation bath of 6 eggs. After going through a distance of about 0.61 ra (OTtsh the about 5.1 cm wide and about 2.54 cm deep water bath, the thread material is guided out of the water at an angle of about 45 ° and to an electrically driven winder uad collected on a perforated bobbin at 6.7 m / min, while it is wetted on the bobbin by passing through a water container arranged on the lower bobbin part, whereupon it is washed in cold running water and dried in air at room temperature / E / M ₁ / den of threads i3.9 / 6.3 / 195 / 3.20.

Heat treatment of the fiber: The above thread material is processed at 7 »63 m / min, passed through the tube of device B, which is inclined at 533 °, and ait 8.59 r / kin. GesansMslt. Ί7E / M ^ / that of the resulting threads 7 * 6 / 1.7 / 5 * 0 / 6.50.

B 9 1 β ρ 1 β 1 6

This example explains 1. the production of a mixed polymer of 5 ^, 7 $ **.% Poly (p-phenylene-2,6 * naphthalamide) and 44.3% poly- ipophenylene terephthalamide), 2. an anisotropic mass «And 3rd fibers from the same.

One gives 5.08 g of CO, 025 mol) powdered ttorephthaloylchlorid Csufclimiert ^ all at once su a solution -ψοη p-phen- ylendi & misi (S ₈ ^ O g, 0.050 MoIi sublimated by silica gel) in sisrsi? Mieshimg of 60 ml of hexylphosphate (from ¹ CaH ^ b * i ver vdmutartm Dvuak distilled over and stored over 5A molecular sieves) and $ 0 ml of N-ltefchy] L ~ 2-pyrro & £ deN {from CaH ₂ under reduced pressure

Wad stored over 5A molecular sieves in one with

909887/1693

oni _QlNAL

an air-driven stirrer and a Cftloiunohlorld ~ TrOekenro.hr equipped 500 ml resin production kettle and offset maeh about 5 min. Misohen at once with 6-, 33 g (0.025 mol) 2,6-naphthaloyl chloride » The mixture is stirred vigorously and the Temperatar with a cold water bath (20 ° C) moderates »The« present after about% min » Crown-like property is left over at Raunsteraperatup and then combined with water; and on a 3 »785-1 mixer raeeh geröhrt / Bas Polymers is added to "© iraeis Mi" while stirring

Ma inhBvente Yiseoeifclfe "beetiamt at a Wrong of 123 as poly- * Mtswe in 25s, O ml 95 bie _{98gew.Jiiger>} Sehwefel8 ^ ure, betrlgfe .5" 5t "

Esjfsftell »g of itiees Ein® ÜneMiftg of-7, 5 g of the above polymer wia 6? _S 9 8 99 »2g« tf.yigftV SetwefelelöFe is given with one «ϋ ^ -ΙιιβΦΪ ^ -ΙβΛ. In eissra jNMHal ^ round flasks anhydrous old

Üasi mocking ' Um Mmmm $ iberaae & t «α % M9l ums KQhlhaa si @ h while äiNfsta Sei% m> wm ' aisf EaemtomperfiuW« Fwärmep »The infallanäe masts ϊ»% 'mmmm & üm% ll®h ¥ i »@ © ig% lühropalesieiS! » and 'depolarized

FaearSwntdlluiig diufcih Hasss ^ toiegis Di® in the obignn Meia® fcerge-

s @ lil®iftd «rt tmS umm sdt & els a tteehaaieeh driven Xnjaktionsspei ^» ® uwp & U ® a precious metal spinning sleeve from Q »06H m Diele® with 29 Uoliem ^ ro» O ₉ OfS ran dureteesser poured into a watery coagulating bar for 25 ° ΰ. tiäeh passage of a Streek® of about O ₉ Si sa through the water "having a width of about 5» i ora and ein® depth who about 2 "5 ^ -if which the Vorfadengiit under an angle ψ and η about 4 ^ ° is' led from üem water and onto an elec- (o tritoh angeferiebeae Aufwiekelvorriehtung and gesamnelt on a per- tm ^y IVT% ®n @ pul® since 6.1 ra / Hin. ₃ while on the Reel · oo dureh Durohlauf dureh ice & s The water holder arranged on the bottom of the bobbin is wetted "whereupon you sew in cold running water, wash a part for the heat treatment and the best c" on the 9po3e 4tw tuft at Haumtempfi'ratuE ¹ 't? oekn «t The u> threads have Krietallinitltsspai ^ and ' ηηύ @ in®n

von 37® Cam Wide Angle ^ X-ray Diagram BeeteterminedJs T ^ E / M ^ / den 8,7 / .79. ■ · ■■ "^<: - *» 2 -

E. I. du Font de Nemours and Company Q ~ 10J5l

Heat treatment of the wet and the dry fiber: wet The above "" in the present state ereponnenen (washed) is Fadengut-with, guided 7,6j m / min by the heated to 547 ⁰ C tube of the device B and with 8.84 m / Min, collected. The resulting fiber shows a high crystallinity and an orientation angle of 11 ° (determined on the wide-angle X-ray diagram); T / E / M ^ / den of the thread material 12.7 / 1.8 / 895 / 37.2. Which is the above dry thread material in its unpinned state with 7.6? m / min, passed through the ^{nitrogen-filled tube structure heated to 525 0} C and collected at 8.54 B / min, - T / E / i ^ / den of threads 9.5 / 1 * 8/635/4 * 67a

B β, 1 ■ ρ 1 t 1 7

This example explains the 1st production of a Misohpolyaaiides with repeating units from the group -NH ~ <^^> -CO-, ~ HH- «£ I |> -NH- and -CO -! ^ Φ" ⁰⁰ (relative molar ratio ltlil ), 2, an anisotropic mass of the mixed polyamide * and> fibers from the polyamide.

Polymer production 14.4 g (0.075 mol) of p-aminobenzoylchloride hydrochloride are weighed into a polyethylene bag in a drying chamber, ie chamber kept under anhydrous conditions a 29/26 s internal connection is located, removes the bag and tube from the chamber and attaches them via the connection to a 1000 μl resin preparation kettle equipped with a stirrer and a calcium chloride tube, empties the contents of the bag as quickly as possible possible In a solution of 8.10 g (0.075 Hol) p-phenylenediamine in a mixture of 405 ml of hexA-tsethylphosphoramide (distilled from CaHg at reduced pressure and stored over 5A-Molecular Sleb) and 135 ml of N-methyl-2-pyrrolidone ( overdistilled from CaH ₂ under reduced pressure and stored over 5A molecular sieve) and after 5 minutes of mixing, 19 * 318 g (0.075 mol) of 2,6-naphthaloyl chloride are added all at once with vigorous stirring. The reaction sfflisohungstemperatur is with a · "cold water bath (20 ⁰ C) moderated. After a further 8 minutes, another 2,6-naphthaloyl chloride is added in an amount of less than 0.1 g. The mixture, which becomes so solid in one hour that it is no longer possible to stir, is left to stand at room temperature.

90 9 887/16 93 - ^M * ^u - Description page 43 -

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Another sample of the polymer described above (ütnslists «ίο obeis manufactured j ⁷ I ^^ ■ 1,3) is old 99» 2 weight figer su a n & sm with elite »Polymerge!? old of 12 Oew.JC

oil® accruing «» «%, as # results in a DM value of 32.2.

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gre- & jf, 0 r (0.02 ^ 6 Hol) powdered! ·· Itere zu eiis «? ^ ÄfscEs2.ii »Rung vea · S7» 3 g Cö _# 0 * P MeX) N, H · - h ^ isylendianin in 280 »1 Hexajsetbylphos-phor- ®lmm n £ ^ -« irrest l »f '^ driven bold * froukenrohr split Seheieiste "Oalsiiisföhlofld ^ provided 500 ml Riuniher-" wfihreM mi% is an ice ^ Kasser bath carbonated · te · gtHT »it deat unsoldering the reaction in solution; isaeh SO Min. withered · Terephth ^ loylshlorid (5.15 g »0.0254 mol) all at once, sssgeso & st · The Rs & k & äonssBisehung is at high speed » Mt ein® »3,785-l» Mix «^ gertShrfc» The resulting solid is visit * »EOhren in a ^ m Mlso ^ sr three * ·! With water "once old alcohol WTAE s ^ hliesslieh nit acetone recently was isolated by filtration on a" coarse-pored sintered glass "Buehnertrlohter and then 12 ISTD. dried in? & kuusofeß b @ i about 70 ° C. The yield is essentially quantitative. You inherent Viscosltlt, bestieat m Eliter solution of 12 mg $ folymrtn in 39.0 al 95 to $ 8g "tf _# flser

!! Creation of the anisotropic mass: A mixture of 5.0 g of the obi gen polymers and 45.0 g of fuming sulfuric acid (0.8 Ji free SO «) is anhydrous with cooling in a Sis-Vasser bath in a 200-liter reverse-jacketed flask and is operated by an aeohanic stirrer the? add "lbaua? t geaicöiit. The Mleohtssig will overview or up 'P & iBktj · an a®m vlsi'ütH kvliiz solid particles' more au be obslcsd, stirred »^ © b *! w & n the cold bath see during this

on RaMJtesaperafcp.a: · erwSrw® «lets. The resulting mass is flwl wd selgt agitating apalescence and depolarislert linearly polar light.

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ehlcrid-Trookenrohr equipped 500-ml-hars-making kettle, while it is cooled in a Yaaa bath of about 20 ° C. After 2 minutes of mixing, a mixture of terephthalcyl chloride (5 ₅ O8 g, 0.0025 mol; sublime) and 2 »6-naphthaloylehleride (6.43 g, 0.025 mol) is sugesetst all at once. The mixture is stirred vigorously; _{the a} chewing tuk-like mass, which is present after about 7 minutes and does not allow to stir, is left standing at room temperature above, then combined with water and stirred at high speed on a 3.785 -1 mixer. The solid is washed three times in a mixer and isolated by filtering on a coarse-pored silver glass Buehnertrihter. Me Tttlgaere is Obentaeht in Vakuaeoftn occurring at about 70 ° C g "troek ~ m% wA U ** solid (25 * 0 g) on a VÜey-Muhl" ge until he has a sieve of 0.81 at the clear mesh width (20-.

Sieve} happens, whereupon it is rubbed in for about 6 hours with a mix of hot Hiüisenaittre, the stubborn glass is removed on a coarse-pored Sinterglaa-Bffiehner tray and the polymer is washed with several portions of distilled water and then dried in a vacuum oven at about 70 ° C. Pol / meraaebeut · 20.2 g ($ 6% of theoryij

Visoositlt, certified on-a x £ * utig of 125 ag ram in 25.0 ml of 95 to 98 weight percent sulfuric acid, 2.88.

? @lieah «ratellttjig: £ lae Miechmig from 0 * 20 g des 9.0 ml of solvent, obtained from 3 * 0 g of Uthlnmchäerli, 2/3 ml BexamethyiDboaphorsa & l and 33 i /? ml , vistf in a · «Be« eenmre £ xF at RatHtamperctiir with «See» flpftei »» t * l ^ «w« fs · Da · MisoBvn becomes fs «»% et «et« t _t until a class MUM ₉ die you daam with * imr O, O12T-ea-Rak * l ümt on "92as * spreads" 41 · thereto ta cold Vasser getaueiit wiHi "coagulation of the M &fig" triggers * i "fc di« «ntäl ^ weary? clie glass plate. The film is pressed durah Hmmtmumn Fapiernaiwlttobarm 1 »vacuum furnace at TO ⁰ C tr ^ km film is clear, süi \ md flexible,

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«N ma imfcleert den Boutelinhslv» o quickly as Sn «int £ & iiü3g - T3K 5 ** 0 g (0.050 mol) ^" Flie ^ leiidisnisi

ati ikAiysethylpoOfiphcrasiiii C & ut CaH ₂ at and over Si

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and amn.mlt Wä # s © i * ""! "agrees and a 3" 8? 5 ^ei 2r "l! iseisep stirred" Büiren on a Mi $ eh © i- three times, old Wae-Fütrisi ^ eh on a coarse-pored one Sinter, then ütresnaeht in the vacuum furnace ^^ el and tiieraitf (Kenge nvnaehr 2i, 0 g) on a genfthiesi, until s? a sieve of 0.84 m M & sohenweifce a & s * efrtf & 6 Sid. with hot formic acid

₈ the i? Ol? «Sre old a number of portions distilled Vms des? ®iy» t <ra in a vacuum oven at about 70 ° C dry % 5.2 g (93.7 ί of theory}} inherent VIs bmtiant on a l ^ aüßg Yoo 125 ng Polya * rew in 25 »O al.

: Am "Kieohuag of 'O ₄ SO g of the above wttd 8 ₉ O nl SOLUTIONSAitteJU obtained from 1.0 g Litnlunenlorld and 9 $ nl H ^ <Meth? L-2-pyrrolidon, is in the reagent tube at Rauatenpvrataas" nit Qiswr? Spae ^ t ^ l moved and mixing continued ... hours) _B to a kJar® _? fluid solution present "the ku \ then a Ό, 0127" GnHRaICeS. propagates on a glass plate ^ The plate then .If in cold water getaueht. During the Kottgull *** ** na äsv hatred "W b entstehonde the film from the Flutte whereupon β »?} they pass through <sss®n between absorptlont'ffthlgen paper- <$% wa 6 hours at? 0 ° Q dries in a vacuum oven

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909887/1693

BATH ORIGINAL

4 * 1810428

Foil made from the mixed polyamide from a Ν, Η-dimethylacetamide.

Terpolyaer-Herat RECOVERY: Zn a drying chamber, ie, a chamber kept at anhydrous conditions, are H, 8 g (0.025 mole) of p-Aidncbeneoylchloridhydrochlorid weighed into a polyethylene Beufcdl · It attached the open prey landing on a glass tube of ETIRA 7.6 cn Length, at one end of which a 29/26 internal connection is provided, entnismfc & en bag-tube construction from de? Drying can? and connect it to one with a stirrer and a) calcium chloride-'Frockenroh? equipped 500 ml Harsherstelltsngskessel and emptied the contents of the bag as quickly as necessary into a solution of 5.0 g (0.050 Hol) p-phen * 2 «ndiamine CdUTOh silicone gel sublined) in a * mixture of 55 Rl Hestainethelphosphoramäd (from CaH ₂ distilled at reduced pressure and stored over SA-Moiekelarsieb) and 55 ml N-Methjrl- ^ pyrrolidon (from CaB ₂ distilled at reduced pressure and stored over 5A molecular sieve) in the kettle. After 5 minutes of mixing, 6 93 g (0.025 mol) of JM'-blood soyloride and after a further 2 minutes of mixing all at once while cooling with a cold water bath (20 ° 0) 6, 3 g (0.025 mol) of 2,6-caphthaloyl chloride sugesetst. Di · Mime Hung, 41 · in 7 min. Su a clear, rubbery material solidifies is fibernaoht allowed to stand at room temperature and then combined with water and at high Oesehwindigkeit on a 3 "7i5-l-Kiaoher gerOlrt, Dr solid is purified by tubes on a J Heehor washed three times with water and isolated by nitriding on a heavy-duty sintered glass Buchner funnel, after which the polymer is dried overnight in a Yalnram oven at about 70 ° C. Yield 17.3 g (9 *, β $ of theory); ^ ^ ■ 3.1.

For preparation: A mixture of 0.20 g of the above polymer and 8.0 al of solvent, obtained from 2. * g of lithium metal and 100 si of NeN-Bisethjrlaeetanid, is moved in the reagent tube at room temperature with a spatula. Mixing is continued until a clear, fluid solution is obtained ( W hrs.) And this is then spread out with a 0.0i2T cm squeegee on an Olas plate, which is then dipped in cold water. During the coagulation of the mass, the resulting film loosens from the de? Glass plate; the slide 'dBisn dis!? i; h Phases sttisahöa Ä- ^ c ^ ptioaefahigon Papierhsmd-

kills ¹ , «111 and flexible.-

© big® »PolpsewftB like 15.0 g S9 _a 2®9Wo ^ li3Qp llstoeffolsEfcO w & sü saisfeos» lihliwg mit ti »©» ElQ-Wa0® @ F ^ro ! «S im oiss © s free old ice» «GieeSMiaisBelh« igetriefegsäQ »Ios ⁵ P

ten © SipIaHEaao © üifi wap EmttfommmQ oäüQ30 @ föa @ ooossoiP © qgq. ββΑ waü umrn oi ^ iolo © £ 105? BsoSaasailooSa CMßQ ^? Äo ^ Q5ao oprifeso äisEpQBs φΙεώ EJQte3toäHop £ siffl # »! OQ ¹ ^ m © ₉ © & § © sa ®ä @ £ so safe 1 ©

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309887/1693

1810428

Xn a Troekenkanmer, d. H. eggs on water conditions held chamber, 4.8 g (0.025 mol)

^^. soylahloridhydFoshlosldl in a polythene bag a-corn attached «The open end of the bag is attached to the exKom glass tube from J $ € t @m lung®, at one end an internal connection is 25/26 ff. the irockenkamihza abasp the Arcsshluts to one with a »stirrer and

equipped SOQ-afr-Btrstwrsfcelr 3 (contents of the bag as soon as possible uQ vr? i 3 _a lC g (OSi ¹ S Mol} p-Fhenyiendiai & iii Cä ** F «h Siliea-

in a & nsr liit ^ fc ^^ g τοώ 130 ml

© al _s SMii -i ^ Fsaiiii ^ ejii ^ eiii S ^^ le überdistilllert and über »s ^; @ m «t.fös ¥ sitet;) iM tHu, ml » l-methyl-S-pys ^ olidoji (from CaH ₂ at Ts ^ mU WbVFUmtiittsm and over SA molecular sieve 5 min. Mls £ fc9u mMm at once 15 , 23 g CO, 075 mol) PiSS ^ ßisähaloylehXiidr-iä sugesetst · Di © f ^ spi ^ atm * den * Reaktlts ^ smieehuiiig with a «» cold water bath (2 ¹ ®® &) ss & i @ rl «s ? t. The Mis @ h ^ ng that in five minutes, "a kauteehukartlge fibiarnatsh ^ is left at Raumtemperatus * and Mauser wiu combined on a 3.765" one-Misoher at high g @ s "ä ^ ä · Dsr solid imter stirring on a with Washed water and isolated by filtration on a Sirit.srglasoBuehnertrlchter, whereupon the itocra & ofafc is dried in a yakuum oven at about 70 ° C. The angslban fibers (25.6 g) are filtered off on a Wileyi until the out of a sieve τοη 0.64 ma mesh width for m & n meiirs ^ e hours in white, 98% formic acid the acid, the solid is washed with several water fractions and dmm ütessmasht in a vacuum oven at around 70 ° C

. PoiyaierausbsMfc® 19.0 g (91 % a * r theory; inherent Visbestlxamt an «inas · solution of 125 mg polymer in 25» 0 ml 95- to 98% by weight Sefrw © fölaäis: po _s 6.22.

o @ r mass: Μ & σϊ missh ^ a Misohmng vcn T, 5 g of the obi

iand 6?, 5 g sr & yghSKdar sulfuric acid (0.8 JS. free cooling with an ice-water bath in a 200- »l round water with a sir.ßia meehaniech driven stirrer. The mixture is stirred until

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Polyethylene bag 1 *, weighed in <g (0.075 NoI) p-aninobensoylehloride hydrochloride. Men fastened the open end of the bag to a glass tube with a length of about 7,6 inches and an inner diameter of 2.5 inches, at one end of which there is a 29/26 inch inner connection, removes the bag-tube structure from the drying chamber and puts it in place but the connection to a stirrer and a calcium chloride drying tube equipped with a II hardening kettle, which is cooled with a bls-water bath, and empties the bag contents as quickly as aOglieh (generally within 3 hours) into a solution of 8.10 g (0.075 mol) of p-phenylenedlaxin (reduced by silicegal) in a mixture of 160 ml of besanethylphosphoranide (distilled from CaH ₂ under pressure and stored over 5A molecular sieves) and 100 μl of K-methyl-2-pyrsrolidone (from CiH ₂ overdistilled with reduced Di ¹ UCk and stored over 5A * molecular life). After 5 Hin. Mixing of the above ingredients gives aanal with vigorous stirring and continued cooling with an ice-water bath 15t23 β (0 "O75 NoI) powdered Tervphthalovlehlorid hlnsu. About 20 hours ago there is "clear oil" which the nan fiberaaoht leaves to stand at room temperature and then combined with water and stirred at high speed on a J ₉ 765-1 mixer. The polymer is washed three times with water on a mixer with agitation and isolated by filtration on a coarse-pored sintered glass funnel, whereupon the polymer dries close to the fiber in a Takuun oven at about 70 ° C, the resulting yellow pearls C37.1 g) several Hours nit helsser 98fig * r Anelsensture rubbed off, the Stur · filtered off on a coarse-grained sintered glass BuehRertriehter, the polymer in the above-described ¥ egg ·· swelnal with water aaf an ehliesslioh nit aeeton and then comes close in Takuunofen at about 70 ° C dries. Polyaerauebetite 24.0 g (90.8 %} inherent Viseoslttt, determined from a solution of 125 ng of polymer in 25.0 ml of 95 to 9% sulfuric acid, 3.73.

Bsrstellung dw Wet χ Bine Klseaung of 5.0 g dee above polymer and 5.0 g * rough budding Seh «« felslure (0.8% free SO,) is under Kfihlung nit a GIS Vasser bath in a 200 nl " The round-bottom flask is equipped with a mechanically driven stirrer that paddles the paddle. Close agitation of the liquid is not a matter of

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Paser production dunsh N & sespinsiens which are produced in the above manner

and then by means of an injection syringe with a seohanleeh through a spinneret made of stainless steel from O _f O25 Dieltit 20 holes from O _ffi OOT6 and Durehii better 21 ° C atti | pit® a. N & eh iweh das -et «a S» t -es bm toe Yorfadengui «us des Hasser unter« us «» 1 ■■ an electric HBi on ■ eleventh perf & riffPtesi apile sau ··· -'in cold ₉

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909887/1693

BATH ORIGINAL

1810428

This example explains the production of a random message polyamides with recurring units from the group -ΝΗ-φ-CO-, -ΝΗ-φ-ΝΗ and -CO-Q-CO- (relative molar ratio 3: i: 1), 2. an anisotropic mass of the Mlsehpolyamides and 3. of fibers from the mixed polyamides

Polymer production in a drying chamber, d. H. a chamber kept in anhydrous conditions, 57.6 g (0.30 mol) of p-aninobensoylehloride hydrochloride are weighed into a polyethylene bag. The open end of the bag is attached to an Olas tube of approx 7.6 on Sofiage, at one end of which you can see a 29/26 If Znnenansohlusa, takes the bag-tube structure from the drying chamber and connects it to a with a stirrer and a CaleiiMshlerid drying tube equipped ll ~ carmaking bowl and emptied the contents of the bag as quickly as possible into a solution of 10.8 g (0.10 mol) of p-phenylenedlamine (dtmreh Silleagel sub-

in a mixture of 260 ml of hexamethylphosphoranide (from distilled over at reduced Dmiok and stored over 5A molecular sieve) and 280 ml of N-methyl- ₂ -pyrrolidone (distilled from CaH 2 at reduced pressure and stored over 5A molecular sieve) in the kettle. Are Naeh Misehen 3 min with vigorous tubes 20:30 g ₍₉ SO O mole) of powdered Terephthaioylohlorid (subllmiert) hinsugefQgt · The Temporatur of the mixture with a Vasserb & d of Raisatemperatur "ORed · The mixture WLS ^ d raseh vissos. the within about iO Hin. The solid mass present is left to stand for 2 days and then combined with water and placed on a 3.785-1-MiSOhO? misled. The polymer will! while stirring m & t © ine «mashers washed three times with water

on a "coarse-pored sintered glass Buohnor

isolated, followed by DA® 'polymers in a vacuum oven at about Obernaebt 70® (S troeknet. Polymereiuebeate 58.0 g (97 »5% of the Tuori") j itthtrente yiseosität determined on oiner solution of 125 mg polymer in 25, 0' 1 $ 5 "by weight of 98% sulfuric acid, 3.77.

■ H®2 "etell" s) t "der, |||| 9f: pin" Mi a a hung of | 0.0 g of the above polyee imü 560 £ 99 ₈ 5js® # .Sig «2 ^i> SohwefaisSare is under refrigeration with

wasffr-

$? 1810428

free with a · »meohaniseh driven stirrer made of stainless steel mixed. The mixture is stirred overnight while taking the carbonic bath allow it to warm to room temperature during these periods. The mass that arises has a linear rühropaleszens and depolarization polarized light.

7aerh «retosition by wet spinning: The spinning mass produced in the above manner is centrifuged to remove trapped gases and any solid particles and then at about O ₉ B m3 / min. at 26.6 kg / cm pressure by a noble metal spinning box ¥ © n 0.06 *} cm thick with 20 horns of 0.005 cm diameter in * © in watery, held at 16 ° C, about ΊΟ cm wide, i ^ em A deep bath, 94 cm long, was poured out, which had orphans made of stainless steel at a distance of 0.61 η from one another. The pre-thread material is sucked through the bath and around the rollers so that it runs through the bath three times, and is then guided by means of a Saiasehw & nsohens at an angle of about ^ 5 °, an electrically driven winding device and on a perforated Fk #E Spul «with OK, lm / min. gissaaaelfe, whereupon m 3 'hours isi cold em, lukewarm «- v> ^ c · - · - .' , fendeai W & vs «r blows and dries in air at R & ttsttotaper & tur. The ? L & * n shows a "mean installation and a sign of orientation"! of 28 °; Τ / ϊ / Mj / den & O, 2/7 »8/264/2, i3.

Vts «ebch & g) dlung d« r Fivers Das in the above. Fadfingut as prepared is a wat / M gefdhrt 7 »6 in. By 586 ° on cured tube of the apparatus B with 7" 86 Å / min, wound up. Pi · accruing fiu? Seigt «in · raised · crystallinity and« inen Qri «ntierungowinlwS. ve «iO °. T / E / M ^ den of Ptden i5.6 / l, 8/838 / 2.00.

Be i s ρ i e 1 « IS until 17

The following three baitpieXes «riantersi άϋ iWrsteliunjf von anisots» © = p «n OlftiMMffMn, which contain mixtures of poly (p-a> onsamide) and poly (phltthlid), which make the production of paeern

diet · «, whereby separately the production of poly- {p-ben» «eii5) «Ad of foly- (p-bensamide) and poly- (p-phenylene terephthalamide5 ^ wrote

mm Fsly-ip-boßKaaii}: Evi elm? Tro ^ ke ^ apier, ά. H.

BADORJQiNA !,

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'1810428

a chamber kept under anhydrous conditions, turn 120 g (0.625 mol) of p-Aninobenxoylohloridhydroehlorld weighed into a polyethylene bag. The open end of the bag is attached to an "Olasroh?" of about 7 * 6 in length, at one end of which a 29/26 ¥ XnnenanMhlues is provided, takes the bag-tube arrangement from the Troekenkejste? and set it up via the connection to a "with an air-driven stirrer and a calcdunehlorid drying tube! -!" - Molecular sieve stored) and 180 al NHtofchyi-2-pyrreiidon (distilled from CaH ₂ with reduced pressure and stored over 3 A molecular sieve) in the kettle, while stirring vigorously and using an egg-water -Bath cools * The mixture, which becomes fat in 13 minutes, is left to stand at Rauntenperattir *, whereupon the rest of the out-it water is combined and stirred at high speed to a rate of 3.7t55 liters The polymer is washed three times old Hasser with stirring in a mixer and isolated by filtering on a coarse-pored ainterglms Buelmertriehter and then dried in a vacuum oven at about 70 ° C. The polymer yields 70.0 g (9 * , 3 % of theory); Inherent visososity, as demonstrated by a solution of 125 μg of Polyneres "in 25.0 al $ 5- * to 9" weighty MamtflOnr ·, 2, ^Ä 3.

Preparation of Pol7 ** (p ^M phenylene terephthalanide): 2O ₉ Sl g (0.10 mol) of powdered terephthaloyl chloride are added to a solution of p-phenylenedianine (10.8o g, 0.10 mol) and N-Hefch / λ Add -2-pyrrolidone (60 nl) and stir to 0.916-liter when it is very cold. Within a few minutes, a stiff material is present which, after 20 minutes of age, combines with water and stirs at high speed to a "ft" 9 * 6 -! - Hi. "Cher. The Polynere is stirred in a mixer with water, once old alcohol and finally old acetone and isolated by filtration, whereupon the Polynere drys out at about 100 ° C. Polymer yield 23.0 g (96.7 % of theory )} inhfirente Yls "iositS & _t order no solution of 125 ag poly" aers in 25.0 "! 95 ^ bi »^ Sgew.iig ^ r Sehvefelsfiure _t - 3.67. ·

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809807 / MS.31

BATH ORIGINAL

& ®v wet fiber: The above, wet, as-spun Zuvorliogende (washed) R & dengut is performed with 7.64 n / min, through the suf 640 ° heated tube of the apparatus B, and "it the rates according to Table 1ΙΣ gesanaelt · O ^ v Orientation ·· wisakel (Ok) and the T / E / M ^ / den values of the resulting fibers are given in table XXX. The asss of the wet · 15 (Table II) troekengespona · thread material is carried »at 7.63» / min through the nitrogen-precipitated temperature of 600 ° and channeled »at 8.1 n / min. The resulting fiber shows a hon ·. Krlstallissitäfe and an orientation angle of 12 ° Ca »Vitwinlcel-HSsittgessdiagraRas: bestinsBt). T / E / ^ / den of the Ffiden IS

T a be lie HI warning treated · fiber

Fiber Ffiser «F fffe rel ge . n.schaft , ·

from ■ s & nnel— ■ -

speed,

"/There. T g If, OA

15 8 »T 15.9 I ₄ S 9H $ 8 ° 5

16 8.2 14 ₉ 3 I, ¹ * 1056 9 ° 3.58 IT 8, * 10.2 X ₉ H 805 10 ° 5, T €

B ₁ H ₁ Eg 1, lfl

This example explains dt · 3eü *. $ Iell «ng.1. a "random Ittwhpolyanidas" it "ie4t7t £ ehr" ends Units "^ at" ft Α · τβι "ρ" · '^ ^■':; ; -HH-Qnco «, -ΙΙΗ-φ -»! * ». and - (30 * 0-00- (relative $: 1 : i> _t "2. an aaisciropen Barnrt & teasse xmd 3. of fibers from de» Misohpolyaaid.

Bin uit an air-driven windshield washer-5ÜSS stainless steel of the Sauart Carpenter 20, a »Stlek-

& «* I ~ HÜfe £ nerstei! Ung8k®88el will» it be the flasane of a Sunsen

and flushed with nitrogen at the same time, whereupon there is a freeze in and in an egg drying tank, ie a chamber that is kept open. Zn the dry. 352 »1 tetranethylurea are poured into an alder egg, which is then locked and cooled in ice.

90988 7/16 93

In #es »

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efel «? i <3 Qaegetj33O3E (3 «p

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«Seco K & q $ szu.

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ti »© 1 * 3« ^ s £ sM! M® £ qe & 99 ₈ β JSS ⁵ f © ⁶ ©

s ESC® gätok äs alsioa oiö oäees

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_# SQ 5 «f« .if oa

liilitatai · Ines · * if € l «rt 'then- 5

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wivd di

909887/16 93 BATH

1810428

Fiber production by dry spinning: The mass produced in the above manner is heated to about 110 ° C and old about 2.3 * sl / win. at a pressure of 5.625 to 5 # 976 kg / s ² through a spinneret of the Vorapnmg type heated to 125 ° C with 6 M-. Eased out from 0.01 on diameter into a drying chamber, the winds of which are kept at a temperature in the range from 198 to 207 ° C and dry the nan with a countercurrent, at 235 ° C and 0.13% / min . The emerging threads are guided over a small guide roller containing a sizing solution and wound onto a spool of 139 n / M in., which corresponds to a spinning stretch factor of 2.91. The opaque threads spun in this way become soaked in water while changing the water (25 ° C) to remove the residual solvent and make it shiny. The polymers that make up the threads have a. inherently «Vieooslt & t of 1.48. The water-leached, air-dried (21 ° ± 65% relative humidity) threads have an average stability and an orientation angle of 27 °. Boiled threads result in a T / E / M ^ of the 8.5 / 2.8 / ^443/1 I Ol _9.

Heat treatment of the fibers: The threads obtained in the above catfish are passed in a »one-step operation under a knitted fabric over a 7.62 cm plate kept at 530 ° C. in such a way that their length is increased by 0 to 1%, with the yersil side above the Helssen plate is about 2 seconds. The resulting fibers show a high kvietallinity and an orientation angle of 12 °. T / W / M ^ / den of the boiled fiber: 12.9 / 1.4 / 915 / 2.9 *.

B e i «ρ IeI 19

Beiapiel 18 old the difference,

that the

are available at a rate of 2: 1: 1.

_t Polymerhei'rteilung: The apparatus and Apbsltsveise correspond to the following example old 18 amendments:

The intermediate substances are p-phenylenedianine (8.110 g, 0.075 Terophthaloyl chloride (15.227 g, 0.075 hol), p-aninobensoylohloritol hydrochloride 28.005 g, 0.150 mol) and bexaaethylphospliorsaid (300 nl>. - 63 - ·

90 9 8 87/1593

Di® Röatefcionalößiuisig mlra 3i / S. Sfed. bsi aaragekabp O ^{€ 0} and S at «fcwa 25 ° C

$ 99 ^ S S

Seratosition d @ g> Massel Bin with a lufteetriabanen eoheibenaeher-

rllhrar a Ktondeneator and a Ctloiiitetiiirie ^^ äu'a-

g®8 $ aftäeti§F SOO-nBl-HaratteretelliiiQgBkMMl '«ird wi ^ 30 g dtia obifpn P © isrni © p © p, unä 270 g! ltotra ■ 0thyllιaήuίtιoff ^ί -'L · ittthlunβhlopld · -L · S8 ifi «» ie teHalt τβη S _$ 5 ^ to% i. '| 'tu tem äals tosehictt ,. An udotertel- tea IMcütolen in f # etcm Kolilmdioxid and iite ^ p at 125 ° C- (Olbftd-

does not produce '.voiljitindip' Zepkleinenang tfee fettten m «i 'miter« »■ 3e ^ imlie0 Ibldlhltingen in f © efcei» Koh-

lfl! irbeliMidliine «iti Iwi iG0 ° C

, di «10 Qw» S Folf »®F« t

dureh f ^ ektnipinwests ii «in 'der © feigen Weis® Ιίλβιιβ is aulßrfO ^ c eritat- and -nit about 3 ₁ 5' at most umrnk rm 9ß ^ '5 kgf®m ^s ..uwmb · ίη · belioiite ® C) alt 9 Wehem von jetfuile O ₉ OlVt «■ DuPotattMr in an anegoeioieen» "deseen Vlbsi · on a fenperatw in the B®F®i (ßh ^ © a 197 to 2Ο7 ^ιβ> C geneltmi werÄen and ier ait einea 0 ©» 'gtntiivoa tjpeeltntH »with 261® C entering ßfeSeketoffe - filled with O ₈ 127. ¹ I ir / WSb.« irdt We jiuetretenden Wien «erden Ober

^8th
continues "ei oit 139 a / Hin · auf '-" Ine * flfrtOe f

Bplmmlm®kt $ klor tea ^, 6 entapritht · Di · s © erapennenen 'FMen

fefepiniert in Weeter (25 ° C) under Waieemteebtel » ₉ vm ieet-

10suneaitt; e3. country. -tal% nu ontfemeini. Di '· lwfftg®tr®eim # t®ii! (2 ° C _for 5% relative © Feuebte) Threads have their own middle XrietallinitBt nnä ®ir> ®n orientation angle won 35 ^Θ · Ab-Pad «result in a T / E / M ^ / d®n of 3» 4S2 »5 / 2l6 / 3 «34 ·.

d®? Fas® ?: Di® Apptr & tiiir and chert the example 18. Όί®'mti & llenuen F & ®ern tseigei »a high K: rl-8 $ aliini $ tt and have an orientation angle of 15 °, T / E / Mj / den der ab9koeh $ @ n Paser 7.2 / 0.7 / 886 / 1.68.

809887/1693

Example 20

This example explains the preparation of 1. mixed poly (pphenylen-p.p'-biphenyldiearboxamide / isophthalamide) (90/10), 2. an anisotropic oleusonasse of the same and 3 »of fibers same.

Polymer Manufacture: One with a whisk-type stainless steel stirrer, nitrogen inlet tube and CaI-eiM & chloride drying drum. equipped 500 ml Harsheratellungs: "kettle is treated with the * Fleram® of a Bunsen burner and flushed with nitrogen on the same side, then closed and placed in a drying chamber" 9 * 733 g (0.09 mol) p-phenyl are added in the drying chamber " ndiamln balanced and poured into the bar kettle. Furthermore, in the dry comb? 192 nl Hexanethylphosphoranld and HB nl N-MethyI-2-pyrrolidon measured and poured into the kettle. You take the kettle out of the chamber again, connect it to the stirrer motor and the nitrogen pipe again, stir the mixture "until the dianin is ready, and then cool the kettle in an ice bath.

In the drying chamber, 1.827 g (0.009 mol) of xsophthaloylohlorld and 22.609 g (0 _e 08l mol) of ^, i ^ dibene soyl chloride are weighed out, combined and added all at once to the dianine solution. Rapid stirring and cooling with ice. to 2 hrs. continued while, solidifies gelati su ^ öeen about xu this time a the ReaktlORsatisehung which do not look nehr stir Igest and ttw * ^l .64 hr. is allowed to stand at about 25 ° C. One voreinigt the gelatinous out on a "mixer with water, the mixture is stirred at high speed and filtering the resulting precipitate on a nittelporlgen sintered glass Buchner funnel from" The precipitation is ur under HÜhren in a blender three times nit water and sweinal washed with alcohol * ä filtered off after each washing treatment.

The product is left to soak gently in a vacuum oven under pressurized nitrogen for 16 hours at 80 ° C. Polymer yield about 100 % J ⁷ Zi _n J ₁ »2.51.

Preparation of the mass: Xn a sole provided with a stirrer for the 25.812 g of the above polymer and 146.27 g

- 65 - ■ 9 0 9 8-8 7 / Ί 6-9 3

£ OO, £ 72 SotaMsfolsfiuv · C3.2 % free SQ-J united ·

pen dex * Mixture at about 25 C falls ®ln® anisotropic mass © & n ₈ the 15 (tow.g at the Misohpolarnerea omitted ·. The flBJMisrt «iss® ** Hasse in ΙΟΟ, ΒιΧΙββτ getawof® !.» !! «» ® tetregt 98.2 «

dwofa laetspinmgii Bi * Stusse C2S ^# © * like © esse ner-

posed) - wäM on a ropes «Mi FOrtfwieii 8MhI d«? ~ Type Ca * - pcate®? 20 # in $) egff »tesr m & dnsrolä« Jbie% it »dis · Bit 20 Uoteni 'of 0.076 ns ßas ^ lme ^ sap in i0e» w «1li | p Selirafelel« «vas 25 ° C · M.® koaipiIitFten FUim wpiiiii,

lets »iii% 13 dd / iiA» \ «if. & Ijiw ^

FSden weMeni umm In lliJWfi7_C3S ⁹ H) inttr itossvsamefis ·! iiiii da® -Viiteer ni & ht. nato was 1st. M » with ltiftgotro € ilat @ teii (21 ° C ₁ $ 5 f 7®Iatii» ftaelitfii WS, A®m be a «

ÄPiefcalliattät at «ines Offiaastieramgewiaife ©! th 28 ° / of the FSdtn Cie Sig «a« iet «al 5» 2/4 «7/373/10» 72.

No fiber. is not filled with 1 ₉ € 2 »/ lim« um®h um msS Rohr dez> VondtsSitsame λ «δ £« on i & s I Pasex »Eelgt ein® ho!» Krlstmllipitlt ^ c ?. tet mMwm of 12 °. T / E / M ^ / dtn toF atosnScoelstea fiber 8.8 / 1 ₈ l / 70S / l2 »26

8,, R-I "" ".1, 21

This example explains. Alt BeFst®lling 1 «9inos

* HiaöfepolyÄaide »snlt wiedertefcTOiiäesi Einteitoii mm um

Vesrtititnle 95: 5 '95 ι 5) » 2nd one

Hisohpolyanidee unü 3. from 'Passra

: Eirs with eisten Efllüw mm stainless steel <ä®v Sehneebeeei »-0aiiapt, einsm Sfciekstoffaiiilaiis ^ AF wiä

old de? Fl & mse eines Buasenbs ^ anoFs boliantelt and gl®ieto®i tig atit Stieksftc-ff flushed _t verBahlesasn ma in ® £ na f ^t ro @ kenkiüt '»: β · ρ g« g * t> «n. in the Trosksiracasnnar f, 2 ^ 6- g Plionylendlamine 'and 0.487 g C® »00 $ § Hol) m vogen and in'dasi Harskessol © ingegabm» Feme? measures' »to in

- 66 -

300837/1693

...,. Γΐ, ν ?. BADORIQiNAL

I "" ■

Drying chamber 192 al Hexajnethylphospheraaid and 48 ml N-Metnyl-2 « pyrrolidone and pours aie into the boiler, which then also the Troekenkamaer unnoaaen and back to the Rflhrernotor and the Nitrogen line is connected. Venn the solution of the Diamino occurs, the kettle is "cooled in an ice bath"

In the Troekenkaaer, 0.91 * g (0.00 * 5 mol) of isophthalojrlohlorld and 23.865 g (0.0855 Hol) of M'-dibenxoylohloride are weighed, combined and added to the above solution in one go, with rough drilling. The reaction solution is stirred for 18 hours while cooling. The viscous water is then combined, then it is stirred on a kit and the precipitate is filtered off, which is washed three times old water and one time old alcohol while stirring into a tube and filtering. The product is dried in a Yakuua oven under a light soft glass of pressurized nitrogen for 16 hours at 80.degree. Yield 100 * i ^ _inh * 2 79

Preparation of the Hasse: Combine in a old a * stirrer provided Sehleuderflaaohe 28% strength * dea above Poljraeren and Ιβί, Ο 100 g ₄ 72lige Sehwefelaaure (3.2 Ji free SO ₅₎ and the mixture is stirred at about 25 ° C ₉ to a smooth, anisotropic mass (old elnea Misehpoljraergehal't of 15 öew.f) is present. The DDA-Vert of an average weight in 100.8l2 sulfuric acid is 95 *.

Fiber production duroh wet spinning: The above, anisotropic cash register is made in sine felle sas stainless * steel of the type. Carpenter entered 20 and expelled through a spinneret old 20 holes of 0.076 aa Dureaesser in £ 0 weight, fig. The coagulated threads run over a guide onto a winding bobbin thawed in water, their speed being 11 * m / Hin, and the threads obtained in this way are soaked in water (25 ° Ο with a change of water until the water is slightly acidic. The old water-leached, air-dried (21 ° C, 65 % relative humidity) threads have a low crystallinity with an orientation angle of 27 ° CT / S / Mj / den of the thread (Bigens state) 5.6 / 5.3 / 297 / 8.98.

Heat treatment of the fibers: Trcefcne thread and wet thread (which have not yet experienced drying? Are lifted at 7.62 n / min, through the

a tube of device A at a temperature of 600 ° C. The wet fiber, which is pre-stretched 1.01 times, sinks high crystal integrity and an orientation angle of 9 °

_{1 of} the threads (natural state) 12.3 / 1.6 / 837 / 7.997. The tropical fiber, which is pre-stretched 1.04 times, has a high crystallinity and an orientation angle of 9 ° · T / E / M ^ Zden of the thread (natural state) 12.0 / 1.8 / 817 / 7.95.

Example 22

This example explains the production of 1. a random misohypolyte old recurring unit from the group -IIH-Ö-ÄH-, -HH-Q-NH-, -CO-OO ^ ⁰ """* -CO-O-CO - (relative wood ratio 9: 1> 9: 1), 2. an anisotropic oleus sea de · Misohpolyanides and 3. of fibers, from the Mlsehpolyanld.

Rolya preparation: The apparatus and method of operation correspond to the « Example 21 old with the following amendments:

Di · Zwiüohenstoffe are p-Phenylendlaain (8.750 g, 0.081 ■ -Phenylendianln (0.973 e »0.009 NOI) ₉ BexaBethylphosphoraald (192» 1), N-methyl-2-pyrrolidone (HB Bl) Terephtbaloylchlorid ₉ (1.827 g, ₉ O Ooji Hol) and 4,4 * -dil> enco3rlehlorid (22.609 g, 0.081 hol).

The polymerization solution is 2 8td. stirred and cooled in an “egg bath · Dm Foly” ertjetea gradually forms a viieos ·· OeI ₉ that doesn’t let you look. This out is left for 16 hours.

The product is dried in a vacuum oven for 16 hours at 90.degree. C. under slight dissolution of pressurized nitrogen. Yield 100 Jh ^ _1n J ₁ «2.26.

Preparation of the mass: 27.861 g of the above polymer and 157.90 g of 100.72% sulfuric acid (3.2 % free SO.) Are combined in a Sehleu derflaaohe equipped with a stirrer. By piping this mixture for 8 hours at about 25 ° C, an anisotropic Hass ”bit with a flour content of 15% by weight is obtained. The DDA value of a 15% by weight liatsee in 100.8 liter sulfuric acid is 52.5. - 68 -

909887/1693

fft 1810428

Fiber production by wet spinning: One gives the above anisotropic Wet at around 25 ° C in a Carpenter 20 spinning shaft

and etösofc it through a spinneret with 20 holes of 0.076 mm Diameter in 10 wt the water drips), and soaks the spun threads in water (25 ° C) while changing the same until the water is no longer acidic. The water-leached, air-dried (21 ** C, 65 % r * relative humidity) Ffiden have traces of crystallinity at an orientation angle of about 36. T / E / M ^ / den of threads (la Bigensustind) 5.8 / 7.2 / 236 / 12.00, '

Heat treatment of the fiber: The obtained in the above catfish, drying thread are carried out at 7.62 m / min, through which a temperature of 600 ° C having tube of the * device A out. The on that !, Otfaohe pre-stretched fiber has a medium crystallinity ttnd has an orientation angle of 14 °. T / E / M ^ / den der Flden (im Flower condition) 10.3 / 2.2 / 596 / 8.85.

Example 23

This example illustrates the preparation of 1. 75/25 mixed poly (p-phenylene-Ptp ^ biphenyldicarboxamide / terephthalamide), 2 x one anisotropic oleum mass of the same and 3x of fibers of the same.

Polymer Making: One with a stainless steel stirrer Whisk design, a nitrogen inlet pipe and a calcium © hiorid ^ Trookerarohs · equipped? ll "* Har £ her8tellungs] teesel is treated with the Flsmae a Bimssosibreftnera 'and equilateral purged with nitrogen, de & m vm ®®hlosnen * and place in a drying chamber ge *., In the" Tr 6> @ k @ sik & EISM © r 8.652 g (0.08 mol) of p-phenylenedi "aira aiaegaw ^ göK, which m & n into the Hare kettle. Furthermore, in the dry comb "tiI ml Msx & snefehylphosphoramld and 43 ml N-Me-

Diss * boiler is then reconnected to the. If the solution is rö © 8 Di & mifüB @ l ^ g @ tb ^ ®% @! N is ₃ wirM d © x ° kettle in an ice =

- 69 -

909887/1693

BAD ORiQINAL

In the drying chamber, 16.7 * 173 g of CO ⁶ %, ^ 8 chloride and ft, 0601 g of CO, 0 2% of finely ground terephthaloyleyl chloride are weighed, combined and added to the dianine solution all at once with gentle stirring. The reaction mixture is stirred for 1 hour and cooled with an ice bath, whereupon it solidifies in a viscous oil which is stirred for 16 hours at 25 ° C., combined with water and stirred on a mixer, whereupon the resulting precipitate is filtered off. The product is washed with stirring in a shear Mi and then filtered three times with water New York Convention cdstnal nit alcohol and then dried in a vacuum oven unte-p slight Entweiehenlassen of standing under nitrogen Drweic IS StA, at 80 C. Yield 100 ΪJ ^ J _n ^ * ** i7 »^» t3-

Hersteilung of Hasse: Han combined in one ai ^ eiaeie üfltoer provided Sehleuderflasohe 169.3 g i00,70lig® S @% iwfeie§iire C3 'l% fasies SO ") and 22.0 g of the above polymers and rttefc älese!. Ml- 'vision at about 25 ° C _t until a smooth, anisotropic Hasse C jnrgshalt 11.5 Qow.2) is present · The DDA-Vert a®? !! "! The mass in 100.83% sulfuric acid is 97» 2.

Fiber production by wet spinning: The above anisotropic solution is placed in a spinning cell made of stainless steel of the Carpenter 20 type and spun through a spinneret with 20 holes of 0.076 mm diameter into 10% by weight sulfuric acid at 25 ° C. Di® flaps are spun with 20 , 4 ra / Hin, over a guide and sit a winding apule. The spun powder is soaked in water (25 ° C) while changing it, until the water is no longer acidic. The thread-like crystallinity, leached with water, air-dried (21 ° C, 65% relative humidity), traces of crystallinity at an orientation angle of 31 °. T / E / M ^ / don dar Ffiden was 7.8 / 6.6 / 239 / 10.10.

Heat treatment of the fiber: The wet threads iul & ~ n®.®h -no niang have been experienced) wtrdeiB with 1 _$ ü2 n / föirc. disreh the in the "mid-temperature ein® of € 600 ® .aufweisende tube u r ^ Vos ishtung A out. The on the l.07 £ m @ h @ ve? Atrs @ 1> ctes $ _s nass® »Mdas a holie Kriet £ lli! Ait && bsi siLneia. Orientieronginiiidcel. voni

TZEZM ₄ / den des * Ffid © n

909887/1693

Q-iO3i ty

Beiapi ·! 2 *

This example illustrates the production of 1. 55 / ^ 5 mixed poly (p-pheiiylen-p, p'-bphenyldioart) oxaaid / terephthalaaid), 2. an anisotropic olftuaaass of the same, and 3% of fibers from the same.

Polyaer production: The equipment and working method correspond to the Example 23 old the following amendments:

A hars making aceasel with a capacity of 500 al is used.

The viscosity substances are p-phenylendlamine (9.733 g, 0.09 mol), He-3-methylphceptaoraaid (192 a1), N-methyl-2-pyrrolidone (48 a1), M '~ Dlbensoylohlorld (13 »817 g, 0.0 * 95 mol) and terephthaloyl chloride (8.223 g, 0.0405 mole).

Daa poljasre OaI becomes 16 8td. stirred while cooling in tap water.

Yield 100 ti *! ^ * 6.39, 6.5 *.

Preparation from Nasse: Combine 24.80 g of the above polymer in a "with a stirrer provided with a single oyster liquid old 223" 2 g 100.70figer eehulfuric acid and stir the mixture at about 25 ° C to MB toggle storage of an anieotropic wet (Mlsehpolysaid content 10 eew "!) By DQI-Wezt a 10.0 weight weight wet in 100.8 g" r «• hweXUMüsre amounts to loo.

Fiber production by wet spinning: The above anisotropic wetness is poured into the stainless steel ropes from Carpenter 20 at around 25 ° C and ejected through a spinneret 20 holes of 0.076 aa Durehaeaser in lOgew. The flutes run old at 30.5 β / min. About a trip to a whale whale. The spun threads are sank in Vaaser (25 °, C) with changes of the same gas, until the water is no longer acidic. The water-leached, air-dried (21 ° C, 65 % relative humidity) threads do not show any crystallinity and have an angle of orientation of about 40 °. T / B / N ^ / den der? Fidon (Eigenxuetand) 9.7 / 8.7 / 256/3, ^ 2.

- 71 -

909887/1693

Heat treatment of the fiber The © big® »dried® fiber is measured at 7.62 m / ml. in.d & as im des? In the middle a T®s »p®rafeur of β © 0 ° C having © Rons» the device A

The fa @@ ra @ ig, which is stretched out onto the i, 07fa @ h®, has a low KrI-etallinit & t at an orientation angle of 18 °. T / E / M ^ / den der Ffiden. (Bigtnsustand) 22,5 / 3> 2/668/2 _a 77 ·

JLi_iL-gJELi-JÜL · --2g;

This example explains the production of "in @ ® mgellosasfi mixed polyamides" with recurring units from the "group -MH-O-ö ° -" -MH-O-HH-- and -CQ "0-Q" CQ "(relative molar ratio above : 3 ί 3), 2. an anisotropic 02euma @@ am and 3 · τοπ Faiern from the

One with a HÜhrer mn® SOSfefreiem S ^ ahl der

iSchneebeien-Bi & iaart, a Stieke ^ effeinlaserohi ⁸ usid of a »Caicitaraohlorid-Troekenrohr equipped SOQ-mS.-Harsherstelleringekesisel is treated with the flame of a Bunsen burner and at the same time flushed with nitrogen, ^ eroenkasirasr ^ and in @ in® Troeken. In the drying chamber are 7 "3 © O g CO i 'O6? 5 mol) of p-Phesrylen- * diatnin balanced and gegeben® into the boiler Next ndsit nmn in dop Troekenkaraaer 192 ml He3sam ^ nyiph © eph" aitid MNAE 18 ml N- Methyl ^ 2->pjm> © l £ don and greed them in the loseel ®in. The boiler is then removed from the Tr © @ fo $ itkafflßier and connected to the RtUi- 'remoter and the nitrogen line ang @ s @ liloE @ on. If DI® Wmmg of Dianins occurred "is the Krase! carbonated in <ain <asa Bisbad. .

In the Tr ^ _s okenkamamr 4 g 32i (Q ₉ Q 22% mol) of p-Aaiinobensioyl · = ohloridhydroQhlorid and Ä8,8 ^ S g _(Ο ρ Οβ75 mol) of 4,4 '- ausgewpgoni 3lbenioyiehlorid combined u ^ d ennt ßinm & l m-Λ ^ rao @ hsm stirring '»ω der DidmiLnlOsaimg .hinEUgsg © b®n«. The Rsakülsnsänlsetomg is cooked for 1 hour and in an egg @ bäd g-ikühlii and then 16 ska. stirred at about 25 ° C. The QqI is with V & ss®? combined, stirred on a mixer, mwS filtered off the precipitate. Stirring to a mixer wia Filfei? I © rfi? Is the Aue precipitation three times with water and once with A2Lk © i j?, Al-gewass'ion. Dae Psröd ^ kt is made in a vacuum oven

- 72 909887/1693

Dryed at 80 ° C. for 16 hours with the slight escape of pressurized nitrogen. Yield 100 * »^ _inn * 4.92," «5.81.

Preparation of the mass: mast combined in a stirrer equipped with a stirrer 17? 100 g of sulfuric acid and 23.0 g of the above polymer and stir the solution at 25 ° C until a smooth, anisotropic mass (misoh polymer content 11.5% by weight) is present. The DDA range of a 11.5% weight in 100.8% sulfuric acid is 95%

Fuser production dusOh hate spiders: The above "anisotropic mass" is placed at 25 ° C in a spinning cell made of stainless steel of the Carpenter 20 type and ejected through a spinneret with 20 holes 0.076 mm in diameter into lOgev.ffige sulfuric acid "at 23 ° C. The threads are wound up at 22 m / min. · The resulting FSden is soaked in Vasser ( 25 ° 0} while changing it, until the water is no longer acidic. 65% relative humidity) Threads show traces of crystallinity at an orientation angle of 32 °. 37S / M _£ / den dw threads (cooked) 8.3 / 7.1 / 183 / 1.86.

d «n> fiber: The above, dried threads are led from Τ, δ2 m / Hin, through the tube of device A heated to 600 ° C in the middle," The threads stretched 1.14 times aeigen "in" high crystallinity and have an orientation angle of 12 °. ΐ / B / M ^ / den of the threads {eigenstate) 17 »9/2» 1 / 858M, 58.

B a J ₁ 8 ρ ί a 1 _{ι :} 26 .

This example corresponds to example 25 with the difference that the mentioned recurring units of the Mieeh polyaldes are present in a molar ratio of 2: 3: 3.

Polymer production: The apparatus and method of operation correspond to the Example 25 with the following changes:

The components are p-phenylenediamine (6.489 g ₃ 0.06 mol), Hexas & ethylphosphoramide C3i4 ml), N-methyl-2 "pyrooiidon (53 ml),

- 73 -309887/1693

DiÄen8oyIelil © rfd (163?%! G, 0, OS

The Polfite »remains in the entire te &» l © »ss © it in

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-909887/1693 BAD ORiQSNAL

Example 27

This «example explains the production of i. FoIy- (p-phenylene-ρ, ρ'-biphenyldicarboxcBid), 2, an anisotropic oleus lake of the same, and 3rd of fibers from the same.

Polyttorheretellungc A SOO-nl hardening kettle equipped with a stirrer made of stainless steel of the Sohneebessen design, a nitrogen injection tube and a CaI-cluachlopid-Trookenrohi- is treated with the flame of a Bunsen burner and at the same time BdLt nitrogen is flushed, closed and put into a troker. In the drying chamber 6 _S * were 88 g (0.06 mol) of p-Phenylendiamln weighed out and added to the kettle. In addition, 128 al Rex & zssthylpiicaphorasdd and 32 ml N-methyl-2-pyrrolidone are drained in the drying chamber and poured into the kettle. The kettle is then removed from the drying chamber and reconnected to the pipe motor and the nitrogen line. When you see the Dlanin gelSot, the kettle is cooled in an ice bath.

The diamine solution is admixed all at once with 16 ^ 7 ^ 8 g (0.06 mol) of felnegeaahlenas ^, ^ '-dibcr.soylchlcrid with rapid stirring. The resulting mixture is stirred for 1/2 hour and cooled in an ice bath and stirred for a further 16 hours at about 35 ° C. The oil is combined with water and stirred in a mixer, whereupon the outlet is filtered off and washed three times with water and once with alcohol while tapping on a mixer and filtering, and after pouring the alcohol over the polymer, it is poured and filtered. The polymer is dried in a vacuum oven for 16 hours at 80 ° C. while allowing it to escape slightly. Yield 100 % j ^ ^ _h ■ 2, £ 8.

A “further, similar aneaös” resulted in an expansion of 100 % and · 2.00.

Manufacture of the Maaea: Hard united in a Sahleuderflieche seen with a stirrer ▼ uiig «for the same ^ ha Kengen (a total of 37jOÖ g? De? Cb.'igcsn br-iden Polymsrci? M% & 305 g iOO _e 25 # igö Sehwafels & ti & ta VUT. & Rühi'-t iLfifeesr »KGhlen In a child the mixture, bio β1κ3 gj.a; ^ o, HTi isotropic mass * V7i *! Lies C mixed polyamide content ^{ίΟ 9β} ** αββ7.Ί6 93 ~ ⁷⁵

Fiber production by wet spinning: the obig® »anisotropic © mass is put at 25 ° C in a row of rust-free steel of the Carpenter 20 type and through a Splrmdüe® with 20 ItOcnem vest 0.076 to DurehneRser in 16.4g®w.2ige sulfuric acid το »19 ° 0 from« The threads are pushed at 16.8 m / min, on one in water submerged bobbin. The air leached out with water dried (21 ° e, 65 # relative humidity) threads »have a low crystallinity and an orientation angle of 37 ° ·. Ϊ / E / H ^ den of the threads (cooked) 2.2 / 3.5 / 120 / 6.92.

Heat treatment of the fiber The ebigesi, dried Ffiden are Salt 7.6 m / min, thanks to which a temperature of 600 ° C in the middle having tube of the Vorriehttang A, which on the l, 05fa @ he Reratrecked Ffiden have an older crystallinity in one orientation angle of 16 °. T / B / M ^ / den of the FSden (cooked)

DDA assessment: A sample of poly- (piihen3rien ^w p »p ^tw biphenfidiearb © ic rmia) with« itHMB ^ j ^ si, 86 (obtained similarly as above) is used for the formation of anisotropic wet with a polymer content of 10 or more. 15.

Example 28

This example illustrates the preparation of% "poly-Cp, P ¹ -phsnyl" enbensanid), 2. an anisotropic mass thereof, and 3 out of fibers of the same, wherein further, the preparation of compounds Swiechen * · geielgt 1st.

Preparation * on i »- (i | '-Thionylamirtopheny3L) -benboyl chloride: A solution of 48 g !! - (ft'-AininophenyD-bensoeBHure and 3 drops of N, N-Dimathylfonaanid in 300« 1 thionyl chloride is 1 1/2 hours . on one Hafiserdanpfbad with back acflue treatment, excess thionyl chloride , is removed when the pressure is reduced. You put in the flask 50 nl of toluene and the suspension at full pressure and repeat this for 3 hours using 100 μl of toluene. By adding about 100 nl of TolisoX rum flask turned into solid matter which you can put on a rdnterslas-l'riohter underneath a stitchery fabric

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909 80 7 / IG 9 3

'-''' BADORtaiNAL '

Filtered off, washed with toluene or petroleum ether (30 to 60 °) and then dried in a vacuum desiccator over phosphorus pentoxide and paraffin shavings. The k - {* \ ». ThionylarainophenyD-benzoyl chloride» melts at 1 ^ 5 to 146.5 ° C

Preparation of ή- ( H '-Arainophenyl) -benzoylchloridhydrochlorid 5 Suspend in a flame-treated three-neck round-bottom flask which is provided with a mechanical stirrer and a gas inlet and outlet, 2 * 1 g ^ - (^ - ThionylaminophenyD- behzoylchlorid in 500 ml of methylene chloride, the mixture Z h saturates., with hydrochloric, nutseht the solid on a sintered glass funnel and washed with 100 ml of methylene chloride under nitrogen. the resulting Peststoff is suspended in 250 ml of anhydrous ether, and using a magnetic stirrer for 1 hour. stirred, then filtered off under nitrogen and then dried for 2 days in a vacuum desiccator. The yield of 4- (4 ^f -aminophenyl) -benaoyl chloride hydrochloride is 88%. '

Polymer production: A resin hardening capsule equipped with a whisk-type stirrer, a nitrogen injection tube and a calcium chloride drying tube is flame-treated with a burner and flushed with nitrogen at the same time. In the drying chamber, 210 ml of hexamethylphosphoramide (from calcium hydride distilled over at reduced pressure and stored over molecular sieves) and 210 ml N-methylpyrrolidone ~ 2 (from calcium hydride overdistilled under reduced pressure and stored over molecular sieves) © are infiltrated into a calibrated cylinder, after which the gyliaider is infiltrated stas removes the drying chamber and pours its contents into the Hargkessel, which is cooled in an ice-water bath, In the drying chamber in a polyethylene bag H 6.6 g ίο, ΐγί »Mol) ^ JC ^ '- Äminopher' yD-benzoyl chloride hydrochloride is weighed in, which is then quickly transferred to a resin kettle with moderate stirring. The resulting mixture is stirred for 30 min., Whereupon the raan Ele-Wassep bath is removed, and waiter 2 h 15 min. ₀ stirred. Then 12.9 g (0.175 mol) of calcium carbonate are added to the Harskeeeel, the mixture is stirred for another 35 minutes, the polymer mass is combined with water after standing overnight, and its fine powder is stirred on a mixer. The polymer becomes with stirring

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Q-1031 ■ V ■

Filtration on the mixer land & wff a SiEfcerglee-'Bifelmertplc Washed three times with water and once with alcohol, after which one Knead in a vacuum oven at 60 ° C. The yield of the poly-Cp

phenylenbenzamide) is 9β ', 4 Xs ' Isnh ^{a 1} ^ ^ ⁿ 99 »8 * iger sulfuric acid).

Preparation of the measure is added ISS * g 99 _s 83 $ strength in a provided with a stirrer and in an ice-water bath located three neck Polymerraasseflasche 5 ε öes polymers. and stirring the resulting mixture ubernaoht, w @ fe @ i during this time is obtained an anisotropic mass ₉ 'lie at Ktthress shows Qpaleszenss and is spinnable.

Paserherotellung by wet spinning ^ Di © in oblgeü Weiee conservation ™ tene textile pulp .If mim in a lined Fluorkohlenstoffhars C "Teflon" (R) OTE) cylinder stainless Sushi entered and the unit aiii · Distance ¥ © n Bubbles "gesohleadert Then the polymer composition are em means of a mechanically angetrletjenen Inj ~ © k tionaaprifeae by a © Platinspinndüse 20 LSshsp O- O76 ₉ mm Durehmeaser iron in a water bath 20 to 30 ° C ausgestosee.nj after passing through a Badstreeke of 61 DI® Fääezi on a The bobbin wound at about Y, 93 m / min. The treated (not boiled) threads show a T / E / H. / the top 2.24 / 3.9 / 145.4 / 4.90.

Heat treatment of the fiber: The threads obtained in the above manner are passed through the hot tube of 8a ', 3 cm in length' of the 'device

■ ο A led, with the temperature of the inner wall in the middle - βοο c

with the threads being stretched to a factor of 1.1 and being introduced into the pipe at 7.62 m / min. The resulting fibers have a high crystallinity and. an orientation angle " ^ft " ? °? ⁽ * of the (non-boiled) threads 4, 17/1 * 6 / 388,2 / 4, f

at

This example explains the production of I _n eiiiss with a content & .n equimolar amounts, reg®Hob Yii @ S © i * te! ITCBr,. ,,. -. of the units of poly-Cpjp'-phcnylenbeiisaiaid) with P © ly- (pt) ens-., ^ amid ₃ 2. an anisotropic oil mass of the same nmä, 3 »vo, n.-Fas8TO, from the same". . .,

- 78 909887/1693 - · · - ® & ^D ORiQlNAL

Polymer production: A 1-1 resin production kettle equipped with a whisk type ₉ stirrer, a nitrogen inlet pipe and a calcium chloride drying pipe is flame-treated with a burner and at the same time flushed with nitrogen -Methylpyrrolidone-2 (each from calcium hydride distilled over at reduced pressure and stored over molecular sieves) is filtered in, whereupon the cylinder is removed from the chamber and its contents poured into the resin kettle. In the drying chamber a further 22.6 g (0.08 * 13 mol) * l- (4 ^f -aminophenyD-benzoyl chloride hydrochloride. And 17, often g (0.0843 mol) p- Aminobensoylchloidhydrochlorid (about 5 % inert monomer containing Lömingnmitfee2verunigung) weighed into a polyethylene bag, whereupon the solid substances are mixed in the bag and then quickly transferred into the resin kettle with moderate stirring. Within 2 hours, the contents of the flask form a "rubber-like" mass to which, after standing over the weekend, 12.55 g (0.17 mol) of lithium carbonate in 100 μl of N-methylpyrrolidone-2 are added. The mixture is stirred 10 min., H can be hrs., Combining the polymeric composition with water and stirred in the mixer, rather fibrous particles are incurred. The polymer is washed with stirring to the mixer and filtration on a sintered glass Buchnertrichtcr 5 times with water and 3 times with alcohol and then in a vacuum oven overnight at C. The dried Auebeute to MischpoXymerem betrögt 98.2 fl * _nh li ■ 3.03 (in 99 , 5% sulfuric acid).

Preparation of the bulk ι Man.gibt in a provided with a stirrer and in an ice-Wasoer-B & d located Dreihala-PclymermasiO "bottle 25 ml 100? £ strength SChv / efelsSure, admixed with 6 g of the polymer, and stirring the resulting mixture overnight , during this period ο ins ani? o ';? ope mass accrues ,, shows the Rühropaleszenz.

Fiber production by wet pinning: The spinning mass obtained in the above manner is poured into a cylinder made of residue-free 3tah! With fluorocarbon resin ("Teflon" TFE (R)) and the unit is centrifuged to "remove air bubbles. The dimensions" ird then by means of a mechanically driven injection syringe through a platinum oinndüae with 20 holes of

909887/1693

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1810428

Ο, Ο? Β mm diameter in © expelled in a water bath at 20 to 30 ° C. After running a distance of 61 m in the water, the threads are wound up on a wet bobbin at about 7.93 m / min and soaked in fresh water for about k atd. Before drying. V / E / M ^ / den. Not boiled? Threads Ί, 6 / 7,3 / 188/2 »66.

heat treatment of the fiber σ that obtained in the above manner.

Threads are passed through the 81.5 cm long, home hobr of device A _s the inner wall of which is in the? Röhrmitte a temperature of k50 ° G having j, wherein one stretches the threads on the I ₉ JLfaöhe and 7.63 m / Hin. · In the pipe that introduces. The resulting fiber shows a medium © crystallinity and has an orientation angle of 22 °. T / E / M _i / den of the not, boiled threads - 6 ₉ 9 / l, 5> 530 / 6.93.

Example 30

This example explains the production of a mixed polymer, the randomly recurring units of PoXy-Cp, .ρ'-phenylonbenzamide) and foly- (p-ben «a» id), .2. an anisotropic ' Masoe of the same and 3 * of fibers from the same "

Polymer production: A JL-1 hara production kettle equipped with a whisk-type stirrer, a nitrogen inlet tube and a calcium chloride drying tube is flame-treated with a burner and flushed with nitrogen at the same time. In the drying chamber 230 ml Hexamethylpho8 £ horaraid and 230 ml N-Hethylpyrroiidon-2 are filtered into a measuring cylinder, whereupon the cylinder is removed from the chamber and its contents poured into the resin kettle cooled in an ice-water bath. In the drying chamber 15.7 g (0.0570 mol) of ^ - (V-aminophenyl ^ benzoyl hydrochloride ■ CMonomere's with a content of about 2.5 % of an inert solvent contaminant) and 3 ^, 9 g are further placed in a polyethylene bag (0.01728 Much} p-aminobenzoyl chloride hydrochloride (monomer has a content of about 5 % of inert solvent impurities.) Are weighed in and the solids in the bag are mixed and then quickly transferred to the Harss kettle with moderate stirring. The contents of the flask are formed from the flask within an hour a "chewing" schiikartige "substance. it leaves this polymeric substance * \ day are lessons they then combined, ηηύ with water. stirred on a

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909887/1693. .

Mixer, which forms rather fibrous particles. The polymer is washed three times with water and twice with alcohol while stirring on the mixer and filtering on a Sinterglae-Buchner funnel and then dried in a vacuum oven at 70 ° C, pulverized on a ball mill and finally put back into the vacuum oven until it is dry. Polyraer yield 91 * 5 % > ^. Χ _ηη ^s 3 _e 83 (in 100.2 # sulfuric acid).

Preparation of the composition: It is in a provided with a stirrer and in an ice-tfasser bath, wherein a is located three-necked Polymermaseefla BCHE k $, 0 g 99> 82iße sulfuric acid with 5 ε of the polymer and the mixture is stirred übernaeht the mixture, anisotropic mass is obtained, showing the Rühropaleazens.

Fiber production by wet spinning: The spinning mass obtained in the above manner is placed in a stainless steel cylinder lined with a fluorocarbon resin ("Tef-2on" TPS (R)). give and hurled to remove air bubbles. The mass is then ejected from a mechanically driven syringe through a fl & tin spinning nozzle with 20 holes 0.076 mm in diameter into a water bath at 20 to 30 ° C. After running a distance of 1 cm through the water, the threads are wound onto a bobbin at about 9.19 m / min, whereupon the bobbin is soaked in water and then air-dried. T / E / M ^ / den not boiled> ädan 6.73 / 7.7 / 229/3,

Öer Fater: The values obtained in the above description are passed through the 81.3 cm long, hot tube of device A, the inner wall of which has a temperature of H00 ° G in the middle of the tube, whereby the fibers are placed on the! ,! times stretching and inserting it into the pipe at a speed of 7/62 m / min. The resulting fiber shows average crystallinity and has an orientation angle of 19 °. TZEZM ₁ / den not boiled »threads ϋ, 8ί} / ί?, 6Ζ5ΗΖ2,7Ο.

On dissolving the above-described polymer C ^ j _n J ₁ ^E 5.83) in 100.2% sulfuric acid with the formation of a /> lg% w / y mass, it forms an anisotropic system with «. Value of 3.00. A 7 ige mass of the same .Stoffe isfc ieotrop unü has vain DDA word of 0, the annoying mass becomes

90B887 / 1.693 " ^{3: 1} "

spun in the manner described above; the spun, g @ waaohenen and dried threads result in a T / E / H ^ / den of β, 58 / 9.1 / 183 / 2.85. TZEZM ₁ ZdOn and orientation «*!» * ®! after heat treatment at * 50 ° C (device A) 11.9 / 2, $ / 61 * / $ 32.

Examples 31 * to 35

The following examples illustrate the preparation of i. orderly and semi-ordered, p-oriented aromatic polyamides from ρ, ρ'-diaminohensanilide, Texephthaloylchlorld (X) and ρ, ρ'-Bi » bensoyXchXorid (Y), 2. anisotropic masses of mixed polyamides and 3 * high-strength, high-modulus fibers made from the mixed polyamides ^

Mixed polymer production: The mixed polymers specified in Table XV are carried out in an identical manner using the ratio of the acid chlorides corresponding to the respective composition manufactured. All apparatus glass tips are used for at least 2 hours. dried in an oven at 120 °. The weighings and measurements are carried out in a drying chamber, and the reactions are taking carried out under a nitrogen blanket.

The diaisin is dissolved in a mixer in an amount resulting in a concentration of 10 to 13% (based on the total weight) of the weft-seeking polymer in a mixture of hexene thy 1 <pho & phoraKld and N-ktthy! Pyrrolidon -2 (Voluaen ^ obtained S si) »sets an equivalent amount of diacid chloride very quickly with constant stirring, the polymer solidifying in one minute SU a rubber-like gauze that can no longer be stirred and is left to stand for at least an hour without disturbance, the polymer is now isolated in Hasser, washes on the mixer four times with water and once each with acetone and alcohol and net overnight under vacuum at 100 ° C. The polymer can be further cleaned by first treating it with a grinder for comminution and then i Sfcd. Treated with AiaoisensSusr-e on the water vapor bath. After thorough washing with water, the foam is dried again.

In this way, Polymers 32 through 35 ^ Qn Table XV

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BATH ORIGINAL

manufactured. The polymer 31 is made in hexamethylphosphoramide alone produced, albeit in a MiBchlösungsmittsl similar results should be obtained.

Manufacture of hatred: To form the spinning wet one unites corresponding amounts of polymers and solvents and stirs in Room temperature in a closed system until an anisotropic There is mass that is spun before wet spinning.

Wet spinning: Wet spinning is carried out with a motor-driven injection syringe which is provided with a rigid-surface spinneret with 20 0.076 mm holes. The threads are coagulated in room temperature water; the immersion length is 60.0 to 8l, 3 cm _e The threads are wound up at the highest possible speed (Cvergl, the table) while the bobbin runs in a tub of water. The fiber is then soaked in distilled water for 16 to 24 hours.

Heat treatment of the fiber: The extracted, wet threads are passed through a heated tube (device A) stretched out and bssw. or annealed, with the feed at 3.66 up to 7.62 m / Hin. The stretching ratio β ©, dio temperatures and the thread properties are given in the table.

The mixed polyamides, the fibers of which are described in Table IV, are made up of repeating units from the group

O- and -NH- ^^ - NHCO-O-NHCO educated c

Table IV

909887/1693

T a to © ■ 1 1 β

Mixed polymers of ρ, p ^e -diaminob @ n2anllid ^ 6, * _r p * -iber ^ .45 «© jlchl Lorids 2iL—- ■ with terephtttaloyl- and p, 11th 32 s_ 9example 31 173 o / t Mixed polymer " 6.7 O J5 14th O _s 29 VeAIItnie X / Y i / o / 0.25 2.1 / K), 5 / 0.75 2. » 622 5, T 3.6 middle 99 * 2 Making the mass 10O ₉ 7 99.2 99.2 11th H ₂ SOj., % SOOJ to SO 10 13.1 Polymeres, öew »$ 10 12.5 13.8 12.8 ' tmfwicke! speed 8.7 when spinning, m / min. 1.08 I. Heat treatment. 1.08 1.07 • i "07 Streokgrad 1.16 1.00 1.01 -600 ■ · 600 6O & 600 Tea temperature, ⁰ C 597 580 550 Fiber properties 5.6 IfB erect state * »9 8.8 9.6 9 T 12th 8th 9.6 216 E. 1 * 5 259 257 7.2 ^M i 5, * 5.1 5.5 small amount the slight trace track track 35 Crystallinity 36 38 Λ5 Orientation win- ► kel, degree 13th wimetreated OK 13th 18th 2, * T 1.2 2.1 2.5 707 E. 827 55 * 800 high M ₁ high middle high Crystal identity

DDA ^and Bo8tiffiaunE · Ba & ffl Vc ^ cinigein another sample of the polymer from Example 35 with 99.2% * sulfuric acid · © su oine mass with a polymer content of Ii Gaw.Jf the mass produced gives a DDA value of 1.00.

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1810428

Example 36

This example explains 1. the production of a random, multicoraponent, p-oriented, aromatic mixed polyamide, 2. an anisotropic mass of the same; and 3. high-strength, high-modulus fibers made from the same.

The mixed polyamide becomes more randomly recurring from equimolar amounts Units of the following structural formulas formed?

Hez-steliung the polymer: Xn the drying chamber a solution νοη * 1.55 6 (0.02 hol) p ^ '- diaminobenzanilid and 2.16 g C0.02 mol) p-phen ^ lendiaiain in a mixture of 90 ml Hexamefchylphosphorasiid. and ^ 5 ml of N ~ methylpyrrolidone-2 prepared, transferred to a mixer vessel, placed under nitrogen and rapidly stirred with a mixture of 0.6 g (0.02 mole) terephthaioyl chloride and 5.55 g (0 _sec 02 mole) bibenzoyl chloride offset. The system solidifies: in 2 minutes to a rubber-like QeI. After 2 1/2 h., The polymer is prepared in water, dreiisal dried on the Mi-Sfshör with water and once each with acetone and alcohol ge ~ w & Sehan and in a vacuum oven of 100 ° C. The yield is quantitative; inherent viscosity 5, ^.

Preparation of the mass: An anisotropic mass is obtained from the above polymer by combining 5.5 g of the poly-KCf ¹ OB ₉ H5 g of 100.7% sulfuric acid and 5.0 g of 20%, fuming sulfuric acid at room temperature The stiff gel that forms at the beginning turns into a fluid, sfcer- / issose, if left to stand for six days,

i Maas © about.

Spinning μηά properties in the conceived state; Wet spinning is carried out using a kit with a motorized, flat injection syringe, which is equipped with an insulated spinneret with 20 holes of 0.076 ram. The threads are in water from Rawatom-

lic-rtj the insertion length is 71.3 cm. One winds DL® Pätfen with- 13?. m / min, on, Kfibrend the coil in a water and to & tütb which then form 16 hours »in distilled ·

90 3 0 8 7/1693

⁰ AD ORlQ / _WAt

in the ep
if Iiafe

The wet threads obtained turn while feeding rait 3 ^ 81 m / min «

55O ^w G having tube of the ^ extended thread material 12, JJ / 2 ®in <& g@rf.gig Brille Crystallinity at gerin

Example 39

The following example © 37 to 39
ffegellos © «Mis © hCp © lyamid5harnstoffea ₈ the ψ @ η reunion ^ ends

-HB-O-HH- ,. ""

In doing so, seigfe

in each case di © ipelafei "# ©! ni ¥ esphältnisse

At @ ρ i

909887/16 9 3

mnü lsi des »

'free

BATHROOM ORIGINAL

Q-Äü3a * or

has, whereupon 16.22 g (0.150 mol) sublimed in the drying chamber Weigh out p-phenylenediamine and pour it into the mixing container and stir the mixture at moderate speed until see all of the p-phenylenediamine has dissolved.

Weighs 2, O g (0.015 M © 1) of p-phemylenediisoeyanate in a ⁶ x drying chamber and pouring it into the measuring vessel, stirs the mixture at high speed, weighs 27.4 g of CO, 155 mol in the drying chamber ) sublime Terephthaloylehlorid and add this to the solution in the mixing vessel with very rapid stirring, the solution gelling to a solid substance within less than 10 seconds after the addition of terephthaloyl chloride, which is left to stand for 5 hours and then poured into water ^{Add 9 to} a 3> 79 liter mixer and stir at high speed. The precipitated polymer is filtered off on a coarse Sisater glass Buehn funnel and washed three more times with water and once with acetone, the polymer being filtered after each washing treatment. The polymer is then dried in a vacuum oven at 80 to 100 ° C 35 »9 g (99X), inherent viscosity 1.83J ratio of units 9: 9: 1.

Preparation of the composition: A flask equipped with a stainless steel stirrer ^lt Schneebessn "type 500-sil-Harskessel is at Va = kuunefen dried and allowed to cool in a dry chamber at room temperature, followed by * 5 g polymer in the Harskeesel 3 and 145 ml of concentrated sulfuric acid CiOö, 5 $ fX £ g, titrimetrically determined), remove the kettle from the chamber and connect it to an air-driven stirrer motor and the mixture is almost stirred, the temperature being moderated with a water bath at room temperature « It forms a smooth, cloudy mass that contains 13 wt.

Fiber production and fiber properties in the spun state: The polymer mass obtained in the above manner is introduced into a spinning cell made of stainless steel and at a pressure of 28.12 kg / cm through a flat injection nozzle with; Ejected 20 holes of 0.076 mm diameter in a water bath of 10 to 20 ° C. The threads are led out of the water bath, and the thread is with

909 887/1693

Winding speed of 3 »^ 6 ra / min *. The bobbins containing the thread evaluate above aadM; la distilled water left to stand and then in air; dried _β The inherent viscosity & fc of the polymer in the padding material is 1.75 "determined in carbonated sulfur dioxide" The fibers have a low crystallinity and an oriental angle of "" danger% 5 ° ". T / E / H. / den & ®r Fädzn in Durohsohnitt 3.52 / 16.5 / H9 »401. ■ .-

Heat treatment "nd prop nsschaft © © n s of the fiber, the filaments are to Wbnsebehandltmg under Zufflhrung ait T ₃ 62 m / min" durcsh the 8a, 3 x 0.79 ¹ I © m pipe of the device A'geführt "wherein

di © RohrwÄMd WiM held in üer mastics to 599 ° C ₅ 20 threads the Fftdengut aiafweist nmd the Fadenlfinge when Dispchlaufen de§ Rota vm W% orti'Oht -WS ^w ö "Then ^ accumulating Fadengwfe has a high-KrI staXlinitftt, © Iswrs orientation tape 3. from lh wnd eirt T / E / Mj, / deri from average 8, .41 / 1,5 / 581 / 5,47.

B ·, ■! ,, »ρ i O ₁ I ^ S

PolyiMrhereto3Llung: A 946 ** nl-Mieehgef & Olge 8a is its heating ⁶ XnsienfXfiehe with Keissluft 15 © C in a Treekesnkasra® d ?, "h · temperature held at anhydrous conditions connoisseurs Haumiteiaporiituuf iibkflllilon geltaeifin with i20 ml

(aut · üaleiunliyAria bei'vemine «rtcii Smiek in. um TrmfcuitSammr .Qbes * Moio! ktiliiriii« l ».ii« if-> preserved), 60 ml H ^ Metlaylp ^ rfoIidon (from Caleiuinli ^ flrli at VOmJUtdillerteia pressure in abordostillerteia der Troeken! öSMi »r ObJtr I © 1 · - Γ; ■ · ■■ in a sieve), 5.0 g lithium emmid (get drysiöfc in a vacuum phone at 200 ° C and in the froskenkiiBBep) and 10.81 g (©, £ 0 KoI) eublimi®Ft <3 £! P-Ph®ii ^ l®ndianiin tocisehickt _f with a plastic deslcol beclo @ kt uni from d @ r wrapped in aluminum foil

All Feststoffe- "stirred drying chamber taken wcrauf r Can in the Qeflea through a hole in the lid and the foil άϋνχ © trccknea nitrogen gis introduces" The Miechüng is at a moderate öeachwindigkeit to calibration have dissolved.

0.80 g (0.005 mol) of p-phenylene diisocyanate are weighed out in the drying chamber and added to the vessel, and the mixture is stirred for 5 minutes.

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• -.909887 / 1693

at a wet speed, weighs in the drying chamber a further % 9 ₃ 29 g £ 0.095 mol) of sublimed terephthaloyl chloride and, with very rapid stirring, adds this to the solution in the mixing vessel, which gels into a stiff substance in about 15 seconds Leave to stand overnight, then add in water in a 3 * 79-1 mix and stir at high speed. The polymer WIs INEM coarse Sintergias-Buchnertriehter & bf iltriert ¹ U on ©, washed on the mixer dr®i more times with water and once with acetone and filtered after each Waschbehandlüng, after which the polymers in a vacuum oven at 80 ° C until 2:00 dries. PoIysnerass yield 25.1 g C92 %) \ inherent viscosity 2.8? J ratio of units 95: 95 s 5 »

Manufacture of the mass: A 200 ral round bottom flask fitted with a stirrer made of fluorocarbon resin (C "Teflon" ® TFE) is dried in a vacuum oven and cooled to room temperature in a drying chamber. 15 g of the polymer and 65 ml of congrained sulfuric acid (100 _s water content, titrimetrically determined) are added to the flask and the mixture is stirred while the temperature is moderated by means of a water bath at room temperature. Stirring soon becomes difficult, whereupon more acid (10 ml) is added. Cooling down with an ice-water bath also supports the production of the mass. According to long stirring, the mixture turns into a smooth, cloudy mass, "the polarizers circled as a thin layer of light depolarization when observed seigt.

wnd properties of the fiber as spun? ' The Polymsrmasse prepared in the above manner is in Rait fluorocarbon resin liner { "Teflon" (r) TFE) verraeciiianisch driven syringe of residual free steel Elst! © ra gegeb UNU by a Platinspdnndüse with 20 holes

Barcta eater in a molten bath of 10 to 20 ° C. Dl © threads «« s ° <S®rE with 3 ₃ 2 m / child. taken out of the water bath, the bobbins containing the fibers are left to stand in a dosfeilli © rtem Maaser and then in air, the fiber-forming polymer has an inherent wn 2.8H ₀ -T / E / Mj / the flor threads (21 ° C, 65 % relative average 5.55 / 10.7 / 181 / ^, 00. The threads have

i 89 -

9098 87/1693

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a mean criatal alignment and an orientation angle of ¹ JS ⁰

Fiber heat treatment and -eigeesehaften: The Padengufe a second, in the above Splnnversuch e.rhalten®a coil (T / E / PL / the average of the threads 9,2 ⁵ IZL ^ 8/168 / 8.55) is z "p lämefeehandiung ■. by a beheisstes 8l _s out for 3 5ε 0., ¹ 79 J cm tube (Device A) whose wall is maintained at the "mid to 599 ° C * with the threads with? ₉ δ2 m / min and can be lengthened by 10% when passing through the pipe. The accruing fiber is. highly crystalline and has an orientation angle of 11 ° and a. T / E / M ^ / den of through-center 9.96 / 1.1 / 8 * 7 / 1.60. .

Example 39

PoljmerheratelluBgs A 9 * 6 ml M £ 8chgefä88 on QIA s is Erhitifen the inner surface with Heiesluft won 150 ° C dried and * h in tiner drying chamber, d. ej.nes »ouch? cool anhydrous' conditions held chamber Cleans esipe rat us »· left" You are in da © Oefäee 90 Ml hexamethyl> phosphorami * i (from Caleiwmbyapio at reduced pressure Distilled and in the drying chamber via kularaiieb kept) j, h 3 ml HS $ ethylpyrrole £ don 'Cawi distilled at vemiisderteai Bgniek ötäes'd. and in about ffolötatlareieto stored), 3.75 S Llthiumchloriä Cin Vakuuraofen at 200 ° C.geferockiaeS and la ü®w preserves), and *, 05 g of CO ^ O'379 mol) eafeiisieft ©©. covers the Qefäsa with an "aluminum foil-wrapped lid " and removes the Qeflee aiae from the chamber ". In the container WiZ ⁶ O dursfo a hole in the lid and in the foil dried nitrogen gas introduced". Speed g © ^ra until the solids have dissolved »

Msn weighed in drying chamber is 1.20 g - (0.0075 mol) of p-Phenylendiiso * © Yanat and outputs it in the Misehgefäas a _s stirred mixture d.ie 5 minutes at a moderate speed, Hea t * Further, in the.. Dry kaiaraer 6.09 g CO ₁ OJO mol | Sublimated tersphthaloyl chloride as and is added to the solution in the vessel with very rapid stirring, whereupon the solution in 30 seconds to a stiff substance: gels, leaves the gel. stand over and then pour it into water in a 3.79-1 mixer and stir at high speed. That

- 90 -.

909887/1893

BADORlQiNAL '

precipitated polymer is filtered on a coarse sintered glass funnel-Buchnes ¹ and washed three times with water and once with acetone, filtering off the Poly.aere after each Waochbehandlung, and dried after the final filtration in a vacuum oven at 80 to 100 ° C. Polyraer yield 9.2 g (100 %) -, inherent viscosity 2.82; Ratio of units 4: 1: 1.

Preparation of the mass: One dispenses in one with a stirring blade Fluorocarbon resin ("Teflon" (R) TFE) provided 100 ml round bottom flask 5.0 g polymer and 35 ml sulfuric acid (100.7 ig, titrimetry determined) and stir the mixture, the temperature being moderated by means of a water bath from room temperature . The polymer dissolves to form a clear, highly viscous solution. By adding another 15 ml of acid, a clear, viscous, spinnable solution is obtained. This mass does not depolarize linearly polarized light.

Fiber production and fiber properties in the spun state: The polymer mass obtained in the above manner is placed in a mechanically driven stainless steel injection syringe provided with a fluorocarbon resin lining ("Teflon" TFE (S)) and through a platinum spinning nozzle with 20 holes of 0.076 The threads are fed out of the water bath and wound up at 3.96 n / min, and the bobbins containing the fibers are left standing in distilled water and then dried in air. The fibers have their own traces of crystallinity and an orientation angle of 65 ° and a T / E / M. / den (21 ° C, 65 % relative humidity) averaging 2.40 / 41.1 / 79 / *, 85.

Fiber heat treatment and properties: The threads obtained in the above manner are passed for heat treatment with elongation by 10 % through a pipe 81.3 x 0.794 cm (device A) , suführt and the tubular * "wall near the longitudinal center of the tube to 554 ° C hold. the resulting fiber is hochkt'istallin and has a Orientierungewinkel of TZEZH and a ₁ / the van durshschnitfclich 3.93 / 1.3 / 300 / 4.34.

The following examples * J0 to * 8 illustrate the preparation of r _; Nisctropic as well as isotropic Frjerfaßser8toff (OIP) lakes

S "fin P. fi7 / 1 r; C r> - 91 -

P IB 10 426. 2 ** "* 9 *" April

EI au. Pont de Iemoure and Company 'QJ

Poly-'Cp-benzatnid), poly '(p' phenylene terephthalamide) 'and a misofe poly ^ CClP ^ .ensainidl / Cp-pheinyleate replithalaiid)! ^ Whereby it can be observed that the anisotropic HF-Maesea stronger © fibers in the erepoa "new state (e.g.," B. "buckets with a higher strength and higher modulus) than comparable isotropic Maesea

This example explains dry spinning a ©? anleoferopea "See" based on "poly- (p * benzainide)"

Add 20 g of poly (p-benzaraldl) ^ i _0n "* 04 obtained in LIPI WU methjlaoetamid with Litblunoarbonat as SSureakzeptor naoh ERAL? '- nm' laier described methods) and 105 aA waeeerfreien IF la iine FolySthylenflasche of 180 ml Paeeuneevei "6g © is rai ^ Sehraututeppe mai stirs 2 feie 4 8td · with © inen 'HUirer w lae * © ll © y, deeeea mile is guided through a hole in the Mppß " where the ElaselH © wo "a®n with a Biff «Wa88er«> bath-cooled wiFi «Ifan pours dl © de, pearl witt-like, - anisotropic Sftw» ee ₀ üq 16 Oew.jt PolfueiPes contains (one corresponding mousse, 18fftlge Mus «©« telat ei © b with öop tion swisolien kre ^ Usten polarizer «tülo 4oppell» reeb <iiaa) and et? «the viability of ®lF®eriift has» In eliae von attfssjeia cell (about 10 ⁰ C) from Imecmel uai preset diaipeh Bruotaaiisib «ing autif one located above the line Piston through an opening of a circuit board pin (Bur0hme8S @ r 0 «015S esi» Linge 0 _# 00? 6 cn) FUen in a cross-section of 15x15 cn eonead shaft from- "Ln-0.9 m I4Cnge _# which with a s * anaeji _f des Peianlaaff"

gengesst geriotiteten nitrogen fetrom to * about. 70 ⁰ C AnfgetietäBifc is' «where a Dniok. of about 1 _$ B kg / on amp Binsfirk and the winding with 14o rn / ÄL »™ takes place · The thread spool is boiled in water for 15 to 30 min a T / fe / t ^ / den of *, 7/2 * 6/276 / 5,2 tmd shows «iae sntttsiere

Krittallinität and a Orlentieniiigewiiikol of 23 ^d "Iffteti anfeinanderfolgenden treatments vcn I to 2 3ek® <Bauer under iterlei- 'ton !! pet a hot rod fetvafff 52'^'3 Ci. Eaftatiiiospliliro ^ extension to «las l« 008fold) ' with BinawreMiMwm Aumh eiis heated . ■■ te «tube of 5 ^ 0" ⁰ C {device A, no streotaaag)

- Today Be8Ghreierung @ ®eite 92 · » 909 887/1693

, Ji.

1810428

T / S / M * 5.6 / i, 7/396 mu ^ the fiber and has a iot hoehkriatallin Orient ieinmgswinkel of 25 °.

Example *> 1

This example explains the dry spinning of an isotropic HF mass based on poly (p-bensamide) ₀

15 g of poly (pb @ nsamid) (^ _51n ^s 2 »8 * obtained by the general methods described here) are combined as in Example 40 with 90 ml of anhydrous HF ssli of a viacous, isotropic mass with a polyamide content of i * J Qev .% and pushes this mass from that described in example 40 spin cell at a pressure on the piston of 5.5 kg / cm ² and a ⁹ winding speed of 53 m / min. the end. After thorough extraction in water and troelmen, the fiber shows a V% m ± of 2.1 / 2 / T3 and a low crystallinity

and © Αωοώ He »tgen * Orientation« angle of 50 °. This fiber is rac ^ elysanäos ⁰ through & in the middle heated to 300 ° C tube {device A; Stretching to 1.3 times, contact time about 2 seconds) and a similar tube heated to 535 ° 0 (stretching to 1.5 times, Kcmtaktseit 2 seconds) and has a TZEZM ₁ of $ .6 / 2 3/283, and an average KristallinitSt © in _en Orientierungswinicel of 33 °.

Example % Z .

This example feeds dry spinning of an isotropic HF ™ Hasäa on dru ^ lag "from Poly" (p-phenylene terephthala! Aid).

U & n combined 10 g poly-Cp-phsnylentsrephthalamid) C% _nll ⁼ 3 »6» half of the five general methods described here) as in Example $ 0 with 85 to 90 ml of anhydrous HF, formed by ■ iropfenwsis © a 2ysa ^f 5s from 0, 9 g Metfcylsncshlorid a viscous, isotrape, Klar® cash register, which contains 10% by weight of polyamide, 'and does this “off”? ifia example ^ iO described. Zeil © at © Inera Driack asaf the piston "! Fi ψοΐϊ ~ $ 3 to ^, 2 kg / SRA and low Fadenaufwickelgeeehwindigkeife of about 6 _'8 9 m / min, from w © bai a Platinepinndüse Next» 0,02.8 & a diameter and 0 _s 0I5 sa length application finest «Dia ΡοίϋΦΓ ¥ lrd srsasih des? Collection boiled in water and dried., 0 0 3 8 8 7/1693 " ⁹³ "

whereupon 1 / EZM _{1 is} 3, ^ / 55/79. Make heatedtang at 3 »7 n / min. by a heated in "a 5-em-Hittelteil to 535 C tube (device A) to the A _s 0faehe gives the Faier a T / E / M ^ of 41 / l 8 / 698j high Krietallinifcäfe and- a

13 °, while the fiber in the efsp © anen © n state is only a small one Crystalline! Did and only shows © in © trace \ "on orientation.

Example explained using the wet spinning of an isotropic HP Maaee

Han combines 10 g of poly-Cp-phenylene terephthalanide) C ^ _11n ^s 3ß® obtained according to the beer besoteiotoeRen ₉ allgeraeinen methods, but ω & Β © iiwr other 'sample than in example k2} as in example ^ O nifc Ä20 ial waaserfr © i @ iia EF 315 an isotropic mass with. © inej? I Qefealfe of 7.7 oew.l on the Polpaej? Eri _? puts the measure into the in'Beispe3t §0 bes <ahrieb®n © cell and pushes it through a "Nißkelsieb-» pitnndQse au®, which over- a 90 ° bent anus piece no . the cell is breathed _a that the mass is spun horizontally and at an angle of 90 ° aifc d €? about the Aohse of the "Spinnsall" ^ whereby the spinneret ^ on ainsm Mi © k © lei @ b with efewa 175 -round holes wn

O _s O25 jra "Durehneeser formed wlwS« The threads are dwreh ® about 70 in the water bath (carbonized to 0 to h ^Q c) anisg®®i © saim and then about 7.3 min. Awfgewi © k®lt. Des · Dxwk on u®m Zellenkolbcn is 2A kg / era. After ssweim & lig © m _a successive Äfo- ". koohesi in d @ stilli-art © ra! tessar τοη each 15 MIn ₀ Dawer and Tr®skn 'n' _v 8eigt di © Fas © «» a Τ / Ε / » _Α ψοώ 3.2 / 63/77. Haeh. 'Advance stretching with 15 w / min. Through a £><ahai: st © s pipe C provision D) ₅ öesstn 5.08- cm- "middle part has a temperature of? 05 ° C, on the!." Sfaoh © seigt di @ E @ ß F®d! @ ^ well a T / E / M. / den of 8.0 / 2., 2/800 / 0.55 ₅ a © höh® KiPisfealliriitSt wad @ irs © n OrienfcieraiKgswink ©!? 5n If,

bljljLj? ό__ i ® a. _._ Jji

* t that

Mess © on femdlag-a of

909887/1893

28 g of poly (p ~ phenyleneteyephthalamiä} C ^ _inn «4.0, obtained by the general methods described here) are combined as in Example 40 with 110 ml of anhydrous HF to form an anisotropic, pearly tape-like mass containing 20% by weight belongs to the polymers, puts the mass into the cell described in Example 40 and expels it as in Example 43 through a 100-hole spinneret (hole diameter 0.063 mm in each case). Di® threads are passed through a water bath (6 ° C) for a distance of 210 ° C and then wound up at 71 m / min. The pressure on the cell piston is 9 * 1 to 9.6 kg / o ». After marrying overnight in running water and drying, the FSden have a T / B / M ₄ / den of 8.7 / 5.4 / 260 / 1.72; the threads show a mean crystallinity and an orientation angle of 21 · Naoh stretches «it 15 m / min, through a nitrogen-filled, heated tube (device C), the 5-era central part of which has a temperature of 562 ° C The fiber gives a T / E / M ^ of 17.1 / 2.2 / 817, a high crystallinity and an orientation angle of 11 °.

Example 45

This example illustrates the wet spinning of an anisotropic HF mass based on poly- (p ~ bensaraid) "

Combine 28 g of poly (p-benaamid) C ^ _NH "2.9, obtained by the processes described herein, the general methods) trie in Example 40 with 110» 1 anhydrous HF to form an anisotropic perlmuttar- a term composition is Put this into the cell described in Example 40 and modified for wet spinning as in Example 43 and push it through <ο $ λ \ ο £ CO-L © ch ~ spinneret (hole diameter 0.063 mm each) into a water bath (6 ° C) atss . The threads are guided over a distance of 310 c "dus ° ch the bath and with 80 _S 8 m / min wound, j the pressure in the spin cell piston is 7 $ 03 kg / cm ^2. After washing over the weekend in running water and drying, these filaments have a T / E / Mj of 6.2 / 4.7 / 304, an average crystallinity and an "orientation" angle of 20 °. This Padongut is then immersed in water, and? .5 m / min ", drawn by a in its 5,8-cra Hittelteil aasfgeheimes to 580 ° C tube (device C) on the l, 06faehe whereupon üie fiber, a T / E ^ Mj of 14.2 / 2.4 / 802, a high

909887/1693

Krietallisiität and an orientation vortex of - ii ⁰ results in "

B β i © P i © 1

This example is based on the Na®i88pißn © E of an ⁸ anisotropic HF measure »® on Orian oil from poly-Cp-benssaraid) ·

28 g of Po3.y- (p-benBaiiiid) i ^ _nh · 3.7 * © Aalten according to hie? described, general methods) 'as in example HQ with 110 ml of water-freshness! "HP üantex ⁰ Formation of an anisotropic, pertraufcfc" artigosi iifcsee, which contains @ 30 QeM.% Poipi © r © s , gives this © Ldsung ■ in the amended in example ^ O B® "ehrieteen®.uwä wi @ in example ^ 3 for DA® wet spinning 'cell 8t5isst the composition as in example ^ S and winds the arüfallende Fassr 91, H' m / Hin, on »where the oruok on deia Spianeellenkolben @ about 9 ₃ 7 kg / © m asked Na <sh How« h © n overmowed in running water and Troeloicsn show the © Pädeini a T / E / M. / den of 7.2 / 3.2 / 350/1 ^ 5, @ 1κ® medium toisfeal- 'linität wnd eiten Orientiaruiragisifink®! of 27 threads would be at % 5 m / min. dwr <5h in heated tube C), the 5 "middle part of which had a temperature of 560 ° C a« f whites ₉ to 1.03 -fold v®3 »etr®ckt; whereupon the © Fa © ®3? a T / E / M ^ of 1 ^ 90/2, ^ / 6269 results in high crystallinity and an orientation angle. · νοη 17 °.

B e i β ρ 1 e 1 »7

Example explains the wet spinning of an anisotropic MF-Masa® based on Mlechpoly-C90 / 10 ^e ip-bensamid) / (p-phenylene terephthalaaild}).

Combine 30.0 g dee above beechpiebenen Miechpolyamidee (% · _Λ ^ "3m1 $ receive Naeh tsiex" beechrielbenenu aSlgeraeinein methods) with IiO 11I anhydrous HF ttsit © x ° Education anisotropic one, MOP

lasse, the 21 GewoS iee MiselipölyaüiSdee enfetaäl .this hat as in example k3 © us (Ktthlttng äea iae SSj ₁ OS flew.J "contains detergent, on 2 ^s ' Q) ₉ where üie FSdsn in« Itcü distance of "8 ea ws > m dsr SpiiroeCIse ara e £ »eia.

discharged and at 90 ° with the Faö © Rla «if»

direction leveled wsräen. Fi * »p f) ^ w« k on de? Sp-L.nsclle is 909887/1693. - 96 -

6.75 scg / cm ² and the filaments are wound at 8.08 to 9.6 m / min. After washing and drying, these threads give a TZEZM ₁ / den of 11.6 / 3.0 / 410 / 1.24, an average crystallinity and an orientation angle of 22 °. After stretching at 4.88 m / min. through a heated tube (device C), the 5 cm central part of which has a temperature of 544 ° C., 1.03 times the fiber gives a TZEZM ₁ of 12.2 / 2.0 / 600, a high crystallinity and an orientation angle of 12 °.

Example 48 "

This example explains the wet spinning of an isotropic HF mass based on poly (p-bensaraid).

10 g of Foly-Cp-ben ^ amide) (3? _1η1ϊ ^! 2.9, obtained by the general methods described here) are combined as in Example 40 with 90 ml of anhydrous HF to form a viscous, clear, isotropic © ^ which contains 10 G@w.3S polymer, puts this mass in the cell described in Example 40 and pushes it through a water bath CO to β ° C) as in Example 43 through a βΟ-hole platinum spinning nozzle © Cto ^ hdiameter each O ₉ O76 ram), whereupon the thread run is guided around rollers so that the path length in the bath is 210 cm ο D @ r pressure on the cell flask is 15.5 kg / cm ² , and the Pas @ r is 13Λ m / min «wound up. After winding for one hour in running water and drying, the fiber has a T / EZM ^ den of 2 _s 8Z28 / 83 / 2.4. After stretching a sample of the rinsed, wet thread material in ®r @ p®nn @ n © n form at 14.6 m / min *

®im b © h @ iate® Kohr (device C), whose 5.08 cm = mean area © in © has a temperature of 593 ° ϋ, to the l _si 37-fold © results in di © Fas © ?? eiss TZEZM ₁ of 8.8Ζ1.8Ζβ21ί © in © high crystallinity and

© r explains the production of poly ^e (p, p ^e * biphenyl and © in®r anisotropic oleum mass of the same,

One feeds a flajrnn-treated, pipe conveyor. - 97 -.

9-098 8-7 / 16 93

Q-iO3i - - If

mlgen 100 ml bottle (the one with a stirrer and with openings for purging with nitrogen and introducing substances.

is) with 25 ml Hexamethylphoephoramid, 25 ml H 2-MethylpytfPolidon nand 1.84 g Bemsidin, the mixture is stirred until aura presence of a ⁰ ■. Solution - then cools with solid carbon dioxide and quickly, while stirring, 2.03 g of terephthaloyle chloride as a solution in 10 ml of dry tetrahydrofuran. The mixture will hoehviaeos in a minute. The land cannot be stirred. * The mixture is now left to stand for 16 hours at room temperature and the polymer is then removed by stirring with water for a mixer while filtering and washing once with alcohol and once with] ithea ° _o The vakuuiiag @ tE »© @ taet @ polymer (2.9β g) has an." - inherent vis @ © ~ si tat of I ₉ H ^ c _ ....

Preparation of the Massei _s t $ g of the polymer in a saturated .werden Reag @ naTOÜir mechanically, with 7.0 ml of 100 _S 95 ^ strength "" © Schwefelsäur

So Masss®, -which becomes cloudy and smooth as the dissolution continues. The MasTC fiddles with stirring trophies and polarizes them, as a thin layer under a cover glass awf a microscope slide. b @ =

Example 50 "

The example explains the manufacturing process. wn P © ly ~ Ci _s 5 ~ naphthyl © r3 = t @ r®phthalamid) and an anisotropic Qlsuaimass® of the same _β

10 ₉ i5 g (O

s ° id at once sw a warm sleep-up (35 ° C) won T ₃ , 90 g Co ₃ Og mol) subliralated 1,! Hfephfchalindiarain in a 'mixture of

60 ml H © 3gasn @ thylph © sphöramid- and "30 ml H ~ Me £ hy!» 2- = pyrr © lid © n in ®ira © m 500 ml Har ^ herst © 2.1ungskee © Brille l hi? As ^, , d @ r with an air g © = * ts? i © n @ n HüfoFes ⁰ and a .CalsiiaiachlorM ^ drying tube ⁿ v7 © rssh © sa ± ®t ■ where in ^ 5 § @ lc “a © -steif © Substance _{accumulates s} the oiaa 'üfoernaehfc Raumteifliiperatur leave standing - and then supplied with water and stirred at high speeds on a 3s735-1 mixer "This is collected, with" stirring a "j" f-a smß, Ie © -

909887/16 93

funnel washed three times with water and dried overnight in a vacuum oven at about 0 ° C. polymer yield 13.60 g (94.5 % of theory); inherent viscosity, determined on a solution of 125 ng of polymer! in 25 »0 nl of 95 to 98% by weight sulfuric acid, 2.22.

Preparation of the anisotropic mass: A mixture of 2.5 g of the above polymer and 22.5 g of fuming sulfuric acid (1.3 % free SO-) is added to an anhydrous ice-water base in a 200 ml vacuum bottle while cooling mixed with a mechanically driven paddle-type stirrer. The mixture becomes 4 Sfcd. The cooling bath is allowed to warm to room temperature during this period. The resulting, fluid mass shows Rühropaleszenz and depolarized linearly polarized light.

Example 51

This example explains 1. the production of a random Mixed polyamides », the equimolar amounts of randomly recurring units do the group

-hh <'> NH-, I ^ T η, ~ nh / Vconh / \ nh-, -C ₀ J > co-,

CO- and JI j, 2. an anisotropic wetness of the Kiscbpolyanidea and 3 * fibers from the Niachpolyaeid.

Polyaer production: In the drying chamber a solution of 1.08 g (0.01 mol) p-phenylenedianir., 1.56 g (0.01 mol) 1,5-naphthalenediamine and 2.27 g ( 0.01 mol) of p.p'-diaminobenssnilide in a mixture of 60 ml of eexamothylphosphoramide and 50 ml of M-Kethylpyrrolidon-2, which is quickly stirred with a mixture of 2.03 g (0.01 mol) of terephthaloyZchJic ^ id, 2, 9 (g 0.01 HQV iJ ^ '-?.. Dibensoyldichlorid and 2.53 (g 0.02, McI) "N £ phtcyIöi5hlorid versofcEt 2.6 The resulting clear" very viscose Löoung wis? ö Stirred for 15 minutes * and then left to stick for 16 hours. The PslyT.e? e is made up in water ftoi; one waters on one ice Miechar Yiertnal with water, once

- 99 -

9G3887 / 163 3

JOO 1810428

Q ~ 1031

add acetone and once with alcohol and dry in a vacuum oven at 100 °. Yield 9.5 g (9 ¹ ? *>; ^ _Inh 2 * 93 ·

Herateiltang of the mass: To form a spism mass from the above polymer, H g of the polymer and 36 g of 99.2 ig © HgSO ₁ J are combined at room temperature, whereby a very viscous mass is obtained, which under a polarizing microscope shows a strong Sshex ⁰ * -Double refraction with a relaxation time of 60 seconds.

Spinning and properties in the spun state: Wet spinning takes place from a »motor-driven injection syringe which is provided with a spinneret. Due to the high viscosity of the wet, a specially designed, atark-surface® spinneret with 20 holes, each 0.076 tm in diameter, is used. The fibers are coagulated in a water at room temperature, which is located in a metal tub, with the length of thawing being 83.8 au. wound up while di.t Spul «revolves with the Flash © below in a water tub. The fiber then becomes 6 Sfcd. soaked in water and dried. Sig®nsoh * ften the thread material is spun condition: T / E / M ^ / den 3,2 / 9.7 / 132/97. The thread is amorphous and has an orientation angle of approximately 50 °.

dor fiber and properties: BIe wet fiber will under ventilation »it 3.81 ra / min. heated to 380 ° C by a. ® » Tube {Vsrriohiung A) extended 1,! Times. That pushed forward The thread has a T / F / M ^ / den of 6.9 / 2.1 / 413/74, with traces of crystal and has an orientation angle of 24 °.

B e i s ρ 1 ο 1 52

This example explains 1. the production © inftß irregular Misohpplyaisides, dao equimclare Kengen an Regelloeen, return * the units from the group

. Jf 1 J a «f ;. _{" Eist Ä} 2. οίκβ & nis &*; rcpe mass of the Mlsohpoly-

903887/16 S3

.; ,,, '. ν, -, / ϊ; v? BATH ORIGINAL

Q-1031 ^

amides and 3 · pasers made of misoehpolyamide,

Polymer production: In a drying chamber, a solution of 1 ^ 62 g (0.015 mol) of p-phenylenediaiain and 3.35 g (0.015 mol) of ^, ^ '- diainino & ensanilide in a mixture of 60 ml of hexaraefchylphospborainide and 30 ml of K -Mot hy! Pyrrolidon produced _a 'Me man rassh under very ras sham RÜSiyen with a mixture of 3, Oi-JS g £ 0.0S5 mol) of terephthaloly chloride and 3.795 g (0.015 mol) of 2,6-naphthaleyl chloride and 3.795 S (0 , 0515 mol) 2 »6-Naphtoyldichl9r> id varsefcssfc, whereby in 2 min. A clear gel is present that does not

lets »After standing for two hours, the polymer is processed in WaH; fish a & f the mixer four times with water and once each with acetone and alcohol and fczOesknfci: .im Vakuwmofsn at 100 ^c . Auebauta 9.5 g C99 *> i ^ _lnll = 2.77.

Der Massu: A measure is made from the above polymo ^ en by combining b © iiaumfceHiiperotfcur £ g poly; aei »es and 18 g 99» ₂ % H 2 SOjJ. According to G Std. Ssfeieühenz-sifcliehen there is © in® Tioeoae, an-isofcrope Kaoso, which has a strong

Spinning and owning ixi spun on State: The nose "spins" n

from Ain # ic »motor-driven injection liquor, which with 3plnmit * s8 with 20 holes of 0.076 wa Durciiraeeaor each

is * D3e * -P £ dsn are in Weaser in front of Raumfcsmperafcur koagu lt <as? fe »which is in« inex- Metalluanne-, where-the Eintaueh 61 «Ε böt' * ΏΙ & Vädon are at least 21.7 m / Min, aufetrikwäjj ^ arid the coil with the untofsn plan in öinsr Waseei * - runs .. Dia Pasaz * will danT ». % S hours soaked in water ¹ and gc-t2 "t *" 2kriet. The Fadcssjgu !; results in the "yapcnnene state ain'T / E / M,

r ¹ S, isfc ^ vno ^ pti «nd η & ϋ a orientation

! · Of about 60 °

j? νηά ice-snacbsfton; Οί · .ί in the

^ ird kute? _t - ^j 2ufithj "iir" g mis 3.81 m / tnin

üumh s.lri to ^f s75 ° C bcfindlichaa, heised »Rohr {Vus * rl <sh ^ ting Al ' t.% \ t ύ & η I ^ ifao ^ e vöX'Ct ^ ri'Tik}; .. ~ DU" 3 Stretched faiion goods result in taJLn

- 102 "

«- υ -J Ij" .j 'ι j (j;! 3

T / E / M ^ den of 6.8 / 0.9 / 698 / 72.7, an average crystallinity and an orientation angle1 of 12 °.

If β ρ i e 1 «> 3

Dlesee example explains 1. the production of a random mixing (polyamid-oxadiazola), the repeating units from the group fVilH-, -CO- ^ Vco- and -NH- / ~ Vc ^

-NH-fVilH-, -CO- ^ Vco- and -NH- / Vc ^ ^ 0- / VnH- (rela-

vas ratio 3 5 ^V ^ ί 1) has, 2. an'anisotropic oleuramasae of the Hiech-ipolyemid-oxadiajüöle) and 3 ° Pasern from deia mixed (poly-

In a drying chamber a solution of 3.2 * 1 g (0.03 mol) of p-phenylenediamine and 2.52 g (0.01 col) of a ^ -Bls-Cp-aminophenyU-i ^ 'l -oxadiaaol in a mixture χοή 90 ml HexametfaylphosphoraBiid and % 5 ml N-Methylpyrroii- 'don prepared, which wan with rapid stirring all at once aiifc 8.12 g (0.0ή mol) terephthaloylochloride added, whereby a © very viscous, clear solution arifall that in two minutes a state it · -

- ν

arrived in de "she ötÖPiängalo" can no longer be stirred, followed by a 16 hour ie. are! fösßt. The polymer is poured up on the mixer four times with water each time

times "ait acetone and alcohol and dries in a vacuum" i 100 ° ΰ.

Creation of the mass; To produce a masa from the above polymer, combine 6 g of polymer, 1 g 100% H ₂ SO ₁₁ and 10 g of fuming sulfuric acid (20 % free SO,) Süett; they stand S weeks etörungaloe. Although the measurement seems a bruchffihig © «© OsI _{dai'BuaSellen%} makes them verifiable jLango & ra into the Spinnst3.1c aOn giassan, under the polarizing microscope the composition shows a very © hall Schercloppelbffochung.bei a Relaxationßgsifc-" m IO

Spinning and properties: en in the spun Zuisfeand: Harr transfers the mass obtained in ά & τ above Moise © r to the spinning cell and

«- ■ YES ')».

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spin for an hour. Wet spinning is carried out with a motor-driven injection syringe, which is provided with a large-area spinneret with 20 holes, each 0.076 mm in diameter. The threads are coagulated in water at room temperature, which is located in a metal warmer, the immersion distance being 83.8 cm. The threads are at 8.1 m / min. wound, while d ^J circulates s coil in a water bath. The fiber is soaked in 16 pieces * of distilled water and dried. *. _ .mhtxf ^ t ösa Fadengutee in the opened state: TZEZH ₁ ZdCn 2,4 / 14,4 / 94,5 / 103. The thread material shows traces of crystallinity and has an orientation angle of 50 °.

Wäsrraabehandlung and characteristics: The product obtained in the above Weioe wet "Fadengut is under feeder with 3» 81 m / min, through a 475 ° 0 befindliches, hot tube (device A) to the, fvfaehe "/ stretches The drawn!. The thread material has a T / E / Mj / den of 3.8 / 0.9 / 500/57, an average crystallinity and an orientation angle iron 15 °.

Example 5fr

The CSO example explains the manufacture of a high module tufted threads made of poly (2-chloro-p-phenylene terephthalaiaid) from a cptiech anisotropic mass which contains about 20 wt. * of the polyamide.

49.7 g (0.245 mol) of terephthaloyl chloride are stirred into a solution of 35 g (0.2 * 15 mol) of 2-chloro-p-pnenylenediamine in 425 ml of hexamethylphosphoramide, which is cooled in an ice-water bath, a precipitate in the form of a wet paste arises almost immediately. The reaction mixture is allowed to stand overnight, whereupon the polymer is collected and agitated on a mixer with water. Dao polymer is several days in a vacuum oven at 78 ° C dried fllfii-fall at 60 g poly (2-chloro-hen pp ylenterephthalarnid) anj ⁰

* Formation Merem a mass with a content of 17.2 wt. PcIy to and combined 2.7 wt.% Of Sale man% grams of poly (2-chloro-

- 103 -

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p-phenylene terephthalamide) (obtained wi © ob®n) with 25 ml of a solution obtained by mixing 100 ml of N, N-dimethyl acetamide and 3 ig lithium chloride, the mass is allowed to stand at room temperature for a week or longer, whereby it is divided into an isotropic upper layer and an anisotropic lower layer (T of the lower layer>? O, determined by the method described here; volume ratio of the upper and lower layer about 2.6 % 1), isolated the layers and the anisotropic, lower layer at room temperature through a S-hole spinneret (hole diameter 0.08 mm each) in a water bath kept at 21 ° C. The threads are with 17.1 mZMin. "wound wax soaking in water and drying gave a DI® threads TZEZM ₁ 3.5 / 1.8 / 23- ¹ I and an orientation angle of 39" 2 · When passing it over a bar of 125 ° C © rlangt the fiber a TZEZM ₁ of 2.1 / 0.7 / 318 and an orientation angle of 28.

The physical properties and common values of the The following table lists the above layers, the determinations being made at 25 to 26 ° C., unless otherwise stated.

Table V

Density, gZml refractive index, njj polymer content, g / ml ^ inn
LiCl content, g / ml

Upper layer Lower class 0.97 1.01 MT25 1, «676 0.112 0.179 0.13 ι, · »* 0.0260 0.0238

Example j? 5

This example explains the production of an optically anisotropic spinning dope with a content of about 10 Qew.J of poly (2-chloro-p-phenylene terephthalamide) and the production of a one high modulus fiber from the same.

To form a cash register with a polymer content of 9.5 Qew.Jf and SalegeheIt of i _s 5 wt. * Combine 5 g of poly (2-chlorophenylene terephthalamide) (obtained as in Example 51) with 50 ml

909887/1693

a solution obtained by mixing 100 ml of N, N-dimethyl acetamide and 1.6 g of LifeJhdumehXoJPid, leaves Hasse at room temperature for a week. standing, where they are divided into two fluid layers of the phases of approximately equal volume, the obey is isotropic and the lower is anisotropic {i.e. T of the lower layer, obtained by the method described here,> 70), isolates the layers and pushes the anisotropic lower layer at room temperature through a hole spinneret (hole diameter 0.127 cm) into an aisf 251 ° 0 held water bath. The resulting fiber is smof-wound with 22 raZMisio. After soaking the fibers in Wasosr and drying, betp & gt T / E / M, 4.5 / 4 _f 8/198 and the orientation angle ©! ^ 3 _S 9 °. If this © Paser over a rod of 4'25 C results in a 3.1 / 1.3 / 27 ^ and an opening angle ^ of 28 °.

The physical properties uirsd ZusananenseläsuifigaKe ^ te dsx * obi gsiii Sshl @ hit © n is what di® calls the following table, whereby, wams is no different E !, di © Feiaunungen have been carried out at 25 to 26 ° C

Table VI

, g / ral Upper layer outer layer sigsii5d © 3S3 mZr not determined 0.99 rg®halfc _s g / ml M584 1.4544 P © lym © @s polymers 0.080. 0.098 ⁿ inh ^d © halt, g / ml ■ 0.74 1.61 Jw.!. v JL "Si 0.0120 0.0146

1'ϊϊι ühnlish © ^ manner as described above, a further textile material, ie Raife 5 g of the polymer in 50 of the amide salt mixture mL, prepared mm% as a weekend © allowed to stand and then, shaking the S © jhii © hfc © n to unite into a cloudy, not optically clear mass CT, determined by the method described here,, ^ 50).

Mass® is immediately at room temperature by a 2-Loeh-Spimi- ^ Loeh by Biesaep 0.012? cm) in a water bath at 23 ° C. The threads are anafgawjlskelt at 9.8 to 3L3.5 m / min. After soaking in water and drying, the threads give a TZEZMj ₁ wn '? , 1 / 2.7 / 223 and an orientation angle of 38 c. «Γ *. - 105 -

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Q-iO3i

Example 56

This Böiapi®! Explains the production of a double-braced Spiramaoee won Poly-Cp-pfcenyleniäerephthalarid), which has a mixture of anisotropic and isotropic «** phase.

Urafe @ r WaeeerbadkUhlung is a solution of 31.08 g (0.287 mol) p-phenylenediamine in a mixture of 3βΟ ml hexamethylphosphoraraid and 180 ml N-methylpynrolldon-2 inifc 3.36 g p-aminobenzoic acid w®w® <eb% t , whereupon 60.90 g (0.300 mol) of Terephfchaloylehlcrid 2üsetsfc, the reaction mixture is stirred over a de-x · cooled solution and then on a mixer from * precipitation of the polymer with

united. The product wiyd mi «; Water flowed. dried in a vacuum at 65 ° C, then dilute with acetone in a mixer, the mixture filtered and the product collected and dried in a vacuum at 65 ° C. In this case, dae poly-Cp phenylenterephfchalamid), _'n ^^ J _1' i, 32 'obtained in quantitative yield ₉ "

To form a mass with a polymep content of? _{9 9} % by weight and Sffilajg® content of 1.24 % by weight are combined 18 g of poly (p-phenyl © 8iter © - ph% h & 2 ml of N-MethylpypF®! id © n-2 and 2.8 g of lithium chloride j mieohfe di © Bsstanäteil © with eirasra S @ h®F vision stirrer and cools in a bath. After the components are left to stand while cooling, there is a smooth, free-flowing one _s homogeneous paste, which is obtained by heating to 60 C a fluid wetness (with St @ - hml% .E- & ür.: without heating leioht tiOb), which shows palescence when stirring.

This mass se igt when you tw Fluldisierung to about 35 ° C?

heated when viewing with a polarizing microscope Doppelbreehuhg, d. H. is there a bright field in the microscope? .a observe,

si? A guide is made from this mass, to which an S-shaped tube is connected, which in its lower end contains a 20-Lechepiiindüsö (each O, oa em). After pouring the warm measure (60 ° 0) into the solution source, the cell was heated , and the S-tube with a <st> Haizpietole,

* S06 909887/1693

.J

Q-1031 ¹ ^ '

until "! the measure from the spinning orifices auasufliesoen begins. The apparatus is then arranged in such a way that the spinneret is dispensed horizontally into a water bath kept at 60 ° C, with the S-tube part dipping into the bath in order to keep the mass warm before it is ejected. The mass is ejected at a pressure of 0.14 kg / cm, and the resulting threads are wound onto bobbins at 22 m / min . ■ th. The bobbins are washed in cold water for several hours at room temperature before drying in air. The thread of one of the bobbins results in a T / E / M ^ / den of 3 * 7 / 4.0 / 191 / 3.7 and an orientation angle of 37 °.

If the above procedure is repeated with the modification that the SpinndOeenlttoher have a Durohmesser of 0.08 mn each, use PoXy-ip-phenylene terephthalamide threads with a T / E / M ^ / den of 3 »2 / 3.2 / 219 / 2.5 * 1 and an orientation angle of °

37.3 ° at.

, £, JL-JiI

P Β · 5 spiel err.fiy.tes'fc the wet spinning of an optically anisotropic mass s ^ r formation of poly * ip-pheiiylenterephthaXamid) threads, those. Properties can be significantly increased by a subsequent heat treatment.

Combine £ 8 g of poly (p-phenylene terephthalamide C2j_ _nn ^a 1 * 32 obtained according to Beicpiel 56}, 134 ml hexamethylene! Phosphoramide, N-66 al MeihyIpyr? OIidon-2, and 2.8 g of lithium chloride and stirred for 2 to 3 hours at -10 ^c α cu? Formation of a thick, moving pasta that eich 'sr.geiLTi a-.ϊΓ Raumtorap ^ ratus · warmer, is left. By Stirring the material continuously for three days will result in a fluid paste that shows Opalossene when stirred. Dia Masec is double s * echend 'T s ^ 6, determined in the one described here Orphan}.

Dio Msaee containing 7 ^ 95 Oew.S polymer and 1.24 Qew.9 Sal ", in O ₁ IIJ kg / crc dU2» <sh a 2C-LoGH-Spinndüee (Lochdurchaes-C, Ö8 mm> in a kept at 26 ° C; water bath

909887/1693 " ^lc: "'

ORIQI _NAL

poured. The threads that arise are widened b © i ti m / min * on bobbins, which are washed for 3 hours in cold water before drying in air at room temperature / M ^ / den of 1.93 / 2.3ZiW ^ tS, 7 and an orien tieruRgiwinkel iron * I2.5 ^O. A sample of de® F & dengwtes, ie © at 6.1 m / min, through a nitrogen-filled pipe, heated in the middle to 560 ° C, 0.3 m long: is', results in a T / E / Mjr / den of 3.9 ^ί 8 / & / ^ί »1 ^ί Ι / 38, ^ί Ι wnd a quality angle of

B e i a ρ i el 58

This example explains the Xn-8itu production of an anisotropic measure of poly- (p-to®nsaraid5 in Ν, Μ ₈ Μ ^β _s I ⁹ -TetFan »thylhsmetoff.

100 g of p-aminobeniioylchloride-lydoporide en 2 1, Ν, ¹ , N * ~ Tvstranjsthy! Urea with a content of 2 g of p-arainobensBoic acid, which is kept at 5 ° C, are added di © reaction mixture tint β 5? Cooling auesen about 15 minutes ", and then about 3 i / * 9 SW ₀ b © i autogenous temperature, mixed nwi wit 90 g of lithium hydroxide," phifeist 3 min DI® ReaktionsmisQhung. At 125 ° C and then belling 2 SFCD. at autogenous temperature, where a · Maeee with .einem PolymergahftXt clay 2.0.8 % accrues (awe "the Maeee insulated® polymer sample results in an inherent yieeosity w & n Ι _φ 40). This mass ₈ the nwnmata about 6 % lithium deficiency contains, & has a Liohtdwrch -Wissigkeitswert (T) _s in the white bostiantj described here, of 57.

Alas ®in @ r in Ihnliohep Meise "Jedoah under .Bimset" isolated from only O _e 35 g_ p-AmlrüobenEoesäure composition obtained poly (p »benBaasid) siiigi · an inherent Viseosität of 1.65 * This composition gives an I> t * z * «sfclä @ 8igk <&ittiW8H; (T) _{f is determined} in the manner described here,

Di®B®8 Bsiapiel explains the in-sitw »Heret®llumg one not new, anisotropic« !! Spirasnass® based on poly-Cp--

- 108 -

909887/1693

(benzamide), whereby in the finished mass per mole as a monomer

5hloridhydlr © ehlorid 2 moles of hydrogen chloride

Z ^{1 of, Ν,'N 9} -tetramethyl urea cooled to zero temperature and treated with 0.92 g of p-aiaobenzoic acid are treated with 256 g of p-aminobanzoyl chloride hydrochloride. The reaction mixture is stirred out? Image of a vls © © S ("n Maas © approx. 55 min. At bath temperature," sinterbrisht dgts drive Mnd leaves the mass, which contains about 11 W © w.

stand before 'the pushing into threads takes place. Eiics sweet d®j? Ma®s® isolated Prob © Poly- (p-b © nÄamidJ shows an inherent Vi »eoeitä £ from 1, p. The mass shows in the white described here te # @ feia ^ t, a permeability value (T) of 55

-g_5..i_gLJ-

"ßiess® B © lspi © JL Erlänatar-i the production of an anisotropic mass, dl @ δίκ sf ^ oilless copolymer of 95/5 poly (p-benzanide / ra-beaz- ®mi (ä) iirs sifsar mixture of NjN-Diutethylacetamid / Lithiumchlcrid ■ C95 / 5> included.

50 ml, Ν, Ν ·, »« - tetramethylurea cooled in an ice bath are mixed with a mixture of 28.5 g of p-aminobensoylochloride hydrochloride and 1.5 g of m-aminobenzoyl- © hio ^ i ^ hydroehlorid offset. The reaction mixture is cooled on ice . stirs 1 hour, then stirs 1 1/2 3td. at room temperature, wc- Vt, anfSllt X ®im stirrable mass, which provides n clear gel after 20 hr. at & Rauntempera- ®, united as "gel sur on a rather MIf

of the mixed polymer with water, the product is isolated, washed and dried, with 15.5 g of Pely-95/5 ~ (p-ben * amide / m-bensam3ld5, 1.12.

_A sufficient amount of olyesnides obtained in the above manner is added to a mixture of N, N-dirae thyacetamide and lithium chloride in a weight ratio of 95 ί 5 to form a mass with a polymer content of about 10 $. Mar-t the ingredients for 10 to 15 minutes while heating to 100 ° C,

- 109 909887/16133

Q-103! MO

and then stirred at Raumtsrnparatur is present until a v®n undissolved Polyraerem free mass. The mass shows a permeability value CTJ), determined: in the orphan at room temperature described here, of 11.

At « P ₁₁ JL ₁ , e 1 61

This example illustrates the Xn situ production of anisotropic Poly (p-bensanide) spinning maize using lithium » earboraat to neutralize the mass.

200 g is treated with p-Aminobensoylchloridhjrdroehlorid i3i0 g N, Ν, Ν, "N ⁹ -Tetramethy! Urea of about 7 ^Ö C ₉ stirs this Heakfeionenieehung about IS min. At RaumieBpwatttPj said Reaktionsraieehung after a total of about 80 min. With stirring ( ) a temperature of *! 0 ^o C ©, stir for a further "28 min" at % p ^& C and then stir quickly, during which time the clarity leaves the lithium carbonate to aw®i proportions (50 » 28 g) sug @ -. is given, and the dia lieetiupg is kept at §5 ° C "iierawf you give 2 g of p-Äfflinotossnacseäure in 30 ml N _> M, H ' ₉ K' ^c * Tttramethyl1iarn '"

^ 0 g further Ν, Ν, Ν *, M'-Tetrametfoylliaraitoff dl® Risaktionsmisehung by means of an oil bath from C awff about 80 to 9 ° amd removed by the action of vacuum i @ © rh & tst © Hisohüstg © fewa S25 g Plßsaigkeit «Man set @t ηψι woitere 72 g NtN ^ N'-N ^ Tetramethylharaatoff hinBu «get the

^ Tag® at 1.20 ° 0 and aolileud @ rt, to nieht umeu ®ntf @ rnen. Eh 'narrowing the fraction ""! - "* mass with a Qeh & lt of about 9» 5 Qew.l on the Poly-Cp-bensamld) and with an inherent vision of l »7' ^ ge ™, the iron deficiency value {T } »In. The bumbling white here determined by room temperature, results from 21«

B e ia ρ 1 ei 62

The beiffipi ©! the ^ t d ©? further explanation of M @ thodem manufacturing steps: 1. for the Bildung'der Mes "" n © gemfis air geeignetons poly - ((p ~ b © nsstiai <ii) md 2,

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BADORIQINAL

AJ Zssj? Immediate formation of a solution is added *! 50 g of p-amine-cyichloride hydrochloride all at once to 2200 ml pre-cooled on ice, dry Ν, Ν, Ν ', N ^e -tetramethyl urea are added, this solution is stirred for 2 hours at ice bath temperature, then removed cool the liquid and stir the solution for a further 2 hours, during which time it becomes warm and slowly forms a solid gel, which is left to breath overnight and then poured on a mixer with tap water and once al ': turi6: u. alcohol (2B -AIkOhOl) washes (the gel is divided into 3 parts for this wash treatment). The isolated polyamide is dried in a vacuum oven at 80 ° under nitrogen; ^ _n J ₁ »1.83. The sample is crushed by 3-day ball milling.

this synthesis is repeated with the modification that one since the gel only leaves 2 hours after it has formed, it doughs isolated polyamide has an inherent viscosity of 1.74 «A similar synthesis provides a polymer with an inherent viscosity Viscosity of 1.53 and a peak height ratio of 0.75 «

B) A mixture of 250 ml of N, N-diraethy! Acetamide and 15 g of lithium chloride is obtained with 30 g of poly-Cp-bens & mid) (^ _11n ■ * »5> according to Tell (A), with about half of the polymer through Ball garbage is crushed). The mix contains 10.8 Qew.J of the polyamide and 5.1 wt. ^ Of the somersault. You get one immediate swelling. The swollen mass is sur forming a Pick suitable for spinning heated to 100 ° C.

C) A mixture of 200 al N, M-Dlaethyl} sobutyraMld and 13 g Ll-

thiuBchlorid is nlt 20 g poly- (p-bontaaid) at room temperature

Pi ₄ _ _K * i »39, obtained according to the general method of xnn ·

Tell (A) / versetst. The combined components, the 9, *? Gew.S of the polyamide and 6.1 wt included.% Of Salies, at autogenous temperature is observed eu until clear Vlscositätsanstieg, then freezes in a Trockeneie-Acaton bath and leaves the material during sehllessllch Stehon overnight check warm to room temperature, whereupon the ingredients are heated to iSC ° C and kept at this temperature for about 2 hours, 'JM ! tir? ö. sshs? visEuoee viewer feedback isu get the like 909887/16 93 "^"

Q-1031 tf%

Frozen auvor and let reheat and over the weekend is left to stand »To form a thick, viscous mass, the ingredients are then mixed in Stir heated in a bath kept at 100 ° C.

D) To form a spinning mass, 15 ε poly- (p-benssamid) ^^ inh ⁼ ^ - »^ °», ss-reduced by ball milling, obtained from a mixture according to the general procedure of part A)

of l ^f f8 ml N-Methyleaprolactam and 7 S lithium chloride from room temperature is added, stirred this 8.8 wt. # of the polyamide and ^f l, l GeWoiS subjecting the Salsses combination containing at room temperature until the occurrence of swelling and the gequol- ^ lene The mass to form the mass requires cooling on a mixture of solid carbon dioxide and acetone and then heating to 110 ° C.

E) Dissolve 10 g Lifehiumehlorid at 55 ° C in 200 ml dry N-methylpyrrolidone-2, and displaced untsr vigorous stirring at 100 ° C with 20 g of poly (p-benzamide) CJJ _nh ^s 1.6; obtained according to the general procedure of CA) ₀ The mixture contains 8.9 GevioX of the polyamide and H ₇ H Gevr.% of the salt. Around I SSd. a viscous composition is present, which is taken over to form a free-flowing mass and stirred at 100 ° C.

To form a clear solution, ¹ 10 g of p-aminobenzoyle chloride hydrochloride are added to 200 ml of N, N'-dimethyl thylenharnet ψ at ice temperature, the cooling bath is removed after 20 minutes, whereupon a thick mass forms, after one hour 10 g of lithium hydroxide are added and the mixture heated at '110 ⁰ C, in order again to form a clear, slightly stirrable mass. A sample of the polymer, which is precipitated by adding water, has an inherent viscosity of 1.36. This composition contains about 9.7 wt.% Polyamide and _dea-S about 6 9% Lithiumcthlavido

Ex iel 6'j

Table VII lists the working methods described earlier on various anisotropic poly (p-bensamide) compositions according to 90 9 887/16 93 - 112 -

, · -. ■■ - BADORIQIiSJAi J!

Invention determined values, whereby the column "source" either the special part ^ r of example 62, in which the preparation of the mass is described, or a part of example 62 is meant. whose general working price is used for the production of the mass o The symbol "T" denotes the expression

2 <lj / I ^s3 - i; ^f / i ^c ■) 3 c 100 received value « , 28 • (p ~ benzamide) YlI in the
Mas a β T T a b s 1 1 e ₃ 2β 8.2 Crowds il2 Anisotropy-the ₅ B S ₃ ? Amide
or
Hara
Material . 68 search source
by
. game 62 poir , 18 9, ^ a 6, l SH 1 F. 1 , 18 7, ^ b «1.6 H, 2 2 D. 1 _s i0 8.2 a 29 3 Ί , 10 8.0 d 6 , 0 21 ■ _B 'i 1 _s i8 8.0 d Ü, 0 Ü7- ! j B ** I. , 18 i2 _s ? © 5 _β 1 68 δ E. ■ 1 , 18 16.7 e 3.0 68 ? E. 1 13.8 d 4.3 78 8th E. 1 d 9 B ** 1 d 10 B ^ 1

Q s M ₅ N "DisK © tbyiisobtifeyr" araid
ds M, N-Disn®t.bs? laaefcamid

This example arläu & eyt a Phaend-iagpaima for sine N ₅

i bsi RauaiCsmp ^ ira & iir ¹ solved; » - «■ i ji 1Ie irrigation takes place with room - ■ |

Mach OCE ailgemainen Arbisiftsweiae of Example 62 (A) is isolier tes poly-Cp ^ bensamid) mit.einer inherent Viaeosität of l l8 ₉ 9 0 9 8 8 7/1693 - 113 -

Q ~ iO3!

The masses are prepared according to the general procedures discussed above ₃ by processing the polyamide, N, N-pymethylaeetamide (with a content of about 0.2 to 2 % of water) and calcium chloride in various concentrations at room temperature rapid stirring (3000 to 1000 rpm) with a toothed spiral blade of S _S H mm diameter in a 2-ml tube of 9.5 mm diameter combined without heating from ausoen, with small proportions of particles ₉ welehe withstand the solution. If necessary, be crushed by hand »To examine samples of the mass at different concentrations, the sample is pressed onto a microscope object holder and the cover on a thin lens then regarded glasses between crossed Palarisatoren with or without U'ergrösserung whether dia compositions contain a single _s isotropic phase, a single _y anisotrop® phase © of an emulsion of these phases = In this white is mseh d The presence of a similar, particulate, fast polyamide in the mass sample was determined.

The results of a solehan evaluation are shown in the phase diagram in Fig. 1, which shows 5 areas. JDar area 1 is completely isotropic ₃ - whereby the "polymer is completely dissolved in it ο Dai ⁵ area 2 i'sh partially anisotropic; microscopic areas depolarize linearly polarized light» Area 3 is completely anisotropic = area * i is also at all Completely isotropic, but contains particle-conveying poly amide-containing substance, the idnifä a see the areas 3 and ^ gives the half again each time. Above this point the mass is increasingly supersaturated _s with solid polyamide present in it area 5 is i / öllBtänöig iso'öpop _s contains fjeuo ^ h particulate polyamide solid,

The Fhaa diagram is tosstiramt based on the appearance of the Ν & Β & ζρϊ-ί ben as follows:

The ten to be isotropic beseiehn © masses (Bereieh I) are clear ur / 1 transparent and appear when viewing swischen gskraiiaters P © lai "ieator @ a (above besehrieben} with or without tion as structureless Dunkslfelä"

909887/1693

The masses listed as partially anisotropic (area 2) represent emulsions of isotropic and anisotropic phases. With lower polyamide concentrations, the continuous phase is isotropic; at higher polyamide concentrations, the continuous phase forms the anisotropic one. These masses appear cloudy, often show opaque essence when stirred, and cause them to settle by centrifugation (or in some cases by gravity). If the continuous phase is isotropic, the large, birefringent parts of this mass appear when viewed under magnification (e.g. 40Ox) between crossed polarizers (as described above) as a multitude of bright areas of varying size and shape in front of a dark field. If the continuous phase is anisotropic, the isotropic "parts of these masses appear when viewed under magnification (2 B. ¹ 100x) between crossed polarizers (as described above) as a multitude of small, dark areas in front of a light background.

The ala completely anisotropic named hates (area 3) appear when looking between crossed polarizers (as described above) under magnification {ss. B. '! 0Ox) as He3! Field with varying direction of the birefringence ο often fadsn « like lines, characteristic of nematic mesophas ^ in Appearance. The field is displayed with a small oäor without magnification ex ^ nf, depolarized. When standing undisturbed for a long time, the mass present in Hasse often becomes transparent, only to be seen in Plieaeen become translucent.

The measurements in areas Ί and 5 are similar to the masses in areas 3 or i, but also contained in sioh part-forma, solid polyamide. Without enlargement, the case may arise that there is these masses do not differ from the Emuloioneu in area 2 at » are. However, this occurs with a high magnification (e.g. 7SCx) Partial, non-fluid material in these dimensions in angles " form in appearance. Its non-fluid nature can be recognized from this. that die-sos material when pressure is applied to the cover slip not flieast.

The masses dex 'areas 2 and 3 are particularly preferred.

- if.5 909887/169 3

Ml

ι © Di properties won from these anisotropic materials ersseugten threads in the ERSP © can © n condition are described "as the following example, those of otherwise appropriate from _a jsdoch isotropic © less anisotropic materials obtained generally superior.

Example 65

This example compares the properties of one out of 'one highly anisotropic mass produced fiber in the spun state with those of one made from a weakly anisotropic hatred Fiber =

According to the general ₃ methods described above, a FoIy-Cp- ^ benzamide) mass in N, N-DimethylaeetBmid from p-aminobenzoyl chloride "hydrochloride using ¥ Ois Lithium ai? B © nat produced and the resulting mass (*?.. Ε 2 , 36) on an ultracentrifuge of the type "Beckman ¹ L *" using a Botor Ti 50 21 ₃ 5 hours "at 50 000 rev / Hin. The two layers of liquid are separated and separately by an OjOl-em single-hole spinning nozzle Ejected precipitation water bath, which is kept at 60 to 75 ° C. After drying, the threads obtained show the following tensile strength properties:

Fiber from the top, weak T / E / M. / den 1.2 / 90/6 * 1 / 22.5 anisotropic layer

Facer from the lower, hoeh-, T / E / M- / den 7,2 / 8,1 / 283 / ^ 8 anisotropic vision

Example 66

This example (with Table VIII) explains 1 “the effect of the special amide or urea indium and 2. in comparison, the effectiveness of lithium and calcium chloride in the production of anisotropic poly (p-banKamide) -Ma3S © n according to the invention, each of which has the maximum polymer content determined as possible for the specific, evaluated system. The Tabsllö further aeigt the relative Lösuagsvermögen of Caleiumehlorid-Systeinen against Lithiumehlorid-Systemeno Daa lithium chloride £ st _f as the table shows., Generally more »

- 316 309887/1693

BADORfQlNAL ι

18104? 6

Q-1031

Following the general procedure of Example 62, isolated F © Xy- (p ~ benzamide) with an inherent viscosity of about O ₅ ? hs geotellt. The masses warden with each of the amide © urea media with a content of about H to 9 wt _o £ of lithium or OAI • eiismehlorid prepared Polyamidsusafcz to sur achieve the Polyamidritasdmalgehaltes "That sais is in the amount sugesetst which the polyamide content of the respective amide or urea diura optimized. Table VIII lists these values.

Ta be _1 _1_ e__ VIII

Part 1

Amid or urine medlum Maximum Poly- Lithlurachloriä-

Amides

M _S N-Diraefchylps? © pienainid N, N-Dimethylbutyranid N, N-DiBiethylleobutyrainld

jN-Biäthy! acetamid

merconsentra-
tion »wt. % GeWci 20th 5.3 28 30th S _S 5 21 9.2 Ii 5 Λ 22nd 3 jO lh

N-methylpiperldone-2 Ii 5/5

W "M (Sfetsyl @ .apr © laetam 3LS 5 *%

N-Xfcbylpyrrolidone-2 25 5.3

IT 5.Ö

N-acetylpiperidine 1% 3,

N, N ^r -Dimethylfitbyiennarn8t; off 19 5 _s 0

H «N'-dimethy! Propylene urea IS 5

909887/16 93

Q-1031 M% ■

T a bj _L U e VIII

part

Amid- © d®3f Haraateffn-iedium · Massimala Calcium- Caleiumehlo-

Pelymerken- ebloxddkon ™ rid- in Bszog s © nts? a- 25SHtFa- on the li

N _a $ -Diffi © £ hy Xasst & snid Sy @ lis © h® Amide

N-methylpiperidone-2

N =

Weight 55 Weight? System *) 3 * 0 A. 19th D. lh C. π ^M. A. 5.1 B. 15th B.

B - same £ © h effective - within 3% unite € = @something effective © ^ ~ üntersehiad <5,> 3

B € # is ρ i ® 1 β?

Dies®8 B © ispi @ l © rS-äyft ^ pt di ©

as well as © v © n. Maeser. des- isnd ^ © n Fas @ r-n and foils aiis

made of isetrep® "masses opposite ^ connected w © jr-ä

One gives siablim

on © ifiiiBal, sv: @i? i © s? Solution "" © rs 5 _s ^ 0 g {0 ₅ 050 MaI ^}; s; f mixture ¥ © η 65 snS. HeKazKsthylphseiiliöjcai 35 352 K "M @ fehy 1 ™ S = PfE ⁷¹ S ³ QlIdOK in eiiiero reihet with © ifieia lMfftgots © INSM Caleiuas © hl © rid.-DD © ek © sif © f ^ s ^ aahaiien lluinigskigssel hinau _9? the Mis © hanL 2 billion on © isisaal gepwl'i? ⁷ ®wt®n ₉ eüiblimi @ r-tee Tsrephtiialsylenlorid wätem?

hisigi & s rfiodes?! ® ^ the TenipgFat-iif ³ dei »reaction its' *

909887/1693 '"" ⁸ "^

BAD ORIGINAL] '|

miaübung with a cold water bath (20 C), the aetsfe flührsn continues until a pan is present, not longer be ÖIE check tubes, the mixture can now übernaeht bai Räumtempemtur standing, then combined on a 3 _S 785-1-Mise £ iep with water and roars at hohsr speed washes öac polymers with stirring to a mixer dreiaal with water and isolated it under Filtriej? er> on Ernest large-pored sintered glass Buehnertriehter and trockret polymers then übernaeht in a vacuum oven at about? O ° would recommend Pv * _rf exploit The inherent viscosity, determined on a solution of 125 ng of polymer in 25.0 ml of 95 to 98% by weight sulfuric acid, is given in the following table.

MiBCh- isophthaloyl polychleride (X), meres g C)

A B C D

Tabel

Terephthaloyl chloride (T) ₅
g (hol)

1.02 (0.0055 1.55 (O, OO75> 2, Often (0.010)

9.65 (0.0 * 175)

8.63 (O

8.12 (0, OiJOO)

Yield,

It , 5 11.2 Ii, H Ii, 7th

3.22 1 * 69

Τ / Ϊ

95/3 90/10

85/15 80/20

Production of the anisotropic Hasse v.na the polymer A: A mixture of 5.0 g of polymer A (according to Table IX) and 15, Ο g of fuming sulfuric acid (0.8 % free SQ ^) is cooled with an egg-Kasser bath mixed in a 200% ai! -fill flask without water with a mechanically driven paddle-type stirrer, while allowing the cooling bath to warm to room temperature during this period. The resulting, highly viscous M &f; s5 :: aigt RihropalesRana ri. \ L depcl {ix ⁱ ieiex '»: linearly polarized

Fasorhes ^ä 8tcl1uug a \ eat IISM polymers Λ by Nescspirmen: The Spiimmasoe obtained above is zm * removing entrapped gas geeehleuJtert ür.ä then ine means eirxer roechanisch driven syringe through i &Edelwet; all spinneret% * on 0.025 cm thick with 20 holes of 0.0076 esn D? 5 £ ° ehaiesBer in a watery

25 " (width about 5.1 em and depth about 909887/1693" ^W ~

cm)

Maeh pass © η © ines ¹ Badstsreüüt © f © n © few®

sw out a death ©! © lcferiseh anget ^ ieiben © «Auff? IEFE © lvorrieh" t "ng out and on a perforated spool 7. _S 22 ss / min.", you woifaiaf 3 ^ tdo in cold, running water wits © is

and dry in air at room temperature · The threads have a crystallinity and an orientation angle of 35 °

Cam W®ifewink © l »RfSntgendiagrei» determined); T / E / N ₄ / den 7 _s ? / Ta _s 3 / i95

Preparing an isotropic mass atse the Poljmespess Ds A © = Mi · · Providence of 5 _S O g Polymer D (see Fig. Table XI) and H ¹ H Q ₉ g rushing = S hw © @ ric acid (0.8 '% free SO ») is watered under iCöhtaj with an egg-waa ^ er bath in a SOO-ral ^ lundScolben ⁸ ©! with a mechanically driven stirrer of the ¹ Faddelbauarfe flb © rnaehfe ig, whereby the Mlßehwng eieli during the same period

arwlnnen lets «Μ © accruing hatred © and isotropic

Fiber production © by the polisher Turning wet spinning: The spinning mask obtained is only blown away from eirageseliloasenep gases and then by means of a m @ ehani @@ h "-driven injection syringe with 20 holes 0.00 - 6 cm in diameter in a hole of 25 ° 0 (Br © it @ -about 5.1 em _P depth about 2 _S 5 ^ 8 cm) "

Duj? Ehlfö? Ifen a Bsdefereeke ^ sb about 0 _s ? 6 m wIfö äa @ - Ahead of the water at an angle of about H $ ^& hera «sge ^c >, doh. with a guide, and an oXektrleeh Aufwiekelvorriehtung 'supplied «The thread throws on e ^ .n © r £ @%> i®Ft & n bobbin with § * 9 m / min. g®f3amme3, t » ^; then 3 hours running Waoeer gawaeiihsK ur «öi in air at Raiirafeeaptratm ³ getfö ^ k-;. The threads have a low crystallinity and unity

ungswinlcal mn 55® (determined on Veitwihkel-ROntgendia-I T / E / Hj / den 2 »4/25» 1/82 / 5.68.

Example 68 ■

This example explains the production of surfaces

- 120 -

909887/1693

anisotropic Masae based on poly- (p, p ^! -phenylenbenzamide) and fluorosulfonic acid. [

By dissolving a total of 28 g of poly-Cp.p'-phenylenebenzamide) with an inherent viscosity of about 2.0 (determined in 99.8 wt Obtain, opaque, anisotropic Maese, which shows a stamped Äühropaleszenz. This mass is poured into a spinning cell with an internal diameter of 4.7 cm and a depth of 11.7 cm, aue "Inconel", except for an amount of about 5 ml, and by exerting a mechanical pressure of 13.4 Ms 23.2 kg / cm a flask located above the spinning mill through a 100-hole platinum spinning nozzle (hole diameter 0.064 mm each) in water. Spun from 5 to 10 ° C. After passing through a bath section of about 140 on at 13 _t 7 to 21.3 m / min, the threads are wound up and on the bobbin during winding and then a further 16 ¹ BtS. Washed in running water, whereupon the Paser on the 'Spuleut 1/2 SW # trookaet in Luft *' and at 7.6 m / min, through an iron heated to 635 ° C (gate direction C) on the 1 , Hfache tetreoct. The thread material results in a Ί / εΜ _± of 3.70 / 1.2 / 402 and an orientation angle of 21 °,.

Example 69

This example explains the production of PäCen from an anisotropic mass, which contains Pol, y- (p-phenylene-p, p ^l -t> iphenyldioarbox amide), fluorosulfonic acid and HP »

To form an isotropic mass, dissolve 13 g of poly-ip-phenylene p, p ^f -.diphenyldicarboxamide) (^ _inh «· 2.2) in 40 ml of anhydrous

HF at 0 ° G, this mass cools overnight at -80 ° <i, erwöeat again to 0 °, treated with 20 ml Fluoreulfoneäure dta You must act, the Masee heated under nitrogen to room temperature so that _r the gröeste part of the HP evaporation can, and treated the next day with another 5 ml of pluoreulfonic acid. This results in a viscous, mother-of-pearl-like, anisotropic mass, which consists of about 2'ir al Fluoreul-: '. fona acid, 5 ml HF and 13 g polymers! consists, with 25 al the

- 121 90 9887/1693

viacosen, opaque Masee Rühropolessens se igen <. The Maas © is ejected using the device described in the previous example by exerting a mechanical pressure of 30.2 to 55.2 kg / cm ² on a flask located above the mass in water at 9 to 11 ° C between threads ,, which after having passed a distance of 140 cm is water and about 5 cm in water (into which the threads are introduced by means of a pigtail twisted by 90 ° to the thread path) with 18.3 m / läin »wound up and then on the Coil and then recovered for four more days with running water. The threads are then stretched 1.12 times at 7 "6 m / back" while passing wet thread material through a tube (direction C) heated to 550 ° C. With a titer of about 2 threads each gives a T / e / M ^ of on average 3 | 2/7 ₉ 2 / i41 before about 5.4 / 1 ^ 2 / 50e after stretching. -

B. C ₁ ia P ₁ i; e 1 _ _i 70 -

Theeea example illustrates the manufacture of

and

Poly- (3,3 '»diBethox ^ - ^^ - bipheByleatesephthalsmid) and

A) Polyethylene Therapy Division: The modification is carried out as in Example 49 ₉ -as that as BIsbIe 2 @ 12 g 3 ₉ 3 ^s -BifBetii3ilb © naWin are used. The only COLD eingeeetate ,, safe © carbon dioxide is at 15 ffl ^ n "entfernts'" 30 Min "is a fill forms. It interrupts aean stirring at 2 hours. UNAE leaves the Miechuiag another 16 hours" stehea = The gswaechen® and dried polymers (3 ₈ 39 g) have an inherent viscosity of 2.11 ..

Hsrstelluimg der Masses Dissolve 2 * 0 g of the polymer anhydrous by slowly stirring for 488 days in 8 _{seconds of} 0 ml of 100 sulfuric acid, an anisotropic masoe resulting, the RUhropaleaaem; shows"

- 122 9 0 ;; ö ίί 7/1 S 9 3

B) polymer manufacture; One works with the modification as in Part (A), that used as diamine 2.44 g of 3,3'-dimethoxybenzidine will. The stirring will be 2 strokes; continued, the System becomes highly viscous during this period and then a precipitate forms. The mixture is left to stand for 16 hours at room temperature. The washed and dried Polymers (3.9) g has an inherent viscosity of 0.99

Preparation of the mass: 2.0 g of the polymer are dissolved Slow a, 24 hours anhydrous in 8.0 ml 100, 95 # iger Sulfuric acid, forming a clear, isotropic solution. The addition of 0.2 g of polymer and its dissolution lead to to a smooth, viscoseη, anisotropic mass, the one shows a high degree of itühropaleszeris.

Example 71

This example explains the production of poly (3-methyl-pbenzamide) and anisotropic oleum dimensions of the same, with DDA values' of the masses are called.

Polymer Making: One with a whisk-type stirrer, a calcium chloride trook tube and a nitrogen inlet » 500-bag resin therapy bowl with a tube is supplied with a Bunsen burner flannel treated and at the same time with nitrogen rinsing, whereupon the kettle is closed and placed in a drying chamber. In the drying chamber, 24.728 g (0.12 mol) S-methyl - ^ - aminobenzoyl chloride hydrochloride balanced and in the boiler, which is now removed from the drying chamber, The agitator rotor and the nitrogen line are connected again and cool on an Eic-Bud.

· On & nobenzoylchloriclhydrochloriä ϊϊ earthen poured under rapid fiUhren quickly 140 ml of cold tetramethylurea The resulting solution, which shortly thereafter results in a precipitation _r is 1 hr - in the 3 ~ Methyl ~. 4 stirred at about 5 and 4 hours at about 25 ° C,

- 123 909887/169 3

181

whereupon the mixture is cooled in solid carbon dioxide and B ₉₈₆₈ g (12 mol Oj) Lithiumoarbonat are added, 1/2 stae. while cooling in solid carbon dioxide and then 1 StcL at about 25 ° C, the mixture is left to stand for 63 hours at about 25 ° C, then combined with water, stirred on a mixer and filtered. The precipitate is stirred on a mixer and Filtration after each washing treatment three times, with water and once with acetone and alcohol, whereupon the polymer is dried for 16 hours at 80.degree. C. in a vacuum oven with a vent tube of pressurized nitrogen. Yield 100 °°,% A _nVi & 0 _e 88.

Preparation of the mass. 1.0 g of the above polymer is combined in a Resgeno tube with 5.66 g to 100, some sulfuric acid (3 _e 6 fc free SO »} and stirred while cooling. jS ^ Pol raereo? DBA "80 _s. 6

1.0 g of the above polymer is combined with 5-66 g of 10.14% sulfuric acid (0.565 % free SO2) in a keagent tube and stirred, while cooling, until a solution is present. This anieotropic mass contains 15 ßew. ^ Polymerea? DDA »92.2»

10.0 g of the above polymer are combined with 48.32 g of 100 _{t of} 95%: sulfuric acid (4 »25 % free SO-x) in an agar tube and, while cooling, guess until a solution is present. This anieotropic mass contains 17% by weight of polymer _{or the like}

ft-g-JLg- P-JL! LJL Ii. ■■

This example illustrates the preparation \ <in the poly - (p-phenyIpπι erephthalamid) next anisotropic -01euianm3ß.en and fibers from the same "the DDA value iat called"

A solution of 43.2 g (0 _s 4 mol) of p-phenylenediamine in 480 ml of dry hexamethylphosphoramide and 240 ml of dry H-Methy 1 »- pyxrolidon-2 in a mixer is under .Hiüiren with 82 ₈ 1 g

. ~ "3 24»
9 098 87/1693

(0.4 mole) of finely milled ge asm Terephthaloylchloricl offset, said forms in about 20 sec., A gel ", which is after 20 min., And three times washed with water breaks _e twice with alcohol and with acetone, 93 g of air-dried Polymeres 3 ₅ 13) are obtained In a similar way, several polymers having a somewhat higher or lower inherent viscosity are prepared and combined to obtain a polymer with an inherent viscosity of 3 6.

30 g of the polymer mixture are dissolved at room temperature in 272 g of 1G0.4% sulfuric acid to form a fluid composition with a pole, y merge content of 10 -few. ^ O on _o The dimensions XBt _s on your

(SDA-V / ert of 93 »6) determined, anisotic * op3.

The mass exhibiting skin temperature is at 60. ö kg / cm Druok dwÄ ^: eli a 60 ~ LoGh spimi nozzle with a. Laughing diameter of 0.054 mm diameter in a V / asaerbad kept at 4 ° C gassed out β The threads, which are _{wound at 6 r} 4 m / min, are wound, after drying a ΐ / E / M ^ / den of 7 _r 0 / i0 _P 7 / i97 / 4 _f 9.

- 125 -

909887/1693

; ΐ: ^ BAD ORIGINAL

Example 73

The example explains Beatira .ings of anisotropic / isotropic pair relationships JHIr from versohiedsnen, for the Ztaeoke of the invention HF-j FSO3H- and C1SO, H-Maaaenj made of suitable polymers and copolymers, whereby for a system a JBeetimmig shown in detail and for the other systems the Results (obtained in the same way, but without Viacos'ttätabeotimcmn ^ en) are summarized in a table »

Λ) From the values given below and using FIg. 2 it can be seen that the Yieoosität the k mass ala function of polymer concentration for example ten masses according to the invention, the poly-Cp Iaenzamid) contained in the slope of a curve in HF, a Unstetigkeii present "The curve slope changes eicfa _$ if the The polymer concentration in the Hassen reaches about 14 wt becomes visible at 15 + 0.5% and has a lower viacoaity and is pearly non- opaque ie.t. This anisotropic phase separates itself from the ujcapiüssglielieiie highly »viscoeen clear Pfaais ©» '·

ι ^ - - ■

ψ To obtain the characteristic values for the above

Masj shows two poly-f p-beneamide) cash registers in HF depicting samples from polymers ait te in a polyalloaer puddle tube (3.8 osb diameter, 10 ₉ 1 om Fluorocarbon resin ("Teflon (h) TEE", the applicant) is provided through which a Yiaeositaeierspindel extends into the mass, or in a polyethylene film of about 4 _; 4 cm Darohmeaser and 10.7 Qffl depth, which is provided with a cap. through which you can see a via cosimeter spindle Äetreekt »

- 126- 909887/1693

'■ ■ ■ "*

By JSineata of a Ms-V / asyer-external oeuvre throws, a constant Maintain temperature of 0 ° G. Γάσ Mocjsung de j: · The viability of the stirred Masae is done with a viscometer of the Brookfield S ^ nehrc-Leetrio Viecoiaeter (McdeH '.; HV, Herateileriss the Brookfield Engineering Laboratories, Inc., Staughton, Hasa », IT.8.A.) using the dated Serving manufacturers supplied spindles Kr. 4 un & 6. Die Viecosity is calculated for different Koiis tretioRen, by tipping the displays of the ViscoGinieterse; (getη with different spindle settings, whereby these are the Specify spindle speeds and thus the shear strength) to the table values of the "Brookfield Factor Finder" relates. With the addition of further ci Polynierem, j increases

the viscosity of the solution up to a maximum value of about 3600 P, which results in "I when there is 13.4 Gevc" * on polymers in the ear. In the presence of 20 + 1 _r 0 Gew.?6 of polymers ¹ "in the Hohr the original clear phase completely verfjchwindet and iot! Sichtbor only the anisotropic phase. The anisotropic phase shows: 1. a depolarization of the plane of linearly polarized light when viewed through crossed polarizers in an icicscope, 2 » when stirred, a strong pearlescent character? _c thixotropy.

The details obtained from these determinations are shown in the following table.

( Table XA

g Poliinereij / Ge w. ^ Locker line setting / viscosity dtr »

Poli'raerea Spindelzeigar-An «- Hasee (errccb»

_{ti m <} __ show HS ^ LuJL- ™. "" ..

Hasae 1 (using 58 ml
water for eii «ε HP: ^ j ._, = 5.9)

5 / 4.9 5OV11.5 46

5 / 7.9 '; OY55.5 110

7 / 10.8 0 ^^ / 21.5 860

9 / 13.4 t «Tl / 36 3 600

14 / 19.4 V ^r V2.0 200

909887/1693

(up i JVtil

(Continuation)

g polymer / wt. ° / o Spindle setting / viscosity of the polymer spindle weight ~ Approximate mass (calculated

tK, P

Mass 2 (using 90 ml of water · » free HP; same polymer as in mass 1)

4 / 4.2 100j / 10.5 ■ 2.1

6 / 6.2. 50 * / 48 19th

8 / 8.1 20 * / 90 90

10 / 10.0 1 * / 51 '1 020

12 / 11.8 0.5V44-- '1 760

14 / 13.5 2 _t 5f * / 8Q 3 200

16 / 15.1 1 ** / 28 2,800

19 / 17.5 1 * V17 1 700

21 / 18.9 1 * V8 800

22 / 19.6 1 ** / 4 400

24 / 21.0 1 ^X V3 300

*) Use of spindle Ur. HV 4 **) »""No. IiV 6

(Cf. are Fig. »II in which both distribute plotted on a curve) Plotting the viscosity to the polymer concentration to, the" critical point results in about ⁷ 14 wt. $ Polymers. The final viscosity, from 200 to 400 P, is about 4 to 6 # of the highest measured or bulk viscosity determined from the viscosity at the point of the discontinuity in the curve.

(The above viscosity determinations are made with an uncalibrated Viscometer spindle system in containers .not optimal dimensions; while the relative viscosity determinations with the Masuians are exact, the absolute values need not necessarily to be correct ")

B) Using the above methods, the values given in Table X-B are obtained for the systems mentioned » The systems in Table X-B have viscosity reductions

- 128
909887/1693

■ we —w

(similar to the above) to be observed qualitatively when the respective cash register changes from isotropic to anisotropic while increasing its polymer concentration. The aniootropic masses bind, as above, look like a mother-of-pearl ax and depolarize the plane of linearly polarized light when viewed through cross-polarized polaroids with a microscope. The column "polymer according to" gives an example whose general method of working for hexatellation of the respective polymers or copolymers, the mass of which is assessed according to the methods of the present example, can be used ation in the Masae, in which a visible opaleacence or a second (anisotropic) phase results, and "B ¹¹ a polyra concentration in which only a single phase (anisotropic) phase is visible.

"b" means that apparently two anisotropic phases were formed one at about 1.5 and the other at 19 to 20 wt. ^.

In case c ~ 1 the molar ratio of -CO-.// Vv-CQ-

to -CO - «^ Vs _x - <V VS, .qo- 50:50 and in the case of c-2 9.0: 10.

Table X-B

Phase relationships more anisotropic and isotropic

Crowds

Polvmeree

according to example

62-A

62-A

62-A
62-A

21 ,
1

4.0 2.86

3.9

2.86

3.9

2.0

1.55

3.4

2.86

Solution agent J.

HF

PSO H HF 3 HF

FSO ₅ HF 3O ₅ H FSO ₅ H ClSO ₃ H

909887/1693

129 -

A, 7 *

13th

. +
17th

0.5

7-8
8th

20-21 12-13

19 18-12

14-13 15b
9-1-0 10

JIf)

At- s ρ i I ¹ " ³ ^ inh a b e 1 1 e X-B A ^a , <f> B ^a , if 9 3.4 (Port setting) - Polyjn ~ 2.0 solvent . 7th > 11th after
game t 5.2 9 10 1 2 3.5 ClSO ₅ H 9 '! 0 28 1 5.2 GlSO ₅ H 8th 10 23 / c- 2 3.5 PSO ₅ H 9 23 / c ~ el 74 PSO ₅ R 8th 23 / c- ClSO ₅ H 23 / c- 0ISO ₅ H at

This example explains the effects of the parameters 1. acid strength and polymer concentration, 2. inherent viscosity of the polymer and 3 »of salt additives on the anisotropic sulfuric acid» and oleum compositions according to the invention based on poly (p-benzamide) and poly (p-phenylene terephthalamide).

Acid strength and polymer concentration: The results of solubility investigations of poly (p-benzemide) in sulfuric acid and oleum are compiled in Tables XI and XII. To obtain the oil value, add the acid or oleum in a bottom flask, which has a polished glass bearing and a stirrer with a padded stirrer made of fluorocarbon resin ("Teflon" (1) TPG), an excess of polymers. The temperature of the flask inhalation is moderated with a water bath at room temperature. After long-term stirring periods (. Eg 2-16 hrs.) Are added to ^ IIE of acid or oleum added and determines vi3ueli the maximum concentration as the point can be observed on your no solid. In addition to the calming, liquid, anisotropic masses, further proportions of acid or oleic augeoetat are added until the mass is visually clear: the polymer concentrate cü. with the visual

- 130 -

909887/1693

BAD ORIQiNAL

The Masae become clear as a critical point of conversation recorded. The values mentioned are on Pal, y- (p-oens38niid} samples with an inherent viscosity of 2.72 and T- .53 have been. ·

T a b e 3. 1 e XI

Solubility of poly- (ρ "benzamide) ( critical in sulfuric acid keiaer H ₂ SO ₄ , $ Maxiral solubility ^ none 96.3 4.5 8.67 97.3 7.14 8.67 99.2 10 »3 8.55 100.5 12.7 8.76 102.3 14.4 104.5 14.5

a) Manufactured in N, N-Dimeth> lacetamide and neutralized with LigCO,.

b) Much as a concentration (wt.

c) weight & polymer in bulk.

Solubility of poly- (p-benaamid) in sulfuric acid

- 1.53)

H ₂ SO ₄

99.2 95.9 100.5

Maxillary fluidity

· 6.7

15.5

critical panic

9.68 # 9.60-

a) Visually determines the concentration (Gewc ^ Polyraeren;}, in which no solid particles can be observed.

b) Weight of polymer in the mass. "

Using the fourth of the above tables, the phasend iagr camouflages of the kind shown in S ¹ Ig = IY can be drawn *

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With corresponding determinations on a poly-ip ^ phenylene tere = - plithalamid) «sample with an inherent viscosity of 3» 32 obtained Values are compiled in Table XlII? a The phase diagram obtained on the basis of these values shows the

Fig. V ₀ '·

Solubility of poly (p-phenylene terephthalamide) (^ _n J ₁ = 5 »3

in sulfuric acid

SO ₄ , fo maximum solubility ¹³ critical point ⁰

97.3 4.6 99.2 7.8 100.5 11.7

8.65

a) Visually as a concentration (weight? »polymer) determined at which no solid particles . are watching »

b) Weight </ £ polymer in bulk.

Inherent viacosity of the polymer; For a given polymer in a given acid, a change in the critical concentration with the molecular weight (or the inherent viscosity) of the polymer is to be expected. Values for poly "= (p-phenyleneterephthalamide)" samples of various inherent viscosities are given in Table XIV. To obtain these values, dissolve a sufficient and known amount of the polymer completely, then titrate the resulting anisotropic masses (while mixing with a spatula) with the same acid or with the same oleum until the fibers are much clear under shear stress _{ these Method for * dissolving the polymer can take several days to several weeks due to the extremely high viscosity of the mass. In general, this method iet the polymers satisfactory _t their inherent viscosity-under 3.5.

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BAD ORSOfMAL

/ Sb

Critical Points (or Concentrations) ■ of poly <- (p-phenylene terephthalamides) in 100, 25a sulfuric acid

Polymers η,

1, -24
2.23
2.64
2.70
2.76
2.80
3.06
3.37

Critical Concentration

10.81
9.47
9.52
9.13
8.92
S .-. 95
8.77
8.39

of polymers! in bulk

Table XV gives the entapreciating information for poly · = · (b-bercsainide) , whereby the values of this table show a trend towards lower critical consistencies in the increase in the inherent viscosity of the polymer. glad irj the Fig. VI eav ;. i / ΊΙ graphically represented.

Picts (odei:

, ί) ':

η, θ "

ίϊ Λ

yy? 3 100.3

99.7 'OQ, 5 100.5 100, 2 100.2' «00.2 K) Op 3

iii in the

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. *. isch «Kcπ-

9.88 9.74

3 r 5 " ^? 10.00

9.67

9ρ22 9.30 9.69

^BATH

Salsausätae lead in oleum maases of (I) poly ~ (p-hpen; ylene terephthalamide) oil _{± nh} = 2.80) and (II) poly (p-benzamiä) ty _inh ~
2.72) after adding a certain amount of salt to the
Transition to a solid slurry. The amount of SaIa required to form the pulp is given in Table XVI for Masaen which initially contain 3.0 g of the polymer and 27.0 g of 100.2% sulfuric acid.

Solidifying relationships between
Mass and salt

Polymer
in the iSasse SaIs "Salam quantity ί'ύζ da3
Occurrence of a
Solid slurry, %. I. Na ₂ VlPO ₄ 0.6 II Ia ₂ IiPO ₄ 0.8 I. KOAC ^a 0.6 II Wa ₉ SO ₄ O ₅ B

a) potassium acetate

The Salae are added in 0.2 g portions, if in the mass In each case lower amounts of salt than the oils mentioned in the table are available, the Hassen fluid and violin RühsopaXes-P zens.

Example 15

This example illustrates the effect of l'smpsratui 'and Gswichtspjfoaentsata on polymers on the critical K
points for 'Poly <= (p "ben» araiä) and

Similarly as above, Pol ^ - (p »bensaiaid) becomes with a ixihäreat
Viscosity of about 2.72 manufactured Wardan The masses with different Ver Konaentratxonenj namely 9.2, 10.0 and 12.0 ° / o in

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99 5gewobiger _t H ₂ SO ₄ at room temperature, prepared _t each of said masses eats anisotropic at this temperature ο With gradually increased temperature are the three läaeseproben _t a conversion in substantially isotropic masses at 29, 53 'or ο 77 ° C.

Similarly to the above is poly (p ~ phenylentereph1: lialarniä) vop having an inherent viscosity about 3.16 »The compositions prepared are with different concentrations _f namely 9" 2 "10.0 and 12.0 i> in 100,3gew. <& igGr H ₂ SO * prepared at room temperature »each of these masses being anisotropic at this temperature. When the temperature is gradually increased, the three dimensional samples are subject to conversion into essentially isotropic masses at 411 67 and 109 ° C, respectively.

The points at which each of the above samples of the conversion is subject ,, in a substantially isotropic Hasee that kritiuchen Volumenkonaentratiouapunkt provide each sample represents "As the present example shows _r is this point at a given polymer Plüsoi ^ -mediuin-S ^ ßtera on the temperature of the Maoee and the weight percentage. on (largely dependent on the polymers present »

- 155 909887/1693

Claims (9)

22ο November 1968 JLJL-JL-g. Btans / sayings 1. Gothic anisotropic Mas8e _? consisting essentially of aas I. essentially of carbocyclic, aromatic homo- and mixed polyamides!}, In which chain-lengthening bonds emanating from each aromatic nucleus run coaxially or parallel and oppositely directed, ■ existing polymers and
II. A liquid medium from the group A) Amides, ureas and mixtures thereof from the group N, ii-Minethy! Acetamid, I, N ~ DimethylpiQpionamid, Ν, Ν-Dimethylbutyramid _f jr ^ N-Dimethylieobutyramid, U, N-Diinethylraethoxyacetamid _s N ₃ M-Diethy! Acetamid, ti-Methylpyifrolidon-2, ϊί-Methylpiperidon- 2 _t N-Üiethyleaprolactam, H-ethylp, \ <3? Rolidon-2 ₉ N-acetyl-.pyrrolidine, N- »acetylpiperidine ₉ HyN'-dimethylethylene- = urea, Ν, Ιϊ'-di-ethylpropylene urea, hexamethyl ™ NOBphosramide and , H, H '~ Tetramethylwax, B) concentrated sulfuric acid,
G) hydrofluoric acid and It) chlorine or fluorosulfonates, v / obei the polyamide in an above critical concentrate concentration is present " 2. A composition according to Anapruch 1, characterized gekennseichnet ₅ that the liquid medium is an amide _t urea or a mixture thereof with a content of a salt from the group lithium chloride and calcium chloride. 3. Masae according to claim 1, characterized in that the liquid medium is concentrated sulfuric acid having a concentration greater than about 38 weight <. _R $ is the acid freisa SO featuring contain " 909887/1693 " 1810428 4. Composition according to Claim I _9, characterized in that the polyamides are present in the liquid medium in the form of essentially tabular structures. 5ο fiber or _o filament made of polymers consisting essentially of carbocyclic aromatic homo- or MiBchpolyamiden, extend directed at those emanating from each aromatic nucleus kettenverlängerde bonds coaxial or parallel and oppositely, wherein the fiber or .. the yarn an initial modulus of übex about 300 g / denier and an orientation angle smaller than about 35 ° 6ο Easer toswö thread in the spun state Claim 5 with a strength of more than about 5 g / den and an'Orientierungswinkel less than about 45 »· 7. fiber or thread according to claim 6 with an initial modulus of practice? about 200 g / den .. 0. Heat-treated fibers or fibers consisting of polymers essentially of carbocyclic, aromatic homo- · or random mixed polyamides, in which of each aromatic Core-extending chain-lengthening bonds coaxial or run parallel and in opposite directions .. 9. Faaer or thread according to claim 8 with an initial module of over about 300 g / den and an orientation angle less than about 35 °. 909887/1693 " ^13? " Read 11 e