DE1929694A1 - Mass and items made from it - Google Patents

Description

Mass and articles made from it

The present invention relates to compositions of matter or compositions (dopes), the carbocyclic aromatic polyamides contained in suitable liquid media that are optically anisotropic (different light transmission properties pointing in different directions in the mass) ο These masses and related isotropic masses are ■ for the production of threads or “pasers with extraordinary Internal structure (manifested by a low orientation angle and / or high speed of sound occurs) and extremely high tensile properties (with <*> e.g. initial module) is used.

The present invention relates to new, optically anisotropic Masses consisting essentially of carbocyclic aromatic

009636/2187

see polyamides exist in suitable liquid media. These masses and related isotropic masses are used in the production of useful filaments or fibers, films, fibers and coatings. In particular, threads or fibers with an exceptional internal structure and extremely high suction properties are created.

The inventive masses that are optically anisotropic (measured by working methods described in nachiolger.d) Components selected from the group of carbocyclic aromatic polyamides, their chain lengthening Bonds of iodine aromatic nucleus essentially are coaxial or parallel and oppositely directed, in suitable liquid media, which are illustrated below, which may contain additives. Me The amount of polymerizate in mass exceeds the critical one Concentration point and is preferably at least about 5% by weight of the mass. These are anisotropic masses structurally and functionally of known polyamide "solutions" different and are used for the production of high strength Shaped bodies (for example threads or fibers), often without post-treatment after .üOrnnung (for example Stretching), exceptionally suitable.

The threads according to the invention büw. Fibers are made from the above optically anisotropic masses or related isotropic masses are produced which contain special aromatic polyamides. These threads or fibers are characterized by an extraordinary internal structure and "extremely high drafts" shafts, either in the state after extrusion (as described below) or after heat treatment (as described below1).

This extraordinary inenabruktvr of the threads or fibers occurs in that the threads or fibers

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a low orientation angle and / or high speed of sound demonstrate. Threads or fibers according to the invention preferably show angles of orientation below about 45 ° below about 35, and most preferably below about 25 °, measured as described below, and / or sound velocity values at least about 4 km / sec, preferably at least about 6 km / sec, and most preferably of at least about 7 km / sec ,,, measured as follows described

Iiie threads or fibers have excellent tensile properties, in particular an angular modulus of at least about 200 g / denier, preferably of at least about 300 g / denier and most preferably about 400 grams / denier and / or one Tenacity of at least about 5 g / denier. Preferred invent In the state after extrusion, appropriate threads or fibers also have a high initial modulus and high strength an elongation of at least about 5 #.

The invention is described below with reference to Drawings explained in detail * They show:

1 shows a phase diagram of a poly (benzamide) / ir _y N- according to the invention. ^; ilmethylaoetamid (contains water and lithium chlori &) - Ma8se _t

Figure 2 shows a typical relationship between viscosity and polymer concentrate. in the case of the masses according to the invention, which shows the San ki ^% itic concentration point,

Fig. 3 is a typical curve of an X-ray diffraction pattern of poly - »(p-benzamide ^ homopolymer,

4 and 5 further phaser diagrams of Hassen according to the invention,

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Pig. 6 and 7 critical concentration points of special masses according to the invention as a puncture dor logarithmiechen Viscosity number and

Pig. 8 and 9 show the relationship between the pad structure "_

ture parameters, angle of orientation or »speed of sound and an important physical property (initial modulus) of the thread.

The invention is described in detail below.

Polyamides

To the suitable aromatic polyamides (from which the preferred anisotropic hats according to the invention consist and / - or from which the threads or fibers according to the invention can be produced) include those in which the chain-lengthening agents Bonds from each aromatic nucleus are substantially coaxial or parallel and oppositely directed are. The term "aromatic nucleus" used in describing the present invention is intended to be individual include chain linked aromatic hinge and divalent aromatic radicals with fused rings. Preferred polymers include carbocyclic aromatic polyamides with up to two aromatic rings, including non-fused rings linked in a chain (for example 4ι4'-biphenylene) or fused Rings (e.g. 1,5-naphthalene), per amide linkage » The chain-extending bonds of these aromatic rings are p-oriented and / or essentially coaxial or parallel and oppositely directed «.

Highly preferred polyamides bind through repetitive Units of the formula I.

003838/2197

O OH H
Π HI

-L. G-R-G-H-R «-Ν 4- (I)

characterized in which R and R ¹ (if the chain-extending bonds are substantially coaxial.) below

, l _f 4-phenylene and 4 f4 ⁸ -diphenylene

are selected and in which R and R "(if the chain length like bonds are essentially parallel) below

1,5-naphthylene and 2,6-naphthylene

selected Bind »where H and H * are the same or different can and contain substituents »on the aromatic nuclei can.

Further highly preferred polyamides according to the invention are duroh repeating units of the formula "II

^{0 H}
-J-- C-R »-N 4- (XI)

characterized in which R "under
*. '''- 5 -

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1,4-Ph, enylem and 4,4 * -bipheaylene

is selected. E "can also have S substituents on the contain aromatic kernels.

The aromatic nuclei of the polymers according to the invention can, as already mentioned, carry substituents. These

t SubBtituenten are not to be reactive during polymerization and should preferably also during subsequent processing of the polymer, Example \ * ei ~ se the heat treatment of a molded article thereof (e.g., thermal), be non-reactive. Such a reactivity is undesirable insofar as it causes crosslinking of the polymer and can adversely affect the properties of the compound and / or pad properties. Preferred non-reactive substituents include halogens (e.g., olor, bromine, and fluoro), lower alkyl (e.g., methyl, ethyl, isopropyl, and n-propyl), lower alkoxy (e.g.

k methoxy and ethoxy), cyano, aoetyl and nitro can be mentioned. Other suitable substituents which are unreactive during the polymerization will be apparent to those skilled in the art and are supported by the present invention includes, provided that they have the desired properties of the inventive masses and / - or threads, for example by factors such as steric Hindrance, not adversely affecting · In general It is preferred that no more than two suitable substituents (and more preferably there are no longer any suitable substituents per aromatic nucleus.

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but more than two such substituents are more suitable Catfish are present when the substituent is relatively small Group, e.g. methyl, 1st.

Both homo »and mixed polyamides with substituted or unsubstituted aromatic nuclei such as those above are well suited for the compositions and threads according to the invention. Copolymers with random Distribution are preferred copolymers. 33er expression "with random distribution" means that the copolymer consists of molecules that have a large number of units that are of two or more different types, Contained in irregular succession The units can be of type AB (for example from p-Amlnobenzoylchloridhydrochlorld), AA (for example from p-phenylenediamine or 2,6-2) chloro-p-phenylenediamine5 or BB (for example from terephthaloyl or ^^ - bibenzoyl chloride) or mixtures thereof, always with the proviso that the stoichiometric requirements for high polymer leat formation are fulfilled. It is not necessary that the relative view! of the different types of unit in different molecules or also in different parts of a single molecule is the same »

One or more of these polymers can be used in a suitable manner Way in de ~ 3 inventive masses and / or threads or Fibers are used, i.e. a single homopolymer, a single copolymer or homopolymer and / or interpolymer mixtures are suitable therein.

Although the polymer chains described above essentially consist of amide linkages (-CONH-) and aromatic ring cores, as described above, the polymer which can be used for the production of the products according to the invention can also contain up to about 10 % (molar basis) units

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included, which do not meet the description cited above, for example, aromatic polyamide-forming units whose chain extending bonds ßiad directed coaxial or parallel and oppositely directed differently al _3s oils at · »spielEAtfeiee m-oriantiert may be, or other linkages ε-le Amidverknüpfiin & en, for example urea or ester groups.

Suitable aromatic polyamides include poly (benzene amide), poly (p-phenylene terephthalamide), poly (2-ohlcr-p '»phenyl enterephthalamide), poly (2,6-d-il or-p-phenj ^ . en ~ 2 _f ö ~ naphthalamlc.) "Poly-Cp-phenylene-p, ρ '-diphenyldicarboxaaiid} _s poly- (p, p'" - phenylbenaamid), poly (I, s ^ naphthylenetereplithalamid), ordered aromatic mixed polyamides , for example mixed poly-Cpjp '^ diaminobenBanilid-terephthalarald) uml mixed polyamides with random distribution, such as Miscnpolj-Cp-beuzamid / m-benaamid) (95 i 5) and yiels- others., erv / similar-t are »

The designation of the positions of substituent groups on the aromatic nuclei de :? The polymer, which are useful in the present invention, "ölijh shall look to the position (s) of the or the substituent on the Diami ^ - diacid od _<;.? R other Reaktionsteilneiunems, resulting daa polymer is produced For example. ? a random distribution of polymer-forming units ix of the chain, if ßie possible _P of ö.em name includes _r with which every given polymerisate here bs * - denotes vfS, approx. "

As already mentioned above, the polyamice have a logaratlunisehe "risk number (w.le described below) ■ of mJnrlestins about O _t 7 and above about 1.0, bind thread-forming and with the present invention "'special brtv; .chbar _e lower ones. logarithmic sows

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Aahlen can be used for filiaej fibrids and / or overseas \*?earth.

A precautionary polyamide according to the invention _a substantially homopolymeric 3 poly (p-benaamid) _p which consists essentially of repeating units of the formula III

H 0

Λ yy

bestehta karca by certain polymerization processes are readily obtained from suitable monomers ₉ which are dissolved in specific solvents _s v / oak .g @ vrfiascl.iten if Lithlu ^ oblorid and Kettsnalabruchmittel contain & ö new.

2u suitable monomer belong
aalae of the formula

CX ₂ (IV)

wherein XT arylsulfonate ,, alkylsulfonate, acid sulfonates or halogen radicals, preferably Brcmld- or Chloridreü1; tf _s UIID Xg a halogen radical, vor2ugeveise Bromld chloride or mean, p-1st AjDainobenzoylchloridhydrochlorid the preferred monomers. .Other suitable monomers are p-aminoben · - zoylbroffiidh3? irobrcinide, p-arainobenzoylchloride hydrobromide ₉ p-.Amlnobenzc '/lchloride methane sulfonate, p-AmlnobenaoylchlorAdbenaolsulfonat, p-Aminoben £ 5oy3 ohlaridtoluenesulfoBatj p-Ami »» Nobenzoylbrcitld -Päthansulfonat. Other monomers which do not come under the formula (IV) are, for example, p-aminebenaoylchloride-ulphate

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ß ORJGfNAt

AO

also suitable. The preferred hydrochloric! can in holier yield from an äth-sriseliea solution full p ~ Thionylaini »obeii3oyXnhler.td g © s? .ä £ dsr £ ^: llg8 ~ my working method of Graf and Langer-, JO pate G ^ asu 1 £ 8, 161 (1937 ) j under wasesrfroisn conditional ri liyx ^ eetellt. The Srooknimg wni aie ws.ess: <? Fe "ij storage of this Maaoaereri takes place hematempera urbedingiisgeii, since the tempera tends to Polyaierisn

To LösuKgami.tteln »those for the P suitable are »genöreii from the chosen solvents:

H ₉ H, N ', K ^! -Setraraethylhariistof f, Hexame thylp] ίο sphoramid, H, Η-Dime thyli.äoe tamid, N-Me thylpyr: eolidon-2, N-Methylpiporidon-2, I, 3-Dimethy:: ⁱ .imiclazolidinon-2 (ie, urea)"

N, Hj M ' ₅ H ° "-TatrametSiylmalonamid, IT ~ Me thy! c aprolac tarn, N-acetylpyr? olidin, Ν, Ν-diethylicetainide,

N _r H ~ Dimothy Ipropionaniid, N , Ίϊ-Dime.thy lisobutyramid, NjN-I) imethyll3Utyrainid and Tetrahydro-1 »3-dimethyl-2 (lH) -pyrimidine» ( & . H, * S, H ■ ♦ ♦ methylpropylenurea .

As a precaution, the salts, such as Mthiumcnlorid ,. zvig0Retst _o Such an addition can support the retention of e: -ner flowable.

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With these poly ;; ¹ ·?!?! sation en körraen, as mentioned above erwälm-tij iCetteÄia'Dv ::, ahiaittel can be used. The use of voTi liet-tenachruohia.ifcteln contributes to the ease with which the subsequent processing of the polymerizate takes place by supporting the regulation of the molecular weight of the polyamide _. and increases Stabilitäs aar Pol ^ miürisatmasse for use in your tipäter bescliri flat "coupled" Polymsriaationa-Spinnverfah-Among the suitable Kettenabbruohmitteln are mono "

Compounds which can react with the acid oliloridends of these polyamides, such as ammonia, monomers (for example methylamine, dimethylamine, ethylamine, butylsitine, jibutylamine, cyclooxyamine, aniline and the like), compounds which form a single amide-forming group t> ip-1 r -m. e rl N M _{r r-Diätliylätliyl} endiamia hydroxyl compounds, such as methanol _s ethanol, isopropanol, phenol, water and dergleichens and monofunctional Verbinrlungfjn that can react with the ü.end5ti and the polyamides, such as other compounds (for example acetyl chloride), acid acids (for example acetic anhydride, phthalic acid anhydride and the like) and isoyaxates (for example

"- ?. yiat, la-Tolylieocyanatj Äthylißaoyanat and the- To useful difunctional Abbruohmitteli Ιια2: βά Ter-ephthkloylchlorid» Isophthaloylchloricl, Sebac.vichlorid, 4,4 '' - Diplienyldi & ulfonylchlorlda _P Pyroraelli.t2 v-i- i .rid, ρ-phenylene diisocyanate, BenzidindÜBO «· cyane. \\ ,, bis - {^. iß'ocyanatopnenyl) methane, p-phenylenedia /; i.in _s i / i-Ph. ^ iylenediamine, Benisidia. bis- {4 - aminophenyl) boxes, N ₁ N * -IIaminoplperassin, adipic acid hydrazide, ierephthalic acid dihydrazide, and isophthalic acid dihydrazide.

The PolymerLsationsrealction can be carried out by that od-i? the desired Jüoiioraex'en (as well as the chain · » abbxuo limit t; 1 and lithium chloride, v / enn verv / ends v / er ··

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den) are dissolved in the desired amide or urea solvent and the calibrating solution is vigorously stirred and externally cooled until a viscous solution or a thick gel-like mass develops. Alternatively, the desired monomer can first be slurried in a small amount of an anhydrous, inert organic liquid such as tetrahydrofuran, dioxane _→ benzene, or acetonitrile prior to addition to the amide solvent. Preferably, the resulting mixture of monoeae and organic liquid is stirred at an increased rate and a relatively large volume of the amide solvent is added rapidly. In a further variation, the amide solvent can be frozen and mixed with the desired monomer while frozen. The solvent is then allowed to thaw and the resulting mixture is stirred until a viscous solution or gel-like mass forms.

In the above operation 3eder orphans the Polymarisetionsreakticm, if necessary to <§ = 30 ° C, maintained by external cooling, at low temperatures, ie below 60 ⁰ C and preferably at -15. The reaction mixture is continuously stirred until it gradually turns into a viscous solution or into a thick, gel-like mass. The reaction is generally allowed to proceed for a period of from about 1 to 48 hours, preferably from about 2 to 24 hours.

At the time of the highest molecular weights, d Polymerizations carried out under strictly anhydrous conditions. I) the reaction tank and the susätslicbe system, solvents and reactants have been removed prior to use carefully dried and the reaction vessel will be preserved! the polymerization continuously with a

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Af 1 Q? 9 RQ

Q-1051-R w iy ^ b ^

Stream of dry. ,, inert gas, for example nitrogen, flushed.

The polymer asaticm reaction produces an acidic by-product (e.g. HGl or HBr) which is preferably neutralized. Neutralization is particularly preferred in the embodiments described below, at which the Esaktionsmisohung for direct use the production of moldings from the polymer is made. In this 3? All, the addition of a base is preferred, the under

Lithium carbonate, lithium oxide, Lithium hydroxide, Lithlumhydroxydmonohydral ;, Lithium hydride, calcium oxide, Calcium hydroxide,

Gallium hydride and ■

Galclumo carbonate

or mixtures thereof, to neutralize the reaction mixture au ₀ Dij using a NeutralA-sierungamittels is very erwüntoht because the acid substantial Eorroaionsprobleme in the processing plant (for example, the spinneret) verurso ^ hen can. Neutralization may be necessary in each case in order to obtain more permeable masses which facilitate the formation of organs. If neutralizing agent is used much more than the etohiometric amount, then an insoluble excess may remain, which may be necessary to remove before the formation of a shaped body (for example by bpinnon). The neutralization agent can learn to react

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Q-1031-H 1H

tion medium before, shortly after or long after the addition of the Ko ^ nomeren are added whatever is of the desired logarithmic see viscosity number depends. The addition of the neutralizing agent can lead to a strong increase in the polymer mol ekulargewiohts, determined by measuring the logarithmic Viscosity number of the polymer isolated from an aliquot part of the reaction mixture before and after of neutralization.

In addition to the excess neutralizing agents, the masses can contain other insoluble material which is to be removed, preferably by conventional means, before a molding is produced. If, for example, the acidic polymerization system generates bromide ions and lithium hydroxide is used as the neutralizing agent, the lithium bromide formed can be insoluble in special masses and should be removed before the mass is spun or poured.

The composition or mass can be any of those discussed below Conditions in vacuum are concentrated to a flowable mass with the desired pesticide content and / - or with the desired viscosity for spinning or casting produce.

To isolate the poly (p-benzamide), the polymer mixture is combined with a powder for the polymer * "for example Wisser, in a suitable lüscher and thereby converted into a powder. The powdery polymer is after washing both ater than götroclaiat V / with alcohol üoer overnight in a vacuum oven at about 60 to 9O ⁰ C before it is stored or treated for subsequent processing.

The prepared in the manner described above, im essential homopolymeric poly- (p ~ benzamld) possesses a

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peak height ratio (PHR) below 0.86 and es no sediment can be seen in the tube when the polymer is subjected to a sedimentation test, as it was later Will be described in detail. However, it is clear that the peak height ratio when applied to a sample this polymer is measured, which has been spun at elevated temperatures or heated to elevated temperatures, can be above 0.86, the sedimentation properties also Such a sample can be different from »poly- (p-b-incamide) with a PHR over 0.86 is also useful in the context of the present invention, for example for anisotropic hating this Polymer in ΗΪ or oleum.

Andsre in the present invention useful polyamides may be made of suitable Mitrsaktionsteilnehmern duroh Niedrigteaperatur ~ Iiösungspoljmeri.-ationsverfahren (ie below 60 _o ⁰ G, and preferably from -10 bi.3 30 ⁰ C) similar to those in US Patent 3,063,966 for the preparation of of poly-Cp »phenylene terephthalamide) described procedures. For example, polyamides of this type can now be produced by reacting ρ «phenylenediamine or 2-chloro-p» phenylenediaicin with polyamide-forming derivatives of terephthalic acid. This dicarboic acid is usually used in the form of its dihalides, which are easily prepared by known procedures, with the disaurechloid usually being preferred a solvent or in a mixture of solvents, selected from hexamethylpiiosphoramic, N-Methylpyrroliüon-2 · and N, N ~ DiT _A ethylaoot ~ amide , tissue «. Often a fall occurs within a few minutes

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Polymerisats, while in other cases the reaction mixture can gel. In some cases it may be desirable to wait for 30 minutes to complete the reaction Stir or leave to stand for several hours or longer «The polymer can be isolated by the Reaction mixture with a polymer nonsolvent »for example Water, is agitated in a suitable mixer. Before storage or subsequent processing in a mass of the polymer is collected, washed and dried.

The production of other useful polymers and Copolymers are in the following examples illustrated. These manufacturing methods can also use the Xn-situ production of directly extrudable anisotropic « Include masses as shown in Example 4, for example.

Made to measure;

Polymers and copolymers produced by the procedures described above ■ and after formation have been isolated, can be mixed with a suitable liquid medium (if necessary including additives, for example LiCl) can be combined to form a composition or masses au form (such embodiments "are hereinafter referred to as isolated polymer compositions). In certain other embodiments, the polymerization medium is used used to create such compositions or masses in a "coupled" polymer! onsspimi « method r; u form (such embodiments are hereinafter referred to as in-situ polymerizatraassen) "

To liquid media that are used for the production of the anisotropic masses according to the invention and related isotropic Mac? ώ s useful include:

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1928694

(1) Selected amides and ureas, including methylacetamide, iT ₈ M ™ Dimethylpropionaniid ₉ MpH

amide, MjlI ^ Di ^ ethyliBObutyr & mid, 3ü, N-.DimethylmethQ3Eyacet ~ amid _p NpH -diiethylaeetamid, N-Methylpyrrolidon ~ 2, H-Methylpiperidon-2 _f N-Methylcaprolactam, N-Ltliylpyrrolidylpyrrolidon-2-Niperidin-2, N- , Hf _S N'-Diiaethyläthylenurea, NjN'-Dimethylpropylenurea, Hexamethylphosphor "amide and K, K, N ¹ , N'-Tetramethylurea, which may contain lithium chloride and / or potassium chloride"

(2) Concentrated sulfuric acid, the concentration of which is greater than about 90% by weight, usually greater than 98 to 100% by weight. is OAER oleum (d "h. concentrated Schwöfe? .säure, containing up to 20 $> or more of free SO _{5) v} can contain the additive (for example, NaHPO., NapSO ,, potassium acetate, in a Mesge of 2 bie 3 Gew _o «- $ of the total mass may be present)» The choice of the sulfuric acid concentration »which is best suited for a special mass production is based in part on the logarithmic coefficient of the polymer used 0

(3) Hydrofluoric acid, either alone or in combination with additives such as water (1 to 2 wt.% Of the total mass), ITaF or KJ ¹ (1 Ms 2 wt.% Of the total mass), an inert chlorinated hydrocarbon ( for example CH ₂ Cl ₂ ) or mixtures thereof is used (in an amount up to 5 jreWo-Jo of the total mass) »

(4) chloro-, chloro- or methanesulphone; 3 acids that alone or in combination with additives such as methyl chloride (up to to about 2.5 xew. ~ $) can be used.

Mixtures of two or more of the above liquids can be used in suitable combinations, for example mixtures of amides and ureas, hydrofluoric acid and fluorosulfonic acid, fiethansulfonic acid and

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Sulfuric acid, oleum and OKLor-, Fluor- or Fiethansul-. fonsäure and the like.

As already mentioned above, the use of additives is preferred for many compositions according to the invention. It is assumed that special additives support the solvation of the polyamide in the liquid medium. For the amide and. Is urea media highly desirable that at least about 2.0 crews of lithium and / or calcium chloride be added _? to from speziallen isolated polymers, such as poly (I, ^ benzamide) an acceptably concentrated mass to liefera "In the preparation of amide or urea-iis SLTU compositions, the salt before or during NaOH _s of the polymerization are given, wherein it is preferably formed as a by-product of neutralization (if, for example, the nobenzoyl chloride hydrochloride and the neutral xithium carbonate bind, then lithium chloride is a product of the neutralization reactlo ")" - in the production of an amide or urine insulated polymer, the salt may conveniently to the polymer and / au oclsr the liquid medium are added _o Hei "each Gfyp mass (isolated or in situ) sais is, in a quantity greater than about 20 wt * - ^ in allgemelBei? neither necessary nor desired "with less than about 15 Q-ev /.-= 5 & precautionary and about 4 to 8 'lew' -96 'most ... most. preferred 3iaa _e me andea? e liquid miles as amide line ¹ urea3 the use of other solvation ingredients (for example those mentioned above) may also be desirable ^ whereby in general! your amounts (at least less than about 5 öewo '»$) this additive θ can be used.

Although the masses essentially consist of the polymer and the liquid medium (if necessary, solitary Additives), susätjsllohe substances can be in the

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Mass be present, for example small amounts of inert organic liquids (e.g. tetrahydrofuran, dioxane, benzene or acetonitrile) used to disperse the monomer in the amide or urea compositions be water (either added intentionally or accidentally) and the acidic by-product of the Polymerization reaction (if, for example, less than the stoichiometric amount of a neutralizing agent is used).

The usual additives, such as dyes, fillers, Matting agents, UY stabilizers, antioxidants and the like, can be incorporated with the polymer or copolymer or in the inventive Masses are dispersed for the intended purposes before molded articles are produced therefrom,

Compositions according to the invention can be produced in two ways by adding, for example, polymer and the liquid medium (and, if present, additives) in eissr conventional way (for example with a stirrer ») be united. Some masses are made at room temperature conditions formed and are useful under these conditions (for example spinnable). Other masses require special heating belt methods, i.e. it can in many Falling admixtures which flow at room temperature sun «- · - while in some cases heating, "v" oriiugsweir3 with stirring, and sometimes heating and Cooling policies are not required. The extent of Erhitausig and / or cooling, which are necessary to ensure a usable May> ee greed to form varies with the composition liquid ϊdium, the polymer (the composition, the logarithmic viscosity steel, the crystallinity rad of the particle size of the polymer sample used) and the quality of the stirring device. When manufacturing the

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ser masses must be taken to ensure that local overheating and formation of a ^w be dry "or gelled patch" at the meniscus this Zusammensetsung or on the walls of the container which is used avoided. Such polymer parts often do not dissolve again easily. Numerous suitable procedures which can be used for the preparation of special compositions according to the invention are illustrated in the examples. "

The anisotropic compositions according to the invention can be made from pine: ·? individual anisotropic phase or an emulsion of anisotropic and isotropic phases in every dispersion ratio or degree of dispersion Phase o Tiny amounts of undissolved polymer can be present in these phases or in the emulsion, especially if the mass is produced by dissolving isolated polymer. Film-forming or fibrid-forming polymer! «» Sat / solutionRinittel system, which contains at least one "of the above phases

Anisotropic masses

the mass-forming constituents according to the invention united in special concentration areas, the resulting masses are optically anisotropic, i.e., mikrosIiOpic ahc areas of a given till are duplicated breaking, a larger P.cotoe of the mass depolarized !. '. near polarized light (v; hereinafter referred to as "be" * jli.vitj oe.ij / that iranoh in the description of the present invention times such a'js light or polarized light denotes νλ: since the light permeability properties of the iai

3 ^l ex * e.iche of mass vary with direction

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_::, 0 09836/2187

Property is associated with having at least a part the mass is in a liquid crystalline or laesomorphic state. In "Industrial Research", May 1966, p 53 to 57 (G.H. Brown) describe that liquid crystals ran in many of their properties between the liquid and the solid state. You thus have extraordinary structural arrangements, some of which are the order of crystals and the fluidity of liquids give O

The inventive masses see anisotropy while they are in a relaxed state. Conventional polyamide masses know that they are linearly polarized! They look depolarized when they are subjected to a considerable amount of ocher action (for example, fluid double reaction, where Mol © Milo is hydrodynamically oriented in a solution) ₈ in the case of resting (d = h * stationary) samples however, only the measures according to the invention of this phenomenon.

It is assumed that the elongated, rigidly aromatic!) Polymers which i? the present erfinduagsgemlßen anisotropic Ma.3öen, in dan liquid medium substantially ßtabähiiliche units (aggregates or bundles *) form "diee J = elongate stoLfkettige K.trafiguraticm the polymer v / ith by dJ.e VJsrte of Eacjonenten α in the medullary Hou. '/ Ink equation [i \] ^? “ CBT for the diluted

Pol; v'fierisat mit niedJgoj-em MolelculEr ^ iwickf; In & ΐ 3ser well-known Gledohung [· ί]] regretted the

ars' / isk'jsitätsaahl ,, K nas Molelraiargav / i ^ ht wiü K ur.fi j; .? i'.c-inrr.o ata i'ür ain gefpbtnes Polyaie tex-Syttaiii "The predominantly" Kchrzahl of P at this year takes 3se Oleichung in dv literature Angev / eadvt v;? or the 1.St ₁ halrü V / erte unt ^ r O _f $ _& Uater dea Polyiaeris.?.toij, 1Ϊ.Ά In the Fiats en according to the invention used who ^ ei ^ .lsi; £ \ xv Pol, '/ - (ρ-benzamid) a «-value of 1.6 confirmed " _t ,

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measured on unfractionated polymer, it has an inherent viscosity in the range of 0.4 Ma 2 and when carried out in sulfuric acid (95 to 98 wt .- ^) Weightßdurfhsohnitt-MolelaLLa ^ gsvrichtsbes fcinBfiimge . a given system has a certain krluj.lscli.en exceeds the point of transition, an anisotropic P. formed, di.e the properties of the invention causes anisotropic masses.

A given according to the invention <3 polyamide / liquid medium ·· »mass is isotropic under a 'special polyamide tratlon» Who does the concentration of the polyamide increase _? the viscosity of the mass increases "BoI a point or in the description of the present invention αϊ β the" critical concentration point "is referred to, but in the forerunner of the curve of viscosity versus consentration a sharp discontinuity opens up when the ϊ-Ian ·· se without formation of a solid phase from isotropic to anisotropic partially changes "Pie additional -S ^ aba 'of Pslyssiä leads zi a Herabeetsuiig άβ £ Viaküa: i; Elder;! the mass, üa the mass mahv becomes anisotropic. An example of a curve of viscosity versus consistency is described in Bc ^ spi ^ 77 and illustrated in FIG.

A ge ^ ebojäe according to the invention3 Hasse iß * · ;? as mentioned above, to: .. sotrop, if the .8ostandteile of the? Measurements are present in special concentration ranges: the concentration of the polymer or its polysiörisais, whose logical viscosity Itätsjaahl and the temperature * exist: .ne complicated structure, which is generally applicable one in which it defines the range in which an upscale Maaso made of polymer or mixed polymer and rD.üaslgera Hasliu? ß is riaotropic. Exemplary ph ^ sonbessieiimi ^ en are shown in example 64 at figure 1 and in game 74 and? J'igUL · ·] iH'd 5- . Do; like relationshipsa can be used for others

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009836/2187

appropriate ingots can easily be determined by Rotitineversuehe.

The "Kritiscae Konsentrationspunki;" varies rait aera special polyamide as well as its weight percentage and its logarithmic viscose! tatezalil »the epcisial liquid Moäiura and the temperature. The influence of the percentage by weight of polymer and the temperature on the masses of various polyamides is shown in Example 75. The influence of the logarithmic ©! » The choice of two different polyamides is shown in Example 74 and S ¹ JL-gur 6 and 7.

Anisotropic materials can be manufactured, the polymers and copolymers as described οοβίί Erfindußgsgenäß ,, entAialttm that up to about $ IO> (mole basis) aromatic A "heXf-on sufv / SiSeN whose ketteiiVßrlängerßde bonds not ira v / esentliohen! Coaxial or parallel and oppositely directed. For example, high molecular weight and random distribution of p-amisobenzoylchloride hydrochloride and aminosoylchloride hydrochloride can be prepared using the low temperature solution polishing processes described above will. A compound produced from such a mixed polyamide, for example in N, IT ~ J) imethylacetamide vjy.ä lithium chloride, has optical anisotropy _β

Anissotx * oi> e P & ßiien of aromatic miochpolyamidesB, in which all chainDTlängernea bonds of each aromatic IZc-zn in the wee «ni; lio; ieii coaxial or parallel and oppositely directed 8ΛΜ, are also included by the present invention. BeJ.fjp: Lfcl3we.-Se can an ordered mixed polyarüic _? fc <. rg ο fit'-? X It from 4 _n 4'-Diaminolienaanilid and 3? Ss ~ T'iiphthaJ oy] ι hlorl ^ or .2,6-Napnt; x6iloy3 chloride, in an an.iao tropic I an α β ■ ^f -; ingeßrbeite "· are ,, ei ie (1) dae Mlsohpolymerisai, <?; ine /> raid ti-sohun ^ and Lithiuinohlorid odei '

· »Ρ λ

09836/2187 bathroom

(2) the copolymer, a suitable sulfuric acid or contains oleum

A spinnable group of anisotropic masses contains about 6 to 15 wt. - # Lithium chloride and the remainder an amide mixture from Hexamethylphosphoramiä and N-Methylpyrrolidon-2p which contains more than 45 Vol- # Hexamethyl-ihosphoramid. The relative amounts of these constituents, particularly those of the hexamethylphosphoremide and N-methyl-2-pyrrolidone, contribute to the ease with which these dope are obtained. For example, as illustrated in the following examples, a spinning maize made from these constituents which is flowable at temperature will hold if a special amide mixture is used. However ¥ _e nn another Amidmischung that contains more hexamethylphosphoramide, is used with the same amounts of the polymer and the salt, the combined ingredients must be heated to at least about 35 ⁰ O to obtain a liquid anisotropic mass whose birefringence observed can be. The compositions are preferably prepared by vigorously mixing the constituents at low temperatures, for example at 0 to -10 ⁰ «

Another spinnable group of anisotropic masses contains about 5 to 25 wt to 8 wt .- # lithium chloride and the remainder ij, il) imetnylacetamid. In addition, anisotropic masses can be produced, dia (l) poly ~ (2-cfclor ~ p «p'u. ':">;,? .- .: -v rephthalamite), lithium chloride and NjN, K ¹ , N'-Tetramethylhar ·:! - stoff - (IMH) uiifi (2) contain the same polymer with H, H -dinethylacetamide uric potassium chloride. For example, anisotropic f.anse is produced by adding 2.5 g of poly - (2-ohlor-p-

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0 098 3 6/2187

phenylene terephthalamide) (inherent viscosity ^ inh ^Ä ^ ^{1 "2")} produced mixture are ^ with 25 ml of of 3.56 g of lithium chloride and 100 ml of tetramethylurea combined. This mass liefert'in a polarizing microscope, a bright PEiD and shows measured there , a permeability value (T) of 81.

There is a complicated relationship between the amount of poly (2-chloro-p = phenylene terephthalamide) and its inherent viscosity, the amount of salt and the amount of the amide (s) that determine whether a given mass preparation is optically anisotropic under otherwise constant conditions ₀ For example, an isotropic mass can be converted into an anisotropic mass by changing the polymer concentrate. * Example is a clear mass that contains 10 g of poly (2-chloro ~ phenylene terephthalamide), ^ l ^ _nll »l _s 13i in 100 ml of a mixture of 100 ml of N, N, dimethylacetamide and 4.3 g of lithium chloride contains »isotropic. If, however, a further 10 g of the polymer are added, the resulting mass becomes cloudy and anisotropic, as light depolarization studies show g of poly (2-chloro-p-phenylene terephthalic amide), η_ _inh = 1.13, and 100 ml of a mixture of 100 ml of lIjN-dimethylivcetamide and 7 g of lithium chloride is isotropic.

Compounds containing lOly-CS-ohlor-p-phanylene terephthalamide) can:. Be separated in two layers, an isotropic upper tube; and a diohtora anisotropic lower layer. This separation can be achieved, for example, by leaving a ßpinnmanoe for a tent span, dia auoreioh; to achieve the separation (for example 1 V / ooho) ode :? it can for example be achieved by centrifugation. Since an isotropic poly (2-chloro-p ~ phenylenterephthalain.Ld) composition by changing the polymer concentration at a constant logarithmic ^ Vlekositätezahl of

009836/2187 sad

Polymer can be converted into an anisotropic mass, a change in the volume of a given anisotropic phase in a mass system with two layers can be achieved by incorporating a polymer with a higher inherent viscosity into the Hasse /. For example, separates a mass that contains 10 g of poly (2-ohlor-p-phenylene terephthalamide), r ^ _n J ₁ »1.15, in 100 ml of a mixture obtained by combining 100 ml of Ιϊ, Ν-dimethylacetamide and 3.12 g of lithium chloride is obtained when standing for a long time in two layers * The bottom layer makes up 20 # of the total volume. If the mass is made with 10 g of this polymer with a logarithmic viscosity number of 1.85, the anisotropic bottom layer makes up 33 % of the total volume. It has been observed that the maximum amount of salt that can be present in an anisotropic mass of this polymer increases as the inherent viscosity of the polymer used to prepare the mass increases.

It should be noted that the combinations of the above Beetandteile mentioned are chosen to be aniootropic Bulk deliver. It is possible that with certain combinations of constituents this is not the case. For example, poly-Cp-phenylene-p ^ '- diphenyldicarboxamide) and poly- (p, ρ'-phenylenebenzamide) which are anisotropic in oleum Form masses, in HF or in some amides and ureas, those with other polymers according to the invention are usable, no anisotropic masses. Whether a given Mass is aninotropic, is spawned by the following methods described.

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Q-1031-R

Determination of the optical anisotropy

In the following examples, the anisotropic character of the compositions according to the invention is exemplified in the following V / also described:

(1) by graphically showing the relationship of bulk viscosity to polymer concentration for determination the "critical concentration point",

(2) by numerical values for the light transmission through crossed polarizers identified as "T" or "DDA",

(3) by observing the bright field that appears in a polarizing Microscope can be seen and

through a visual determination of the "Rühropaleszena".

Critical focus point

The anisotropic compositions of the invention are characterized dureh a "critical concentration point" (Uh ₀ at the rise of the curve of mass viscosity versus Polymerisatkonzentraiion is a sharp discontinuity before, "Venn the concentration that point exceeds" is anisotropic the Marse, and further addition of the polymer results in a Ilernbsetzung the viscosity, while the mass is anisotropic - This "dot" (as well as the full curve of Viskoaitlt against concentration) is routinely determined, j conventional Komsentrations- and viscosity wöbe ^ - · meoBungsmethcden be vorwendet For example, a.

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Q-1031-R

Polymerisatraasse according to the invention in a polyallomer test tube be brought with a tetrafluoroethylene-fluorocarbon cap (TeflonvS /) is provided through which a viscometer spindle extends into the mass, being constant Temperature is maintained. The viscosity of the stirred mass can conventionally be measured with a viscometer (For example, a Brookfield Syncho-Lectric Viscometer, Model RV, manufactured by Brookfield Engineering Laboratories, Inc., Staughton, Mass. or an equivalent Device) can be measured. Viscosity measurements are made at the initial polymer concentration and at higher concentrations (i.e. after an additional known amount of polymer has been added) carried out. According to this or an equivalent procedure can for this system (the given polymer and the given liquid medium at this temperature) Plot a curve of viscosity versus concentration and it becomes the critical concentration point (i.e. the discontinuity in the slope of the curve) is determined.

"T" test

The T-fourth tea can be determined by placing an anisotropic mass according to the invention , prepared as described in aev present description and without suspended solid material, between a crossed polarizer and an analyzer. The Maaeenprob-e is usually used as a layer with a thickness of 80 / U. A drop taken from the interior of a mass sample according to the invention is thus placed on a dry, clean, tension-free glass slide

~ ²⁸ - BAD OfiSGiNAL

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Q-1031-H.

square cover slip »that on one edge through a glass tube or by a glass rod of known thickness (1.3 mra diameter are appropriate) is carried on the Droplets pressed around the roof of a liquid wedge to build. The edges are made more transparent with a quick-drying binding agent (for example DucovS ^ Kitt) flexible, water-resistant adhesive dor applicant) closed, whereby direct contact with the mass is avoided ο the wedge-shaped edge is with excess mass. closed, which is squeezed out. During work there should be evaporation, moisture absorption, excessive Shear, dirt and any suspended solid particles are carefully avoided.

The samples will stand for a sufficient period of time serene to allow relaxation of SA surges, the sicii result from slide preparation ,,, uia ensure that the sample is static. For example, di-3 amide or urea will take about 10 minutes to ground let relax for a long time, while to relax from Acid masses (especially of the more viscous samples) generally up to about 1 1/2 hours are required and to relax the other compositions according to the invention, · for example, the fluorine and Ohloraulfonöäuraiaasson, bis to etv / a 1 status is generally sufficient «,

The wedge we! on a microscope stage between crossed The polarizer and analyzer are arranged in a light beam which has the intensity that is usually lost in microscopic examinations. The wedge becomes like this arranged that the thickness of the middle of the mass layer, through which the light beam passes through is 80 vu. The Inten-

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009836/2187 * »« * ■ «.

sity is measured with the polarizer and analyzer crossed (I®) (the superscript s indicates the presence of the sample in the wedge) and with the analyzer removed (I®) and the difference I ^s - if is determined. The stepping light can be measured by conventional light-sensitive measuring devices (for example photomultiplier devices, selenium or cadmium light measuring devices, bolometers and the like). The same measurements are then carried out on an equally constructed wedge that contains air and the difference I ^c - I *? (the superscript c stands for control experiment). If the masses according to the invention are introduced into the wedge, then the expression (I ^c - I?) - (I ^s ~ I?) Is greater than garbage and greater than that which can be explained by experimental errors with the use of appropriate care and precise instrumentation . This value gives; reflect the increase in light transmission through the analyzer due to the presence of the sample. The size of (if - 1 °) - (if "- 1+) varies with the solvent used, the polymer concentration, the concentration of the dissolved salt and the units in which the light intensity is measured.

The device by means of the anisotropic character or the T-value is determined constitute masses in the examples, consists essentially of a "0. A. Spencer Orfchoscope Illuminator" of a tungsten Überspannungsmikroskoplainpc (Färbtemperatur 3800 ⁰ K) an optical wedge ₉ containing the sample, an optical wedge that contains air, a Bausch and Lt mb polarizing microscope with a Leitz objective 1OX and a Leits-Olcular Periplan 1OX, 3> nen G-oases "Sinaysix" exposure mass and a »? Includes Polaroid HP3 Industrial Li nd Camera. The wedge containing the sample is produced in the manner described above and

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19296S4

Q-1031-R Si

placed on the microscope lens (ie between the polarizer and analyzer) to form a sample layer 80 / U thick in the path of any light reaching the analyzer and the light meter. The polarizer and de? Analyzer are set} so that they cross at 90 °? "Provide polarization planes passing through the analyzer on the above described V / ec hinänrantretende light from dev lamp is projected into the camera and in the image plane (on the frosted glass height) measured by the exposure meter (I ^s) * The same measurement is carried out at remote analyzer ( lf) o By repeating the determination with the control wedge with air at 80 / u thickness, 1 ° and I® are obtained. The light values displayed by the "Sinarsix" light meter, which are printed out in logarithmic units on the base 2, can be converted into logarithmic units on the base 10 by multiplying them by 0.301 (ie by log 2), after which the number is increased to 3 Base 10 is determined for these products * These humerus values are defined as I? »I_» IY and l_ denoted. VergloichsintenGitätsmonsungen * free vcr the specific intensity units are sweck-iiäßigerweise "given as relative intensities (ie _e Intensitätsverhäjtnisße or intensity fractions of hindurohgetretenen light intensities) The term 1 ° / I_ is the fraction of light intensities obtained by the examined Maooe hindUTchtrltt. The fraction I® / l ° is the fraction of the Liclr-tes ;. which passes through the control wedge. The difference ei-ζ (I ^ / if) ~ (I® / if) gives the increase in intensity

Since for f-'a depolarizing Ii? Rob3 the maximum value of

009836 / 21I7

Q-1031-R Si

if / I - ΓΓ / I ^{G is} theoretically equal to 0.5, the expression 2 (1® Vif '~ ¹ J Vif) can be used as an index for the increase in the permeability (T), since this Way, the maximum value is 100. When measured in accordance with the above procedures, masses with fourths greater than 4 are considered to be anisotropic in the context of the present invention _{or the like}

"DDA" -? Pe3t

Another measurement, which provides a numerical quantity distinguishing anisotropic masses from isotropic masses, is described in the examples. This measurement is directed to the degree of depolarization anisotropy (DDA) and is used in the context of the present invention. This quantity is a measure of the depolarization of the linearly polarized light passing through a sample and is given by the following equation

loo

defined, preceded by the character ^} Measurements on «ine: ·? Blank test (fully and ig isotropic), C an opaityi.; Facto: c in your sense that e: ln given adsorber mat double thickness cjn; ^{ä has} n as large £ -fourths as in simple oioke, and

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BAD OHiGiNAL

009836/2187

-YY . -Xu

and 0> mean measurements that have been carried out with a parallel or perpendicular polarizer and analyzer. This equation is essentially a percentage difference equation. In practice, the incident light intensity is always adjusted so that a measurement of £ qf (and! '! If}, which corresponds to the unit (doh «a bubble display of 100 ^)» with parallel polarizers: for both (1) Blank sample as well as (2) sample obtained w ±: cä _{; t} what for (1} a complete lack of depolarization and for (2) a complete depelarization for the observed field anseigto In this Pail the DDA equation is simplified to

00

The scale ranges from zero to 100, the former fourth being complete isotropy and the latter value being complete aniootropy for the observed field »

The device used for the ODA measurements consists of a Bau ach and Lonib polarization mitoscope (rotatable polarizer, fixed analyzer) - The light source is a Silge vmä Ku, an ortho-illuminator B with a constant 100 W operated at 115 7 -Lesjpe G.EoBMY, the change in tint Lieh ansität regulating £ "&" (and € qf) is performed by lie Heutralfilter and the iris of the light Quellee the bindurchtretende light is at a

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009830/2187

ΘΑΟ ORIGINAL

Q-1031-R

22 1/2 V operated, light-sensitive resistor Ct.EoB = 1036 and a 50 / U ammeter is used to display the relative intensity "The light passes through the following components in the following order: light source, polarizer, condenser, sample" microscope objective ( 2Ox, leitz HA - 0.33 * FL, long), analyzer, eyepiece (1Ox, compensating) to the photo resistor ₀

All measurements are carried out with red light, which is generated by a red wave band filter (with a permeability range of approx. 600 m / u up to a maximum of approx. 650 m / u in the visible area) in the lighting fixture Calibrated with a series of Kodak Color Compensating filter films (ÖG50R), with a single film assigned an opacity of 1 (100 '/ S transmittance on the meter), two films an opacity of 2, etc. * Van rend der Eiü The films are then brought onto the Kikeos! vopobjeki <table and the microscope is focused approximately on the center of the filter film stack (vertically). Nragen n-Arbeitsbed3 / are designed so that a linear calibration curve xint logarithmisc> ien wiri measured values obtained plotted against the opacity ₀ The Opazitätsv / erte the sample are then directly from ä jr calibration curve entnommeno This ergiöt a. relative ^II H) t opacity value "for each sample _o

Samples for the measurement t \ rex'den made * in-lein a drop of the 'let from the inside of the larger pro ^ 3 «Diuser drops are applied to a Pyrax ~ GJas; schöi-" be ■> An annular spacer aua Fluorocarbon (Teflon®) 51 m thick is placed on the disc

- 34 ··

SADORIGINAL

09036/2187

and a second pane of glass closes the cell. This unit is brought into a special screw structure that holds the glass in contact with the spacer to ensure a constant sample thickness of 51 / u (the sample essentially filling the cell) _B These samples are allowed to relax for 1 to 1.5 hours before measurements are taken. Blank samples are prepared in the same way with pure solvent.

When carrying out visual observations (in the microscope with crossed polarizers) of the masses whose DDA is measured, every positive value for DDA shows the presence of anisotropic phase. The higher the DDA value, the greater the amount of anisotropic Phase that is present in the bulk, apart from the extreme borderline cases with less than about 5 5 * of a phase present »This is partly due to the sensitivity of the apparatus β Even if the proportion of the anisotropic phase is small and not evenly distributed or dispersed» small fields of view can be selected, oils have less than average or no anisotropic phase * A 100 ^c / 5ig anisotropic mass does not always result in a DDA - 100, probably due to irregularities in the structure.

The IP and DDA'iests described above describe the Quantitative light permeability of anisotropic masses. However, a qualitative assessment can also be expedient

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009836/2187 sad

Mood can be performed using a light source, one Analyzer and crossed polarizer (or equivalents thereof) as described in these tests were used are «when such polarizing elements crossed allows a resting (relaxed) bulk sample to be placed between the polarizer and the analyzer, essentially no light passes if the mass is isotropic. However, if the sample is anisotropic it becomes light transmitted and a relatively bright field is observed (the intensity of the light depends on the degree of anisotropy depends on the sample). A more detailed description of the type of field observed in Hassen containing anisotropic and / or isotropic phases can be found in Example 64.

Rühropalesζenζ

The term "stirred rheological" is used in describing the present invention to describe a property characteristic of anisotropic masses which is visually observed with the naked eye. Many of the inventive masses appear when observed en masse in a transparent container _r cloudy or hazy and still contain no or practically no undissolved solid. If, when viewed in reflected ordinary light, the mass is disturbed by tilting or rolling the container, or even just by slow stirring, a characteristic, easily observable satirical shimmer or glow is produced, which is observed even after the disturbance has ceased and then decreases in intensity «In some

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009836/2117

compositions, no color sensation is evoked, while a bluish tone or a degree of chroma is different may show by observers to be pearly or is scintillatingly written. Outside color in the mass - like yellowing - due to smaller amounts of impurities or as a natural color in some Pc-lymex.-isates, modifta Leren the observation of the color that watch Shear developed masses, which are disturbed in the above described process, show on the surface often the appearance of striations and / or grains. These visual effects are anisotropic in the case of the invention Watched the crowds. Neither have such effects conclusively prove that the mass is anisotropic, but such masses are generally anisotropic or become anisotropic when more polymer is added (provided that the limits of solubility permit this). For the sake of simplicity, the examples are visual Observation of all the above-described variations of the phenomenon called the occurrence of "EUhropalesaeng".

Masses, which are described below as anisotropic, can show this ι Rühropaleszenz-Effect or can prove to be anisotropic according to -Jan above-mentioned qualitative or quantitative methods, ie ₀ , the critical concentration point is determined or the sample is between the light polarizing elements , for example in a microscope for the depolarization of linearly polarized light, either qualitative or. quantitative, observed as described above. Each of the qualitative or quantitative methods described above indicates anisotropy in a suitable manner, although an odea? several such working methods for a given mass more expedient and / or suitable

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009836/2187

BATH ORIGINAL

IV J I

can be more precise «The determination of the critical concentration point is the preferred test for" the "" determination of the anisotropy, since it can be used appropriately and precisely for all anisotropic masses according to the invention »The qualitative test (visual observation between the elements polarizing the light ) is preferred for reasons of practicality when examining a large number of samples. The observation of the Eühropalessens is also convenient and generally shows anisotropy »Among the quantitative tests (apart from the determination of the critical concentration point) the DDA test is preferred for sulfuric acid masses, since it is more sensitive for masses of this kind in anisotropic concentrations lying at the limit, while the ϊ test is generally preferred for amide or urea compositions. Although the T-test and iii) A - Test in general for all inventive Hate £ are uitable,, since hydrofluoric acid (in HIMTaseer or generated by the Fluorsulfonsäiire in other Maxell) Glass attacks mm in such cases precautions /. or modified test methods may be necessary (for example, replacement of the glass slide with a tension-free H3? -resistant slide and cover of the ilicroscope lens from? EP gas) »

Usability of the Itoseen and Fadenher-steepum

The compositions described above or according to Hassan of the present invention can easily be used to produce Threads or fibers, films, fibrids and coatings are used become α

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tU; »

Compositions according to the invention which contain at least 5% by weight of polymer are preferred insofar as they are particularly useful for the production of threads or fibers - these anisotropic compositions can be used for the production of other molded articles, the preferred use of these compositions ( as well as related isotropic hates), however, is the use in the production of threads or fibers by conventional working methods and / or the processes described below. The term "threads or fibers" is used in the description of the present invention in a general sense in order to include the numerous conventional thread or fiber structures. For example, it can be staple fibers or continuous threads. Likewise, the threads or fibers can be of a single component or consist of many components (e.g., a thread Eweikomponenten ~ _s with the two components from various inventive PolyamidzuEe.raffienpetzungen exist). In addition, one or more polyamide compositions according to the invention can be present in a given thread (or pad component), c'.h. The thread, for example, "the fiber can contain a composition of polyamides or a mixture of white and black-and-white sets of this kind". Strands or in multi-filaments bundle ( "for example yarns) used v / Ground all of this conventional Fadenstrukti reindeer, which consists essentially of the bo ~ ai here; M. I.eli" nen Polyujaiü & isbanijUtiu & riiiAKigen lic-stolien ι \ κϊ herein bc- '-iohrioberii- internal structure \ az \ i. having the properties described here $' are encompassed by the present invention ο

According to the traditional hatred and ockspitin method, the other, in accordance with the rules, ammunition or hairs are also included

«. 39 -.

009836 / 21Θ7 ^ßAD

Q-1031-R HO

extruded conventional such devices as filaments, Beiß] IJaßspinnen a suitably prepared mass, and for example, an amide · »or urea medium contains the polymer and can vary the temperature of Hull to about 100 ⁰ C, in a suitable Eoagulierungsbad, for example a water bath held at 0 to 90 ⁰ O, extruded, the coagulation bath depending on the solvent used in the manufacture of the = mass. Other useful coagulants include ethylene glycol, glycerol, mixtures of water, methanol and an amide or Harnstofflöaungsmittel, mixtures of water and alcohols and aqueous salt baths, which are maintained, for example, at a temperature of about -20 to +90 ⁰ C. Dry spinning. "Can be achieved by extruding the compositions or masses according to the invention into a heated gas stream, as a result of which evaporation occurs and" threads of the polyamide are formed ".

After they have been made, the threads can be passed over a suhltelr; ^ roller guided and wound on bobbins was-on. lie development of maximum thread and yarn properties ^ words can be assisted by placing the coils in or in water Mixtures of water and water-soluble inert organic Liquids (for example acetone, -A'thano3 » Glycerine, Ν, Ν, Ν ·, N »-Tetramethylurea, IT, N acetamide) to remove residues of Aifi and salt or acidic solvents, after which is dried «. Pie Bntfernurg dor remaining solvent and / or salts can also be obtained by forming or passing the yarn on its way through aqueous baths by moving the bobbins in the formation of the yarn with V / aaser be rinsed and the strands of thread instead of the thread ~ -

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SAD OHlGlNAL

009836/2187

bobbins washed or immersed. Dry spun yarn can be used by many even with a small amount Water solidified.

The from the anisotropic compositions according to the invention or Hassen and related isotropic masses made threads or fibers are through an extraordinary Imienstruktur and characterizes extraordinarily high tensile strength properties, both in the state after extrusion and after heat treatment »

This extraordinary internal structure of fibers appears * through its low orientation angle and / or its high speed of sound. The physical meaning «·: - '■ c ^ leatlerunewinkele int that it gives a" WiJ ₁ VsI, (ie d: - Jl'f.lftc des orientation ".Lukel a) around the paäeaach ■: & - in which a given percentage of KrlBtdllii? .ri is established. In the inventive paden a holler prose eats teats (ie, more than about 50 ϊ *, generally about 77 #) of the crystal is in cHeaeai V / inks ». (one half of the Orientierun ^ sv / angle) uw the thread axis aligned. This percentage is determined from its intensity curve of the diffraction pattern of Paclens (as will be observed below). Boiaplelswaise, the intensity curve for most threads according to the invention (ie for essentially all heat-treated threads and for most threads in the state after extrusion) is essentially a Gaussian curve. With such a curve which is interpreted! Fall about 77 </> the diffraction intensity in these Viin "y.el, that this shows that a similar percentage of Krißtalliten in this corner is aligned. With the few threads (for example with some threads in the state after 3 extrusion), in which the curve cannot be Gaussian-like (for example

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009830/2187 _fiÄn

“AD

the curve can be composed of several curves which partially resolved peaks are more than about 50 the crystallites aligned at this angle (see, example 83) ο

The threads according to the invention baw. Fibers are characterized ί / α wx the characteristic orientation angle by the speed of sound. The speed of sound is a structural parameter that occurs with the molecular orientation of the thread along the thread axis in 3αsmmm; 5i2 ^T ! A higher value dor speed of sound UEAs result of a higher feades of molecular Orientier-Ji: ^ along the JFadenaehse. Speed of sound and verbindbz parameters in "Textile Research Journal", Bava! DCIX _s No _s 7, page 525-535 (1959) (Chareh and Vcseley) and in "Journal of Applied Polymer Science", Volume III. Nv ₀ 9 »Pages 266 to 276 (1960) (Nosel.ey) describe 1"

Orientation angle and / or speed of sound indicate the extraordinary internal structure of the pad ^ ₀ These structural parameters each relate to the orientation and each show its exceptionality = the speed of sound is a measure of the overall molecular 3 orientation, in contrast to ■ crystalline orientation. This entire molecular orientation disorder is not affected by the orientation described by the orientation angle, ie the orientation angle is a measure of the crystallinity orientation "which is determined by X-ray measurements" by one of these orientation parameters or by both, with each parameter describing the exceptionality in a suitable manner and with the parameters for the inventions

BATH ORIGINAL

009836/2187

Threads are interrelated »

It is assumed that the unique internal structure of the threads according to the invention is responsible for their extraordinarily high tensile strength
and the speed of sound) and the tensile properties of the pad are shown in Figures 8 and 9. These !! figures,
the results given in the following examples indicate that the initial modulus of the pads according to the invention increases when the orientation angle decreases (FIG. 8) and / or when the speed of sound
increases (Mgur 9).

The threads according to the invention , as shown in the following examples, have these high eye strength properties in general "as spun" or "as eztrudierf'e ^s ' V / xe spormene ¹ 'or" as extruded " flnäimgü *' Appropriate loading are defined as 3? oes that are used in the normal spinning process (ie with porrnuags, design or

are formed, but not yet
('Dnnung) or Hitsebehaiidlung untex'v / ori
ü®n are, dlo the raolckulare order or the anoi'dtmng; der PolyrserisatEHilöküle changed. Me? Ed can, however
Vision and learning stages have not been affected by the
required; are to solvent cd er impurities
KU «sntfo- ^ n-jn, 2u arulsren work steps, üiv you
vj ^ röfiii kannnfv.i, οΐιηε don fimciamsntaXen Olmrakter djr Täüen & veräiid em, belong

(1) Application of finishes, dyes, coatings or Adhesives *

009836/2187

BATH ORIGINAL

^Q - ^1Ü31 - ^H "1929684

(2) physical treatment of the thread by twisting, crimping, cutting into stacks «

(3) Use of the thread in the manufacture of molded articles, fabrics, papers, resins or rubber compounds and the like

Filaments according to the invention in the "as extruded" state are for special end uses, e.g. for mature cord, are preferred. It is generally used for such applications it is desirable that the thread also has a high modulus and a high strength or tensile strength value and elongation of about £ 5 shows. Treatments according to the form however, (e.g. heat treatments) that improve modulus and strength often reduce elongation (for example to below 5 5 ») · Ba particularly preferred Filaments according to the invention in the "as extruded" state have desired high moduli and strengths and elevation values of at least etv? «$ 5 show, these are "as estruded" threads are fine for such end-use applications suitable"

The Zugfestigkeitfsoigenschafton in Condition-- "vrie" ixtrn diert "of both the wet al3 also ηen filaments may have been improved by the undrawn Fgden vain subjected to heat treatment Keißluftöfer, heated bars, slots xiuü plates and liquid Sri itzimcabäsJer are of such useful He Zugfastigkeits ^ igenseiiafteii the threads vreräer · preferably improved ,, indei-i mmi turn, "dripping held t of göstreckten Ffiden in one? Stickfitoffiit- üie at a temperature in the person vein about

300 to 1OCX ⁰ C, preferably from 500 Ma 60O ⁰ C,

- ■ 44 -

SAD ORIGiNAL

0 0 9836/2187

is heated for about 0.1 seconds to 5 minutes, preferably 0.1 to 10 seconds, as shown below will ο

The erfindun ^ sgeaiäßen threads have excellent chemical and thermal © Eigenschaftenο They retain their 2ug ~ strength properties at when heated for 0.5 hours and ⁱ in one jSiger aqueous hydrochloric acid solution and 1; warden cooked iiger alkali solution. The threads are after 1-3tündigem immersion at 60 ⁰ C in komiaerHiell used Tiockenreinigungs-Iiösungsmittel as perchlorethylene and £ richloräthylen substantially unaffected. The threads do not sustain the combustion if they are removed from an · open flame «

The excellent tensile properties of the invention Threads make these particularly useful as reinforcing agents for plastics, tire cord, V-ribbons and the same.

The compositions or measures according to the invention can be made by means of a? Conventionally an ilaSextrusionDiethocle in Pilrae was written. Such films are usually held under hold when they are subsequently dried and washed. Zanyan wets produced in the manner described above can also be formed into fibrids by precipitation methods, as described, for example, in XTSA patent 2 999 788, or they can be formed as a thin coating on a variety of substrates that can be applied in the form of foils, papers, wires, hate, faeces or fibers, fabrics, shiu "* laen, solid > üqt uiikro ^ uröeen objects and aegloioli", The documents can be glass, ceramics, bricks,

maam it ~ ⁴⁵ "

009836/2187

BATH ORIGINAL

-fÜ Ht

Concrete, metal (e.g., copper »steel, aluminum, brass) ₅ Holis and other cellulosic materials, Ohe ¥ _{t s} polyamides polyesters, polyacrylonitrile, polyolefins" poly "vinyl halides, cured epoxy resins, cured aldehyde barnstoffhar5e and the like.

An anisotropic mass can in general ?! sur Herat oiling a thread can be used, which in the spun state Has properties that correspond to the properties γοη F ^ .ösr, superior are »those from an otherwise correspond-roobawSöii ! ■ let are made that are isotropic or less anisotropic is (i.e. from an emulsion of isotropic and anisotropic *: Phases in which the isotropic phase predominates) “Sis opposites of the Si.xenschaftan a thread from a high Degree of anisotropic mass compared to the Eiganschafteii ainsa Fi. dens, which is made from a mass that is somewhat m; - ~ Isotropic or isotropic are roped in the examples.

Measurements ^ and Testa

The logarithmic © viscosity number Cl ^ y,.) Is through oils the following equation - -.

In C \ rel)

defines, in which ('! «« ι) ^ ⁰ relative a Kon sent:. -ation of 0.5 g of dös polymer lau fcs In J 30 v-2 t »L mean. The relative ViakoelüHt (η _f,,

■ j Λ Χ. * A

BATH ORIGINAL

009836/2187

is determined by dividing the flow time of a dilute solution of the polymer in a capillary viscometer by the flow time for the pure solvent bestiramt at 3O ⁰ C, whereby concentrated (95 to 98 #ige) uses sulfuric acid as LötSiingsmittel, i * ENN otherwise indicated istο '.

The thread properties, strength, elongation and initial modulus are denoted by E / E / Mi and are given in their conventional units, ie. as g / den, $ and g / den »These properties are measured in accordance with ASTM ~ labor regulations D 76-53 (October 1962),» using a test machine ρ for example es.n Instron tester (a product of Instron Engineering Corp. » _T Canton _f Mass ,,), which provides constant expansion visibility. up to approx. 8 ^c p ruit of an expansion

of 10 jS / Minö tested, while samples old hell \ er <Sst Brudhöehnung are tested with 50 ^ / Hin ₀ «The samples & ίηϋ. Pad en with 2.54 cm length or yarn with 3 M ± nu \ n.ß (-m / 2 _f 54- am unü 25.4 <; ib length imd they -Xeste üti. * -Ei 21 ⁰ C and 65 ϊ * relative <: r moisture permeated

Oia 'Prcben ^ erdmi not boiled (GebeiKt) _s but ira ■ «?'. ⁵ ', göriii, incn boi Si ⁰ C and 65 5 »relative humidity; min * ^r 5c »? ite'iie 16 Otimden lang kondi '.; ionized fwan in the following m« nü3 >>; ffl ^r al is bozeiohnet as "Eigenzu ^ tand"), when nothing else is appropriate, V / Ann mentions an extraction treatment

4-7

00 9 836/2187

BATH ORIGINAL

U-.O ₅ ^ n HB. ■ ■ 1929684

is, ao it consists in boiling the ¥ 'düen for ^{30 minutes or 1} • 3-arne in 0 _? i tigern aqueous Natriumlaurjrlsulfab "SpPIeTi ₉ 1-ötünäigem drying at 40 ° 0 and at least Ib-siüiiüigevi conditioning at 21 ⁰ C and 65 i" relative Peiiohtiglctd ^ o unless otherwise indicated istο

Heat request & nö 1 ing of the thread:

The heat treatment process after extrusion, if the pad en van 3 yarns are used, which are built from the eri'inchra ^ e = appropriate flowable compositions and masses, includes, if nothing else is stated in the examples _s washing or immersing de: e it spur "EAMT F ^v aeden or Garae in water, they essentially bit νοϊΐ atm spinning media and / or salt are free, they wüixaoli ge ~ dried and then erhitsst in one of the devices described below ₀

Device Λ

This assembly consists of a stainless steel inner tube! Steel, 81.3 cm in length and 7 * 94 mm inner diameter, which is concentrically disposed in a second tube with 2.69 om outer Masser, wherein the whole structure is centered Ii a 30.48 cm electric furnace "By SWEi Uippel in the outer tube which om at a distance of 25 * A tone of each string of the center of the pipe arranged sindi _¥ v \ xd Stiefc "atoffgao introduced such that the enter» ^ 1e Stickr ofi 'through the annular space between the tubes hindurchtriti bite. J) he nitrogen comes out of the xiingi'öifaiusf.-ii space through a small opening in the wall öoa Innenrohrea in de ,? Is arranged in the middle, into the inner tube and then from the inner tube end with a rare Ga

- 48 -

8AD ORIGINAL.

009836/2167

speed after ausaen that ü ± q atmosphere irj the erMtsten 3Oy48 CIE Zona of Irnienrcmres least elmföi-L In animal Hinute a-asgaveohselt will have "The e.us öero üfsn arising ALUs-uenenden device 3 to about ¹ aiii it SVCs" υοώ j ed QH] end s.is rait asbestos fiber and glass tape ιϊικ ·? icskoH; _J i) ie temperature dee furnace is .re- · giiliertj the kmig be in the middle of Aussjemmtid dureli Lc "is strengthened by a thermocouple and aiii; A Min ^ eapolis-EorsQ ^ wel sailor in Veibindtmg stands "The heated drilling has a temperature profile with the dijaxinial partiapatiiTe ¹ iia middle range ten from pad eil through the pipe Rilirirßgseir are used j, no the X 'threads are centered and eiiesiar B © agitates.twg "with the pipe walls ku haltan»

Device ö

This device is, with the above rule, pipe crossover, type of furnace and the like is operated in the same general manner . the ends aufgsir / lc3r.eltei! Isolation and the fact that the nitrogen: "" let in in the direction of the gate A on opposite sides of the outside of the ear, they are at VoxTiciitur ^ ·. ^ ^Aii ^ on the same side ". Between the There may be differences between the two devices when it comes to nitrogen fluids.

009836/2187

SAD ORiOINAL

'Ii SO' ^ 929694

Device 0 ■

This apparatus consists of a stainless steel Innenrolir ca 89 cm in length and 1 _f 27 iKnendi'.rchraes ^ he concentrically angiabrssliu in a wide tube of ros ^ freiiug itfehl 2.54 cm diameter and 45? 7 cm length int ., whereby the entire structure is centered in a 30.4S CK-Elö'rtr -eden · Through two nipples which are connected to the end of the outer pipe (one with each end of the outer pipe) nitrogen gas enters in such a way that _t 5rß the nitrogen entering through the annular P wa * see the two tubes-passing "from dE-A r ± Y \ g tree reaches the nitrogen through swöi. ! your _? in ä nenrohrwand in the center thereof arranged Öffmrii ^ -sn in inner tube then UNAE from the Inrenrohrenden n'.it lor ^ r aus'sen GeBchwindigkait after that the A overheated 30s43 CIFL ~ 55one of Innenrohreo ■■ mindests.ifi ί1: ύ; · Α1 changed-v / ird per minute. The Aiissenenöeri of the Yarrichtungί dia protrude from the oven, siuC mf e - ';w; -. 5.08 cm from each end with Gl & sviolle iim ^ iokel b * 14e Temperature of the furnace is regulated by a Mirincü ^ jüh-H.: ^ Ic ^^ e'l "Pyro ¥ ane" »- B3gler, Ei it help ei ^ eu 1 ' ¹ IoS-SrOeIeKOnI; the one with the middle of the oyster. Surface Cq ζ lymeuwohvus is in contact «The e: ehitf.te pipe has eii'i ΐ ^ ρελ ^ πϊχ ¹¹ -profile with the · Maximalteniporaiur in the middleVet ^ u'h» J) i® nominal heat treatment sterapciratrir is by si f. I ; ^ eites (Formerly determined, dr.e with the outside ?: ^v T; -ml ^ i'ct ^ o surface of the inner tube in contact; r / ^ elitc leg passing threads through the tube are used to keep the threads centered with the tube walls.

- 5t) -

09830/2187

BATH ORIGINAL

O3 i

Device 3

HtQHe device consists of a drill from rostfreieis steel having 1.26 mm inner diameter and 81.3 ca Läng "^ ₀ Ib pipe Mitts is via a pipeline a biter stem · · introduced * material flow, of having such a Ge translucent" · speed ay a AEEN Hobrersden emerges that the Atioosplaäxe is replaced in äam RoYkT once per minute Dag .Rohr lat in a concentric steel tubes arranged _s by the 3tiol € 8toff through passage before joining the Garnbehanäii;.?. NSST - 'zone enters β the entire construction is arranged within a _β ^ s ?? small Yerb ennungßofens 0.3 xn length Bin Therißoelement is ingelötet äussersn on the surface of the steel tube and positioned in the Uähe represents Ofenel-eißeiite. the output of the! flierisoelements relates to a HiriHSQ. .) olis - Honeywell ^{l I:} j ^T * 7. ovane "-Hogler in conjunction" of fü3 temperature of Gfena xmä üqb pipe-regulated in Derax-fcIgen word that one on the Aur ^ öh-

'ts of the inner wall treatment orchestra soldered it ^r i ^ä hcrjU'j ^ lejaeß-b the l'eciperatur in this} area i ^:. :: il deo heat treatment tube s "the tsx.m -yten protrudes" is with additional H

^ ί "aiawlekelt. Sin typical profile aor 'Io tur ir * dft / π; 1 -« hr (ffir a sentral © or "rtosiisiale"?' ^: ^ z- TOTf. 536 '""'}, öa. * 5 by varying the position ci "r

e was found to be

009836/2187

BATH ORIGINAL

(0) Sl 1-929694 (6) (10) Heat treatment tube cm (inch) temperature, ⁰ G (12) Temperature profile öes (14) Distance from the entrance, (15) 0 (16) 15.24 (17) 25.4 (18) 50.48 (20) 35.56 (22) 38.10 (24) 40.46 (28) 43.18 (32) 45.72 50.8 55.9 61 71.1 179 81.3 356 452 515 532 537 536 527 474 368 270 213 184

The use of devices A, B, 0 and D in the treatment of threads is indicated accordingly in the following examples, together with the nominal heat treatment temperature, which is observed at the central section (approximately 2.5 to 5.1 (5m)) of the inner tube for the device.

ff eakhöhc nver i lältnis;

The peak height ratio is a measure of the relative intensity of the two main equatorial diffraction peaks at Poly ~ (p-benK {aiid) o is a suitable Beetinungiticthode des

■ '- 52 -

009836/2187

OWOiMAL

Peak Height Ratio (PHR) involves the use of a reflection technique to plot the intensity curve dos X-ray diffraction pattern with an X-ray diffractometer »

The measurement is carried out using isolated poly (p-benzamide) as follows: The polymerization mixture is slowly combined with a large excess of polymeric flour solvent, for example water, which is vigorously stirred in a suitable mixer and thereby turns into a powder or converted into a fine-grained porm. The powdery polymer is washed thoroughly with water and, if necessary, with ethanol, by repeated stirring in the mixer and subsequent filtration, and ^{dried in a vacuum oven at 60 to 90 0} O before it is stored or treated for subsequent processing »

About 0.5 g of water- and amide- or Harusioff-free poly »

• χ η

merisat who i sn with a pressure of 219> 8 χ 10 g / cm in a sample old “With wounding of Cu-KT * radiation uni with 0.5 ° slits is at a scanning speed of 1 °, 2 © s per minute, a recording sheet resistance of 2.54 cm per minute and a time constant3 of 2 an intensity curve from 6 to 40 °, 2 ©, recorded, where ZQ denotes the angle between the non-diffracted beam and the bent beam. The full scale of the recorder is set so that the peak with maximum intensity ^{makes up at least 50 c} / «of the scale, which is a linear scale. To calculate the PBJR value, a base line is first created from the diffractometer curve by creating a straight line between the points on the curve

- 53 -

009836/2187

-Mrt ^ oM BAD ORIGINAL

at 8 ° and at 38 °, $ 2. From the peaks in the * Near 20.3 ° and 23.4 °, 2Θ, are then (at constant 2§ values) vertical lines drawn to the baseline and the height of the peaks, in index sheet subdivisions j above the baseline is determined. The PHR value is daira from the equation

PHS

calculated, where A is the height of about 20.3 ° »28» located Peaks above the baseline in register sheet subdivisions and B the height of the approximately at 23 * 4 °, 2Θ » peaks located above the baseline in registration tabs Subdivisions mean.

A typical curve of an X-ray diffraction pattern of powdery poly- (1,4-bensamide ^ homopolymer, isolated from preparations in amide or urea media, is shown in Figure 3 »For compensation of instrument ten disruptive effects eats in the specified manner an equal · » moderate line drawn from which the measurements are carried out »

Sedimen did ioTis test:

3u of a solution of 1.0 g of dry lithium chloride in 30 ml of dry Ν, Ν-bimethylacetamide is added 0.5 β of dry polymer powder and crushed to a rope size of about 20 yu or less. Bas tube is closed with a stopper and to be 60 to 80 ⁰ C In erhitater "

- 54- -

009836/2187

SAP OBIGtNAL

• ν -ν .f

SS

Halt is stirred by a mechanical stirrer for a period of time ranging from 10 minutes to 4 to 5 hours. If PoXymerisatteilchen remain visible, the content of the tube is cooled to -70 ⁰ C (for example by immersion in a bath of solid carbon dioxide and acetone} / then allowed to warm, can be resumed until the stirring and heated as above. Bas tube is then left to stand upright for a further 24 hours without stirring. If, after this period of time, there is no deposited polymer residue on the bottom of the tube, the frozen product has passed the sedimentation test.

Crystallinity:

The one indicated by the X-ray diffraction diagram Degree of crystallinity is assessed qualitatively by visual inspection and using the following expressions:

amorphous: only has iIf Xubb rings or arcs *

Traces: a lot of diffuse scattered area with a certain amount of heat the main flakes.

low: Low degree of sharpness in the spots with a considerable surrounding diffuse scattering area "

medium: completely sharp spots, but with retention of a certain diffuse character.

high: very sharp diffraction spots and essentially J: a presence of diffuse scattering «,

With increasing crystallinity, the number of

■ - 55 -

009836/2187

BATH ORIGlNAt

Beuguagsf lick to _c

It is pointed out that these evaluations are only intended to differentiate the range of crystallinity which are observed in the types of pads according to the invention and do not represent any limitation in this regard.

Osrlentierungswinlcel des'Faäene bs ^ ₀ the FiiEer is after dei? general working method determined in 'textile Research Journal', volume 21, page 805 biu 822 09-51)
(Krimin and TobolskjO described iet ₀ E ^; i is a Wgit «. Viinkel-Iiöntgonstrahlbeugyngsäiagraiiffi) C ^ iu-'chAi? Ss.igisita- = diagram) made in Baden, wobsi« äias I. "&. Rbu3" -Pole camera v > is irrunderstood. The camera consists ^. »S ^ l ^ ea-Kollimatorro ^ r with 7.6 cm lengthways with swei lead (Pb ^ IÖ-Ehern rait O _f i) 6 35 cas diameter at each end i; nd bat
a distance between sample and film of 5 cru V / p / mrend the exposure is in the Kamsra a Yalmuia erseugto pie radiation - "is made by a. X-ray unit of
Philips (K & tnlQg No. 12045) with einis Knpfer-Peineinstiellungsdiffrak'iiocsrolir (Catalog Ur ₀ 32172) 'uaä "a SlickeJ-ß-Piltesf-erj ??; ugt, whereby the unit is operated at' 40 kV tsnd 16 jüA, - A thread sample ^: * older ifiit 0 "051 i'S" Ώ1 eJ "?
is filled with the 'sample, where'öei all l-'iißen that lie in rles Eöntgenß'ärcih'j .., held in parallel ir & väeti »Ώάζ Bee · - gungsdiagrsE0 · is medically a Hoir _i ; gens - ;;? fjWoiü ".il.jn Kodak Ne-Scr · en © {liS-54-Τ} ode ^ einea äf | uivaionte: i 1 · 2η.ΐβτ · ίο1" au% eseichnc "i-- _o About film is for one a ^ nreichenüis "Seitspanne exposed to-a diagram su ergebe", iae-Qesxil iiex "- Sistandardvpratellation3n as ßkr-optabol b ^ t.va

009836/2187

'BAD ORIGINAL

tm

- - ■ ■ SI

(for example, © in diagram ^ wherein the su laessena ©. diffraction spots sufficiently © photogr & phiache blackening = pollution, "for example swisqhen O ₈ 2, and 1.0 _s au'fitfeist to accurately read au 8 @ in) _o In general, An exposure time of about 45 minutes is suitable, but a shorter exposure time may be suitable for highly crystalline, land-oriented samples and may also be desirable, xm . a more precisely readable biagrassiUB sa obtained film exposed. 'is at a' temperature of 20 * 1.1 ⁰ C (68 ■ - 2 ° F) 3 minute "long in Eö'ntgenstrahlenentwickler Du Pont Gronax \ 5l 15 second long in © ines ünterbreebüngsbad (30 ml of glacial acetic acid in 785 Zt Itr. De-distilled / aeser) and processed for 10 minutes in X-ray fixation and hardening solution G-enaral Electric Supensixvf ^ "The FiIa works for 0" 5 hours washed and dried in flying water.

The arc lengths in degrees in dt-r a-albums tat {der Wincel »of the passages Lit 50 5 * ß © r sität ainselilieSt) des äq.uato;« - ial © n Η & υρΐίΊβοΙε ^ ε is measured and as OriÄatxör'UigowJnkel the sample g3; .or "i, _o Bid eii · special Eagon AEI _P aur Bßatiiniaung the Orientie ^ mgswinkel at Fiden Trorweadot WEII-den, di ^ in the example of nacLfolgenden bsBchriöbön iiiv.d (in the in the subsequent Abnchnitt ai; given Series fc-lge) step in the following positions-sn, 20 (degrees)

009836/2187

st

Thread from example 2Θ (degrees)

1 (A-1) 22.56 1 (H-1) 22.41 1 (A-2) 22.56 1 (a-2) 22 * 51 2 (A) 22 _S 49 4th (A) 24.35 4th (H) 15.59 6th (A) 22 _S 73 7th (A) 22.44 7th (H) 21.45 8th (A) 22.10 8th CH) 22.19 9 CA) ■ 21 * 20 9 CH) 22.00 10 U) 22 _S 32 10 (H) 2i, aj? '11 CA) 21, f'5 11th CH) 21.73 13th (A) 22 _; "-ϊ9 13th CH) 22 , 2k 14th (A). 22,; J-i 14th CH) 22, -i 15th CA} 22, ^. 4th 15th (H) 22 Ao 16 (A) • TO -i S
-ii -'- 9 4-S- 16 Ch) ;? 2 ./> 2 17th Ca) 22.93 17th (H) 22 ^ 9 18th CA) 22.5 * 18th (M) .22, f5 19th (A) 22, .Wi

009836/2117

BATH ORIGINAL

Thread from example £ C (degree)

, 22.29

22, "^ 22 * · '*

21 * 6O 21.93 22.00 20.83 22,12 20, .68

22 c OO 21.05 20.05

-21.31 20.28 20 _f 33 21.95

'20, 38 21.95 22.15 22.10

21 ', 93

21.95 22.17 22.93 £ 2.27

22 * 34

21.38

22.20 21.4 B 22.17

20.9 8

22VlQ

19th (H) 20th (A) 20th (H) ■ 21 (A) 21 (HI) 21 (H-2) 22nd (A) 22nd (H) 23A (A) 23A CH) 23B (A) 23B (H) 24 (A) 24 CH) 25th CA) 25th (H) 26th (A) 26th (Π-ί) 26th (H ~ a) . 27, (A) 27 (F) E.g. (H) r: D IH) 70 CF) Z> ^ U-) ?1 Cn) "2 (A) (H) 33
ν · » ί ■ \
U - i (A) ''; '- 4 (H)

009836/2187

'<\ YY «" JO. Thread of example (A) 1929694 2 © (degree) 35 (H) 21.50 35 (A) 22.17 36 (H) 21.16 36 (A) 22.19 37 (H) 22.54 37 (A) 22.39 38 (H) 22.71 38 (A) 22.24 39 (H) 22.27 39 (H) 22 _f 34 40 (A) 23.41 41 (H) 23.39 41 (H) 23.36 42 (H) 21.93 43 (A) 21.93 44 (H) 22.98 44 (A) 22.44 45 (H) 23.51 45 (A) 22.59 46 (H) 23.46 46 (A) 22.51 47 (H) 22.39 47 (H) 22.05 48 (A) 22.78 51 (H) 22.29 51 (A) 20.20 52 (H) 22.69 52 (A) 22.07 53 (H) 23.22 53 (A) 22.34 54- (H) 25.69 54 19.97

0 09836/2187 _{BAD 0R! 6! NAU}

Fad & α from example ^ C)

55 (Δ-1) 26, QB

55 (Ε) '18 .47

55 (Α-2) 2β, 0β

56 (A-I)

5β (Α-2) £ 2.93

23.07 22.44 22 * 64-

22.56 22.12

76 (H) 18.48

13.84 18.18 25.37 80 (A). 19 _? ΟΘ

81

A «Fad eil wit ®r spur

A-j »first thread is shown in the example

A- 2 «second Fatten ^ yie © ruffled In example

H-1 «first or wäifflebehaiad parent Fad © ia In example

H-S = s two'sar would be 3fflabeliaiid © lt © r Paden in example

009838/2187

ßAD ORIGINAL

Me orientation angle from erfin & imgsgeiaäßaB Md en related in various ways by cirsi methods (or equivalents thereof} from the

film, the development of which has been described above

In one method (method 1) the asimutala T did svert part of the inflection curve received, iföbei r.in sutoaatlsch on asiöunendee Itilcrotieiiäitoicaeter Joyce »Loebi is used (model MK III C iait a roiie «

Bülrne, hergcstoll-t roa Jc ^ e ₉ Loebl ana So ₀ ,

England.} "Typical InstriaaionnteiKstolliaigen that are used" are:
Leverage ratio 1: 1,
Objective lens 5 / 0.10,
Record success rate ι integrating, slot setting: 187,
Wedge 0.087 refractory units / c ©.,

Variations of these Einstelluagaß that aufgrunä üer to the manufacturer will be given a Beugungscliagra IaaS erfordarlieli according fib? this device (dated August 1963) vorganoiomen, Ie operation will de ?? The film is brought onto the stage, the instrument is set carefully on the iPilm and the center of the diagram is brought into line with the stage santruia, whereby these two zantras are brought into congruence with the aid of a light beam from the instrument The attached film is moved »ms dem. Let the light beam pass through the most intense area of the light spot, the opposite corner is checked to ensure correct centering and after any necessary fine adjustments have been made

- 62 -

009836/2187

the recording of the azimuthal intensity curve by a 360 ° rotation of the film on suitable coordinate paper

linear scale "A curve is obtained which has two main peaks" A base line is drawn under each peak in such a way that the background heat of the film extends below the peak "A plumb line is dropped on the base line from each peak maximum. Through the center of each solder (d "i _e the point of the" half-height "), a line is drawn parallel to the base line" which each leg of the respective curves intersect. The length of leg su shank of each horizontal line in "half height" is converted into degrees of arc in the following way: The horizontal distance (ie _, parallel to the base line) between the two peak maxisa is measured and represents 180 ° of the arc from side to side in "half height" calculated in a degree value. The barchechnut is formed from the values for the two arches and this represents the orientation angle to which reference is made in the description of the present invention »

- 63

009836/2187

The percentage of crietallites that are related to the thread axis is oriented within one half of the angle calculated by the method described above Pur determined in the following manner, each peak of the curve described above are determined by the points of contact at the peak of the horizontal leg ~ to leg line ia "Half-height" plumb bob is dropped on the baseline »This creates a rectangle that is divided by the rounded line, the two vertical lines and the horizontal line "halfway up" is connected. Using a planer becomes the relative area of the pike plus the area of the peak under the curve and above the horizontal one Line "halfway up" determined (total «area!) <, The The total area under the peak above the baseline is then determined with the planimeter (area 2). The percentage of crystallites that are within the orientation angle is aligned, corresponds to:

Area 1

- - χ 100.

Area 2

A second method (method Z) _9, which is used to determine the orientation angle in the threads according to the invention, uses an improved version of the “Flyingspot ⁿ densitometer, which is described in“ Acta Cryst ”, 10, pages 560 to 562 (1957) (Owens The equipment used is similar to the equipment described in the cited literature parts in Figure 1, with the following differencesί

(1) The constant voltage transformer Sola No. 30808 1st replaced by catalog no. 23-22-112 and this unit is only in series between the main switches of the regulated 500 V connection.

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0 0 9836/2187 _ΛΩ , ™ _Δ ,

: _? ; . 8AD OBiGUNAL

(2) The Dumont Anseigeossilloskop Nr. 304 A and the connecting one Calibration signal generators are through a display osailloscope Tektronix 532 in combination with a Tektronix 53/54 K preamplifier replaces “Die combined units are only connected in series between the dsm main switch and the photo amplifier.

(3) The flying apot oscilloscope {Dmnont Hr, 304 A) and his Cathode ray tubes are through an oscilloscope Tektronix 536 with a cathode ray tube 536 P 5 er « puts.

(4) The regulated 500 V outlet is connected to the photo amplifier and also with the circular generator (a type of device which is referred to by Owens and Statton as a sampling frequency generator) connected »

(5) The circular generator is at one point by a ho « rlaontal preamplifier type Tektronix 53/54 K and at a second point, a line circuit scarf ter and a Tektronix 53/54 K vertical preamplifier connected to the Tektronix 536 oscilloscope »

The operation of this device is carried out according to the instructions by Owens and Statton, with the exception that the calibration is carried out with a rectangular wave from a signal generator not necessary 1st. Appropriately forms how in the named literature parts described, a metal block the infinite visual value of the anaige diagram « A clear bearing of the filmea provides a reference for the Density zero,

In the mentioned literature it is stated that daa "Flying-spot" densitometer is a quick measurement of the orientation angle and the photographic blackening (op

-. 65 - ■

^ 009836/2187

8AD ORIGINAL

table density) delivered 19296 84

A third method (Methods 5), by which the 3.sorelation angle of the 3 aaa according to the invention are determined, comprises a Leeds & Horthrup microphotometer Ksfei · J.og "670 (KPl), - its electronic components aproh a Keithley 410 micro-microamparameter (KeithXsy Ine _OJ Cleveland, Ohio) have been replaced * D ^ r Out, put this device is to a Leeds & Norttrup Spe-sdopiajc Eeoorder ₉ type G ₉ directed from this device on, for example, semi-logarithmic registration paper . plotted curve can IMD, the orientation angle dJ.e egg istsl --litausrichtvmg ^ iteweisen by AERB obtained v: & Rarm _f oils are comparable to those which are used in Dessi obec beschriebeiseB Joyce Iioebl "(Jerät

Of the above three methods or InstniPiSviteiisyetemen the above-described mathodes 1 and 3 provide the most precise determinations of the orientation angle ₃ The accuracy of the "flying spof method is about £ 1.5 ° dee indicated angle values ». Tie in the following examples _: 5 angles of orientation are determined using -" - on Mashode 2 (the "flying-spot" device), who is not given, due to the speed and convenience of the Measurement of the large number of analyzed paths made possible by this method.

In the following example, 'the' speed des Sehalleu in threads according to the invention, referred to as Soundproofness (SV) dea Padens »determined by (in a traditional way according to the indications of the historical) a dynamic module test device KLH JPM- f> (produced by KLH Rasoaroh and Development Corp., Cambridge, hereinafter - referred to as "PPM-5" in conjunction

■. ■ .- 66 -

BATH ORIGINAL

'...., 009 836/2107

with a pasentiometric recorder Speedomax type & (manufactured by Leeds & Korthrup 0o ", Philadelphias, Pa.), which is hereinafter referred to as" recorder " ₈ is used = Since the latter instrument is operated as a 10 millivolt recorder. These devices allow measurements to be carried out as graphical representations of the visual propagation time as a function of the distance.

The operation of the present invention, the Schailge are bsi by the ^ chwindigkeitsmessungen carried out can be summarized in the following manner, "wherein all measurements are carried out in a luftatraosphäre, the (70 ⁰ F) and 65% relative humidity at 2I ₁ I ⁰ C (rF) is held. The yarns are exposed to these conditions for at least 16 hours prior to the determination of the speed of sound

The area holder of the modular unit of the PPM-5 opens 100 «which causes the recorder to be at full Deflection 100 microseconds or 10 microseconds each 2.54 cm (1 inch) on the paper perpendicular to the paper direction attends. The recorder is set so that the recording paper (Heeds & Nortlirup Co., No. * 690489) deal with the speed of 17.5 mm (0.688 ineh) per minute. moved forward,

The yarn sample is placed in the scanning unit of the PPM-5 and is suitably loaded to produce a tension of 0.1 g / denier ssu on the yarn conventional catfish the manufacturer's instructions) Then, in accordance while the movable carrier (or Garnsonde) of the P: M-5 Abt'asters cyclically _r from the stationary carrier (Garnsonde) at the rate of T 62 cm (3 inch) per minute and on this

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009836/2187

SAD ORIGINAL

(8th

to moved, the yarn fed a sound impact signal of 10,000 hertz. During calibration moves the probe along the yarn _p is recorded on the recording paper, a diagonal line connecting the paper from the sur one side other "crosses the pin of the Rekordenr changes direction, when the probes at the locations of the largest and the smallest separation from each other are.

Since the recording paper is moved forward at a speed of 17 »5 mm (0.688 inch) per minute, the probe speed along the yarn is corresponding to a ratio of 3 / 0.688 or 4» 36/2 see / her as the forward · "geschwindigke.it of Registrierpapievs (d _o h", per 2.54 cm chart paper movement has d; le si3h BEV LEGEND probe 11.05 cm along the yarn traveled) "

The speed of sound between two points in the yarn (the speed of sound SV) is then determined by multiplying the slope of the recorded chart line by 11.05 kwi / sec in the following manner

vertical distance in inches between two dots, on the director's paper line

Γ χ 11.05 kra / sec.

horizontal distance in inches between two points on the recording paper

The factor 11.05 km / sec. results from the combination of Recording paper and probe speed and the required Biological rewards are shown in the following derivation:

4.36 inch / 1: 'nch vertical 2.54 cm / inch χ 10 "- kBi / cm (Registriex'pi .pier)

, - «=» = —.— i χ -. ———. »«. ·. «,» «11.05 km /

10 microseconds / 1 inch, _n -6

horizontal (registration ¹⁰

paper)

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BATH ORIGINAL

0 09836/2187

Cited in the description of the present invention Sound velocity values are based on a measurement of the slope of the chart line that is made while the two probes separate (doh. ,, while the moving probe is separated from the yarn spinning " weight moved away). Usually the incline value is that of 11.05 km / sec. is multiplied, the average * worth of three separate moods of inclination, which at three separate diagonal chart paper lines can be made.

The following examples are intended to illustrate, but not limit, the practice of the invention.

B e i B_pi e 1 1

This example illustrates Cl) the production of Poly-Cp-phenylene terephthalamide), (2) the manufacture of anisotropic and isotropic oleum masses thereof and (3) the Manufacture of threads from it.

Polymerisathers tellunfi :.

71.1 g (0.35 mol) of powdered terephthaloyl chloride are all at once to form a solution of. 37 »B g (0.35 mol) of p-phenylenediamine in Misohung of 420 ml Hezamethyl" phosphoramii and 210 ml N-methyl-2-pyrrolldon added ₃ which is contained in a 1 liter _o Resin Preparation vessel equipped with a on the stirrer with Air drive and equipped with a calcium chloride drying tube. The temperature of the reaction mixture is moderated with a water bath at room temperature. A solid mass is obtained within minutes and left to divide ο at room temperature for 4 hours. The mass is then combined with water and stirred at high speed in a 3t785 liter misoher.

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009836/2187

The polymer is washed three times with water by stirring it in a mixer, and isolated by filtering it through a coarse-pored sintered glass groove. The polymer is dried overnight in a vacuum oven at about 70 ° C. The logarithmic viscosity steel _B measured on a solution of 125 mg of polymer in 25% ail 95 to 98% strength by weight sulfuric acid, is 2.24 »

Preparation of _b ani s otropen Massei,

A mixture of 36.0 g of the above polymer and "264 g of fuming sulfuric acid (3 # free sweetness) is mixed under anhydrous conditions by means of an air-driven disk-type stirrer in a 500-liter resin-making vessel while cooling with an ice / water bath The mixture is stirred overnight and left to stand at room temperature for 15 days.

Pad production by wet / planning of the anisotropic mass:

ir 1 IfTiMW <nnWi i * "tt« * - ' ^g iw * ^v nf'

A portion of the dope prepared above is ■■ sur remove trapped air centrifuged Then, it is 0.076 mm Duichmesser esrtrudlert means of a mechanically driven syringe through a 0.254 cm thick Edelmetalls7) inndüse 20 Liicharri van in an aqueous Koagulierungabad, the door a tenses of 41 ⁰ C «. The bath is approximately 5> 1 cm wide and approximately 2.54 cm deep. After traversing a distance of about 0.61 m, the yarn is guided out of the red water at an angle of about 45 ° and onto an 'elek' freshly driven winder. The yarn is on a perforated bobbin with 19.8 mm / million gaapmmelto, in which the yarn is washed in cold running water for several hours (ie 3 hours) and dried in air at room temperature. The threads show slight crystal! -

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BATH ORIGINAL

0 098 36/2187

nity and an orientation angle of 34 ° and a speed of sound of 4 "56 km / sec." .

The above slarn is conducted with 7.63 m / min * by a heated at 600 ⁰ O tube (device A) and collected with 8.34 m / min _0th The calibrating threads show high levels of crystallinity, an orientation angle of 15 ° and a visual speed of 8.37 km / sec. (Boiled) threads show the following S / E / Ml / den values: 12.8 / 1.9 / 827 /

lun _:! .. one, is ptropic "mass;

A mixture of 9.0 g of the above polymer and 111.0 g of sufficient sulfuric acid (2 $> free SO2) is mixed under what-free conditions with an air-driven disc-type stirrer in a 500 ml resin production container while cooling with ice-a / water bath, the mixture is obtained overnight or until a clear vislose mass, stirred _P during which Zei; sen Gelas the cooling bath to warm Ratimtemperatur is ο

Faflenherst iXlting by wet sniffing the isotropic mass:

A portion dar-top clear spinning mass produced is centrifuged to remove trapped air "Then, it is vi" ttelß raechenisch a syringe driven by a 0.0254 cm thick Edelmetallspiimdüse with 20 holes of) 076 in a ram DuxOhmeseer at Raumtemx> erature located 33 aqueous coagulation bath extruded. The bathroom is about 5.1 cm wide and about 2.54 cm deep * compartment

- 71 009836/2187

SAO OfilÜINAL

Pass it! a bath length of about 0.61 ι that Yarn at an angle of about 45 ° from the water and su an electrically driven winding device guided 23 & 3 yarn is made on a perforated spool with 11 »3 m / minο collected. Eb is then flowing in cold Washed in water for several hours (i.e. 3 hours) and dried in air at room temperature low crystallinity and an »orientation angle of about 50 °, determined from a wide angle beam diagram. (Boiled out) threads show the following f / B / Mi / den «values: 3.1 / 20.8 / 106 / 7.0.

Heat treatment: _mii de r . Threads from the. ^ Aotropic mass \

The above G arn ^l is conducted with 7.63 m / min, through a heated at 550 ⁰ C .Rohr (device A) and 8 _P 34-m / min "The collected filaments resulting seigen high crystal - nity and An orientation angle of 19 ° (cooked out) threads show the following T / E / Mi / den-Verte: 5.3 / 1 "4/401 / 5.7.

T he s e 1 oil 2

The present example illustrates (1) the preparation of Pcily- (p-phenylene-tetr-phthalate) _f (2) an anisotropic oil mass therefrom and [ 3) therefrom. made threads with. high. liodul β

Polyinerisa production %

g C ( ', 5 mol) pulverför.-Qiges TerephthaloylefeQ.orid "are to-g" iner solution of 54.0 (O ₈ 5 moles) of p-Phonylen "diamine in uiner mixture of 600 ml Hcxaaiethylphosplior" amide and 5 ^ 0 ml H «methyl-2-p, irrrolido: a ^ egeberf mid os is stirred at high speed in a mixer. Within a few minutes a solid mass is obtained. After 20 minutes the mass is combined with water and mixed

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0 098 36/2187 Bad LOCAL

stirred in a 3.785 liter mixer at high speed. The polymer is washed 4 times with water, once with alcohol and finally with acetone by stirring it in a mixer and is isolated by filtration on a horse-drawn carriage. The polymer is dried over Uaeht in a vacuum oven at about 100 ⁰ C. The polymer yield is 116 g (97 »5 # of theory). The logarithm!" BChe viscosity number, measured on a solution of 125 mg polymer in 25ρ0 ml 95 to 98% by weight sulfuric acid, is 3 »8«,

A ni tro groups so producing a Mass;

A mixture of 50.0 g of the above polymer and 45O _f O g of fuming sulfuric acid (0.8 fo free SO ") is mixed under anhydrous conditions with an air-driven stirrer of the disc type in a 500 ml HarzherstellungBbehälter while using an ice / water The bath is cooled. The mixture is stirred overnight, the cooling bath being allowed to warm to room temperature during the period. The resulting mass shows agitated tropics and depolarizes linearly polarized light It shows a solvent viscosity of 5000 poise at room temperature measured by means of a Brookfield viscometer (model RVi ¹ ) using a 'Spindle No.' 7 at a spindle speed of 2 rpm. At a speed of 20 rpm, the measure shows a solution viscosity of only 1660 poise.

? aden hj3rste] lunff by wet spinning ;,

The pulp produced above is centrifuged to remove trapped air. You will then be with the Speed of about 0.8 ml per minute at one press of 26 kg / cm through a 0.064 cm thick precious metal spinneret with 20 holes of 0.0051 mm diameter in one

- 73 »·

009836/2187 sad original

Aqueous coagulation bath held at 43 ⁰ C is extruded. The bath is about 40 cm wide, 14 cm deep and 94 cm long and has orphans av.a stainless steel spaced about 0.61 m apart. The thread is drawn through the bath and around the orphans in such a way that it passes through the water bath three times. It is then fed out of the bath at an angle of about 45 ° and onto an electrically driven winder. The yarn is collected on a perforated bobbin at 8.24 m / min, while "it is wetted on the bobbin by running through a water container - which is located at the lower end of the collecting bobbin." The yarn is then placed in cold running water is washed over power and part of it is removed for heat treatment. The rest is dried on the bobbin in air at room temperature -> door. The dry threads show little crystallinity and an orientation angle of 31 ° and a speed of sound of 5.00 km / sec. The threads have the following T / E / Mi / den values: 7 »0 / 9.1 / 173/1 "93 (stretch rate 10 '5A).'

Heat treatment of the wet thread

The above hergastellte wet (washed) yarn is passed with 7 "63 in / min," dirch a heated to 500 ⁰ C tube (device B) and 8.09 m / min, collected the Fädea resulting show high crystalline! Did and an orientation angle L of 11 °, determined from a wide angle X-ray diagram. The threads show the following T / E / Mi / den-Wecte: 13.7 / 1.6 / 888 / 3.23.

B e i s ρ i e 1 3

The present example illustrates the preparation of poly (2-methyl-p-phenylene-2,6-eaphthalamide) and an anisotropic mass from it.

BATH ORIGINAL

009836/2187

is

12 _P 65 g (0 * 0? "MoI) 2 _S 6-naphthaloyl chloride are added at once to a slurry of 9" 75 g (0 ₅ 05 mol) p ~ XjhenyXenc) iamindih.ydroohlarid in 120 ml!, L « • amide (distilled off from OaHp at reduced pressure and stored over 5A molecular sieves), which is contained in a 500 ml Hars manufacturing container with an air-driven stirrer and a potassium chloride drying tube Room temperature moderate α A paste-like mass is obtained within minutes and left to stand over power at room temperature after which the paste becomes a hard, stiff mass. 3.0 g (0.3 mol) of lithium oxide are then mixed in with a spatula and the resultant mixture is combined with water and stirred in a 3 "785 Ltr _& mixer at high speed, the polymer is .sohen three times with water by weight by £ _i:.? .a a mixer stirred v / ill, and isolated by it on a big bpox'igen sintered glass suction filter is filtered. The polymer is overnight in e: get3 .nem Vakuumofea at about 70 ⁰ G: ₀ The ocknet

Polyinerissa yield is 13.9 g (92 “2 # der The logarithmic viscosity steel, gladly si3en on one Solution of 125 mg of polymer in 25.0 ml of 95 or 98 Sulfuric acid, is 2.08.

Manufacture «, ·; an anisotropic mass egg

A mixture of 7.5 g of the above polymer and 4-5 »Ο β 99; .. · wt ~ $ Schwefeloäure strength will continue waeoer-Bed 'free .ngungen with a mechanically driven Eüh <rea.? vo; n S ¹ Igel type in a 200 ml round bottom flask a gesiisoh'i; while generally: 1; an egg / water bath. The mixture is stirred overnight, wälireiad this time

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009836/2187

SAO OfiiGiWAL

the cooling bath is allowed to warm to room temperature. The resulting flowable mass shows EÜhropalesaensa and depolarized linearly polarized light _o

Example 4

The present example illustrates the production of poly-C2 "6-diehior-p ~ pheny! En-2,6-"BaphthalaE> id) in the direct production of threads from the anisotropic N, N-dimethylacetamide / lithium chloride reaction mixture "

Manufacture of Polyme riiga ^^ and ^^ S ^ innmasse ^

12.65 g (0.05 mol) of 2,6-liaphthaloylchlorld are added all at once to a solution of 8.85 g (0.05 mol) of 2,6-dichlorophenylenediamine (sublimed) in 120 ml of N, N-dimethylacetamide (distilled off from OaH ₂ under reduced pressure and stored over 5A molecular sieves), which is contained in a 500 ml resin production container equipped with an air-driven stirrer and a potassium chloride drying tube. The mixture is vigorously stirred and the temperature is moderated with a cool water bath Cd.h "20 ⁰ C). After stirring for about 35 minutes a stiff mass is obtained and left to stand overnight at room temperature. 1.50 g (0.053 mol) of idthium oxide are added to the stiff mass and mixed in with a spatula. A flowable mass is obtained within a few minutes. This measure causes Rühropaleszenz and riepolarisiert linearly polarized light. A small ΨλΊΧ of the mass is combined with water and with high intensity; stirred in a 0.946 liter mixer. That? The polymer is washed three times with water by:> Stirring it in a mixer and isolated by filtering it on a coarse-pored sintered glass filter. The polymer is placed in a vacuum oven overnight

, The Ic

- 76 - '

dried at about 70 ^{0 O.} The logarithm! See viscosity

009836/2187

BATH ORIGINAL

⁰ Od ₈

3 ο ι

number, measured on a solution of 125 mg of polymer in 25.0 ml of 95 to 98 weight percent sulfuric acid, is 1.99 »

thread production by _i KaQa pi nne n:

The mass described above is centrifuged to remove entrapped gases. Then it is applied at the rate of about 3.5 al / min. at a pressure of 3.52 kg / cm by an O ₉ 0254 cm thick ISdelmetallspinndU-se extruded with 100 holes of 0.076 mm in diameter into a bath maintained at about 51 ⁰ C aqueous coagulating bath. The bath is about 40 cm wide by 14 cm deep and 94 cm long and has stainless steel rollers about 0.61 m apart. The yarn is drawn through the bath and around the rollers so that it passes through the water bath three times. It is then guided out of the bath at an angle of about 45 ° and to an electrically driven winder. The yarn is collected on a perforated bobbin at 11.9 m / min. It is then washed for 3 hours in cold running water and dried in air at room temperature. The threads show low criatal alignment and an orientation particle of about 50 °, determined from a wide-angle X-ray diagram. The threads have the following ϊ / E / Mi / den values: 8.7 / 8.6 / 222/3, 75 «

Heat treatment of the .._ g.aden_>.

The yarn prepared above is passed at 7.63 m / min, through a heated at 500 ⁰ C Bohr (device B) and, gebammelt with 8.49 m / min. The resulting threads show average crystallinity and an orientation angle of 10 °, determined from a wide-angle X-ray beam. The mows show the following X / E / Ml / den-Wevte: 10.5 / 2.2 / 518 / 3.43.

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009836/2187 bad oriqinal

Example 5

The present example illustrates (1) the preparation of poly (p-phenylene-2,6-naphthalamide), (2) an anisotropic one Sulfuric acid mass from it and (3) the manufacture of threads from it.

Polymer production:

25t3 g (0.10 mol) of 2,6-naphthaloyl chloride are added to a solution of 10.80 g (0.10 mol) of p-phenylenediamine (sublimed through silica gel) in a mixture of 120 ml of hexamethylphosphoramide (distilled off from CaH ₂ and stored over 5A molecular sieves) and 80 ml of N-methyl-2-pyrrolidone (distilled off from CaHg and stored over 5A molecular sieves), which is contained in a 500 ml resin preparation vessel equipped with an air-driven stirrer and a calcium chloride drying tube. The mixture is stirred vigorously and the temperature is ^{moderate with a cold water bath (ie at 20 °} C.). After several minutes (ie after 3 minutes) a small amount (ie less than 0.10 g) of 2,6-naphthaloyl chloride is added to the cloudy solution. A Btelfe mass is obtained within seconds and left to stand at room temperature overnight. (In another similar but different experiment, a stiff mass is obtained within 1 minute without the need to add additional 2,6-naphthaloylochloride.) The solid mass is then combined with water and poured into a 3.785 liter . Mixer stirred at high speed. The polymer is washed three times with water, washed "by being stirred in a blender and isolated by being rlasfilternutsche on a coarse-pored (filtered. The fact that the polymer is dried overnight in a vacuum oven at about 7O ⁰ C. The yield of poly ( p-phenylene-2,6 ~ naphthalainide) is 27.6 g (95.7 % of theory)

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0 0 9 8 3 6/2187 ^{8ÄD 0RlGINAt} -

Viscosity number, measured on a solution of 125 mg of polymer in 25.0 ml of 95 to 98% strength by weight sulfuric acid, is 2.48.

Making the mass:

A mixture of 7.5 g of the above polymer and 67.5 g of 98.7% strength by weight sulfuric acid is made under anhydrous conditions mixed with a mechanically powered paddle-type stirrer in a 200 ml round bottom flask while using an ice / water bath. The mixture is stirred overnight, during which time the cooling bath is on Allowing to warm to room temperature * The resulting flowable mass shows Rühropaleszenz and depolarized linearly polarized light

Pade production by Kassapinnent

The spinning mass produced above is centrifuged to remove entrapped gases. It is then extruded by means of a mechanically driven syringe through a 0.064 cm thick noble metal spinning nozzle with 20 holes 0.076 mm in diameter into an aqueous coagulation bath kept ^{at 25 0 O.} The water bath is about 5.1 om wide and about 2.54 cm deep. After passing through a bath length of about 0.61 m, the yarn is guided out of the water at an angle of about 45 ° and onto an electrically driven winder. The yarn is on a perforated Spul® with 6.7 m / min. collected while it is wetted on the bobbin ₉ by passing food through a water tank located on the lower part of the collecting bobbin. The yarn is then washed over power in cold running water and dried in air at room temperature. The threads show the following T / E / Mi / den values: 3.9 / 6.3 / 195 / 3.20.

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009836 / 21Θ7

- 1929684

Heat treatment of the threads see chap

The above pleasure is 7 »63 m / M: ln. passed through a RoJir heated to 533 ° C. (device B) and collected at 8.59 m / min. The resulting tildes show the following ϊ / E / Mi / den values: 7.6 / 1.7 / 540/6 _f 50,

~ 80

009836/2187

SAP ORiGiNAL

Example δ

This example illustrates

(1) the production of a copolymer with random distribution, which consists of 54.7% by weight of poly (p-phenylene-2,6-naphthalamicl) and 44.3 öew.-jfi poly- (p ~ phenylene terephthalamide) consists,

(2) an anisotropic mass thereof and

(3) threads from it.

Polymer production

5-08 g (0.025 mol) of pulverulent eerephthaloyl chloride (sublated) are added all at once to a solution of 5-40 g (Ο »050 mol) of p-phenylenediaioin (mixed with silica gel) in a mixture of 60 ml of hexaraethylphosphoramide (i.e. reduced pressure distilled off from GaH ^, and stored over 5A molecular sieves) and AO ml H ~ methyl ~ 2-pyrroXidone (distilled off from GaH ₂ under reduced pressure and stored over 5Λ molecular sieves), which are contained in a 500 ml resin production kettle which is equipped with an air-driven stirrer and a potassium chloride dryer. After about 5 minutes of mixing, 6.33 g (0.023 mol) of 2.6 naphthyl chloride are added at once. The mixture is stirred vigorously while the temperature is cool .sserbad (d »h. with 2O ⁰ C) is moderate. After about 4 minutes a crumbly Maofje is obtained and left to stand overnight at room temperature. Dean it is combined with Vfceser and in a 3 »785 Itr. _O Daa polymer v / ill be washed Kieeher stirred at high Cesohwlndigkeit three times with Vfaseer, iriäeia In eo

~ 81 -

009836/2187

BAO ORIGINAL

H "" ¹ ^

stirred in a mixer, and isolated by placing it on a coarse-pored sintered glass suction filter is filtered «

The logarithmic viscosity number, measured on a solution of 125 mg of polymer in 25.0 ml of 95 to 98% by weight sulfuric acid _} is 5-51.

Herste Settin g ^ t he crowd:

A mixture of 7.5 g of the above polymer and 67.5 g of 99 1 2% by weight sulfuric acid is mixed under anhydrous conditions with a mechanically driven hill-type stirrer in a 200 ml dog-top flask, while an ice / water bath is cooled, the mixture is stirred overnight, during which time diener Ktihlfcad allowed to warm to room temperature \ _e rird which ergeböiKl © mass is extremely viscous, shows .Rühropalesssaß _...: - and depolarioiert linearly polarized light "

Division of the Padgnhar through hate spinning

The spin dope prepared above is sur distance ^χη: * centrifuged be closed ones gases will äaiiu issit a mechanically driven SprLtrae by eliiö Oy 064 thick precio ^ allepinndüse extruded with 20 holes of 0.076 "si IDurchioiGoser in a gehaltdaes at 25 ⁰ C aqueous rungsbsd. The water bath is about five to one and about 2.54 cm deep. After passing through a 3adst, recko 'from etv / a 0.6 "m, the yarn is fed out of the water with a Y / inkeX from ®tv / a and ku an electrical winding oil device perforated spool at 6.1 m / min, collected while it was on the

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009836/2187

BATH ORIGINAL

Spille is wetted., Inc'em e ?; is passed through a water tank g © ~, üzx && u *. w ^^ part of the SaMcelspuls arranged eats α the Qb.t'1 -'- 'ird gut HhQT lia.cht in cold running water gewasehe'a and it becomes a' .Coil ftü? the heat mist removed, 3) e: e Best is dried on the bobbin in air at temperature. The dry threads show spirals Ύοτα crystallinity and an orientation vinlcel τοπ 37 ° as well as a speed of sound of 5192 km / sec. Me threads show the following S / E / Mi / den values: 8.7 / 8.4 / 327/4 ^ 79 (DehnungBgesQhwindiglceit 10 ^) ₀

Heat treatment of wet and dry threads:

Rsponnen the above Naase (washed) yarn in the state as © is with 1, 63 in / min. by a erhitstes to 547 ⁰ C Raw "(device B) and passed, collected with 8.84 m / min = The filaments resulting exhibit high crystallinity and a Orientierungijwinkel of 11 °, determined from a Weitv / inkel-Röntguiistrahlendiagramm" The yarn shows the following T / E / Mi / don values: 12.7 / 1.8 / 895 / 87.3 »In addition, the above dry yarn in the state as oxtruöiert with 7-62 tii / min <by the to 535 ⁰ C heated, nitrogen-filled drill structure and conducted at 8.54 m / min, geaainmelto The pads show the associated T / ß / Mi / den values: 9.5 / 1.8 / 633 / 4.67.

At a pi «1 '7

Bas Lieger.de Beiopiel illustrated

(1) the hearing division of a MioonpolyamiöKi that looks like Cnöen units consists of those under

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009836/2187

BATH

SH 19-29684

-HH- ^ J) -CO-, -jm - ^ - M- and _-

are selected (relative molar ratio "~ Vi 1 χ 1),

(2) an anisotropic mass of the mixed polyamides and

(3) Threads of the mixed polyamide.

Po lymer isatli er production:

14.4 g of (O "O ^ri 5 moles) of p-Aminobensoylchloridhydroehlorid earn in a iProekenbehälter, that is weighed into a chamber which is kept under anhydrous conditions in a polyethylene bag. The open end of the bag is connected to a glass tube with a length of approx. 7.6 cm which has an internal connection connector at one end · = Connected to a production container which is equipped with a stirrer with a potassium silicate chloride drying tube Hexamethylphosphoramide (with verMinder ^ m 3-Wucfc ^: distilled off from CaH ₂ and stored over 51 molecular sieves) and 135 ω1 N-methyl ~ 2-pyrrolidone (at vee? Ain £ erteTE pressure removed from CaH ₀ and stored ^ over 5A molecular sieves; Emptied. After mixing for 15 minutes, throw in one g (½ ") 75 mol) of 2,6-faphthaloyl chloride on oil, while stirring vigorously. The Teiaperatur de) · Reakticnfjlaischung v / ill ICIT a cold water bath ι (d.lu with 2O ⁰ C) moderate! Inch further 8 MinTben be less than O = Naplitha "oylohlorid added ₁ ^ 2 $ ₅ sixth Me Miechinig corroborated in i Stirado ssu a cash register that cannot be operated and we left to stand at high temperature for a while

~ 84 -

BATH ORIGINAL

then combined with water and stirred in a 3 »785 liter mixer at high speed. The solid is washed three times with water by stirring it in a mixer and isolated by filtering it off on a coarse-pored sintered glass suction filter. The solid is dried over in a vacuum oven at about 70 ^{0 O.} The polymer! · Satausbeute is 30.5 g (93.6 i * of theory) of _0, the logarithmic © Viskositätssahl, measured on a solution of 125 mg of polymer in 95 to 98 25.0 ail gevr .- ^ Igor sulfuric acid is 3 .22 *

Making the Masses

A mixture of 7 * 5 g of the above polymer and 67 * 5 g of 99s2 gevio- ^ iger sulfuric acid is mixed under anhydrous conditions with a mechanically driven RUhr®r of the wing type in a 200 ml round-bottomed flask, while with oineiQ Eia / Wa38er * »bath is cooled. They mixture is stirred Kacht, during which time the cooling bath was allowed to warm to Ra-.iisieinperatur is located · The flowable ^r -iaööe Rühropaleszensa and linear polarized aeigt LiOlIt ₀ '

e] ivng öiirch hate spirits:

iiio ßpirmißatae produced above is aur removal of

rier tuft iüöntrifugiert * She is then hit «'vE, oitiör, Tiaehaniceli ongrittenon syringe through a /'} € λ ma dic-fe Bäelßieiiallöpinrdüoe with 20 holes of 076 wjj ltoc; htoeafjer h \ a vrJirißullQ held at 25 ^{0 C} .-ijboii oxtruclated. read Bad iot about 5 »1 cd; bretr i-ji t; tuYi f ^ -4 ciii fclsf »liaoh traversing a 33adati * e« lf; e u ofewa Ο »βί ta wirr) *! ao fiarn rait an angle vow olr * a

- 85 0 09836/2187

out of ü & m V / ater and led to an electrical g-riget'-tflgtssms winding device · Sas ■■ Sa3pn.wirä 'auf' eiu®? perforated coil with 9 »15 as / Mti, gesanaelf :. Ie v "Irae üksi *! 'Laughs in cold running water gewaseh em @ n UNAE a bargain v / ill aur heat treatment removes _a The Eat .i mf * feei Hauintemperatur i? Dried. The dry Kiden seis'? '' Traces of Ki * istal.linität and one of about 40 ° _s bestiiajat from einsm g

chart. The mues show the following ϊ / S / Mi / öeii value 6.6 / 9 »4/215 / 3.99»

of wet threads:

Beb above nag se '{washed} Sam is rait 1 ₉ £ 3 ia / i-IIJ »through a pipe heated to 438 ° ö (Vorri-oh-butig 3) passed imä rait 8.54 m / i'Iin _n gesaannelto. They have a high crystal, in it at ,, a 0v ± -3iiT - \ & sivn kel of 13 ° tnö a «S

The threads 2tIgen

10.0 / 2.2 / 580 / 2.93.

g5 If a different PnO ^ t <e3 nn ^ a ■ - * «- alymerin & trj (produced in sV _; ril Jeher i '^ is *; like the above« - Poiyifiii ^ i ^ a fc, Π,,. * = - 1,5i c ^ it ^ 9- ^ öfc- ^T _; ■ '* Schwoftili-iäurf "veroinigt» ".κ a Ht'fi? * V r>» ^: Jl'. \ LUr.i, * · 12 "lew ,, ^ Pc3yi3erii ~! A-ä e? Äthillt "eo wirl ■:!> X ¹ Xi * α \\ - Ά jr ·· a Βί) Α ·» \ ίert 'of 3? * 2 l'üul-ncuiie · '..

86 ~

00983672117

BATH ORIGINAL

At s ρ i el 8

The present example rex-look shows the production from

terephtnalam jLcä],

(2) an anisotropic Oleyamesss aavon iracl

(3) "by Päösn of it.

Polymer!

5.0 g (Oi0245 mole) of powdered Tercsphthaloylefclorici will eiaer Aufßcliläsmmng of 17 _9? g (0.05 mol) 'N, lT ^f ~ - Bis = (p-amiri & t) € ^t naoyl) ~ p-phenylcndJLainin given in 200 ml of kexamethylphosphorami, which is contained in a 500 si H & r & lieratellungsbeij age _? the ait sin © as air-driven Scalitzselieibeurülirc-r iinß a Kalääiuinehl-orid "trookenrolir v ^r ereht'm, while dipped with an ice / water bed wec3 _o Daa Diarnin goes on with honorable:! tender reaction in Lo ¹ UiRIg ₁ / 'i 10. Miutiten ueiden on one real ticitero 3? 15 g (Op025-! · MqI; '.Cf- ^ öplithaloylchlc i'icl ziigesetat. Bio Rcjaktions-Kf *; .-: ehmig viii in a' i,? 85.? »Tr _e mixer i / iit bofeor G® ^.-a - :! hv / in ^ i, fy- <ü: b agitated Be? erl-ßltcne J'eotsto'ff wirci dj? f: .l · - s * u;. 2Ei- ⁵ * y; '5'-? I ^{ j iii.KBißl with alcohol r? Ni- ßchlic ^ l: ^l .csh rvJ.t /. ■;' · ο si ^ UVi} fc «? Ic Ιγίάοϊα <2? · Χώ eivi ' in-Hiecher stirred «i ^ d« ^ Vu ', ia ^ y Lki ^% * indra er auf sit er ßroöporlgon Si vx -' v \ ü \ i: -. abf- "ίtriebe viir3 _o The lfeaboto ^ f is 73 »Nu: 3 i- ^T - <ii '«' ^£ Vpiki, ai) iofen; jei (tv / a 70 ⁰ C getroc Awr; beuU iü-; im &<;<£ent-liv'aen niöir ^ itaiiv ₀ The laughing YU-h) i5. 'i; ti.ta «ßh3, gera-jaoei as ein ei * Lütuni ?, vor, 12ö rag

009836/2187

8AO ORiGJNAL

Q-10 31-H

Polymer In ^; 25.0 ml of sulfuric acid with 95 to 98 percent by weight »H ₂ SO ₄ is 2.4.

Manufacture f

A mixture of 5.0 g of the oMgen Folyoierisats and 45 "0 g of fuming sulfuric acid (0.8 $ free SO") is mixed under anhydrous conditions with a mechanically driven stirrer of the 3-blade type in a 200 ml round bottom flask, while with an ice / V / ater bath is cooled "the mixture is observed visually overnight or until no more © solid Seilchen v can / ground stirred _{s s} during which will Since the cooling bath was allowed to warm to room temperature. The resulting mass is flowable and shows agitation tropalescence and depolarized linearly polarized light.

Paden production by wet spinning;

The spin dope prepared above is ssiir distance »centrifuged trapped Gas is then passed through a 0 _s 064 cw thick spinneret stainless steel NSIT 20 Ijöehern of 0.0076 era diameter into an aqueous coagulating bath at 27 ⁰ C extruded" The bath is about 5 * 1 cm wide and about 2.54 cm deep. After passing through a bath section of about 0 ₈ 61 in, the yarn is guided out of the water at an angle of 45 ° and onto an electrically driven winder. The yarn is collected on a perforated bobbin with a 10.7 m / Hin »It is then _{washed for several (α.η β} three) hours in cold running water and dried in air at room temperature. The women show medium crises ballinity «. an Ox * ient.ie-

- 88 -

009836/2187

BAD ORlGiHAL

AU

Angular angle of about 40 ° and a Scliallgasclnräiuigkeit of 4 »22 Ιαη / secos determined from a Y / angle oil X-ray radiation aiagrsiüjBc Di © Bidets have the following 2 / E / Mi / the ~ value i 4.8 / i 2.4 / "* 67 / 6.06 ₀

Heat treatment of the pads

Similarly ¥ © ise be as the above yarn filaments prepared with 7 * 62 m / min 'by a heated to 55O ⁰ G tube (device A) and directed gesäbelte 8.54 m / min "The resulting filaments exhibit high crystallinity and an orientation angle of 10 °, determined from a V / eitwinkel-HöntgenstrahlendiagraiDSn, The threads have the following! / E / tai / den values: 5.4 / 0.9 / 583 / 6.3 »

Example 9

The present example illustrates the production of sine polyetherate with low distribution, which is made from 34 » 3 Sewo- ^ i pQly ~ {p ~ phenylene» 2,6 ~ naphthalainiä) »28.3 6eWo-Poly-fp-phenylene terephthalarid) unfl 37.4 weight "~" jS poly-Cpphenylen-p, p-äipheiiylc! icarboxa8] id) is. It will be the production of an anisotropic Maaae and from Tüäen this {cei'polyinerioats as well as the production of films dea 'ouch üerpolyraeriaats a Hexamethylphoaphorai! nid / H «methyl-pyrrolidon-2 / lithium chloride-Maase illustrated.

Terpolymer production s

g (0.025 mol) of ^{4,4! t} ~ Biben3oylchlorid be at once au a solution of 8.10 g (0.075 mol) of p-in 3Phenylendiarain

009836/2117

8AD OflJGiNÄi.

a mixture of 80 ml H®xaF.ethyXphö8phQX'a $ iIil {te rl? ss »reduced pressure distilled off from CaH ^ unü axifije'ja'irt

over 5A molecular si flat) and & 0 ml (at reduced pressure em distilled from _GaH; ιιηθ kept "given over 5A molecular sieves) In the 3kamt 500 ml Harzh ^ rstellungsbeliältöj? is included, is provided with a liaftge'iriebeiien stirrer and an ens KalsiTiSülilotfidt drying tube, while with a water heater * j ^ because about 2O ⁰ O is cooled "Hech 2-minÜtig © a mixture of 5.08 g (0.025 mol )

(sublimated) and 6 _S 43 g (O _s O25 mol) 2 _s 6-IaphtI: & lorlcliljri added all at once. The mixture becomes vigorously ggy-üir-fe and after about 7 minutes becomes a non-stirrable mass He stops and laughs at the high temperature. Dii> feose left to stand still is combined over & ^ m ml '·', Wac = ser "', and in 3» 735 liters ₀ Miaölisr fiit iofe ^ i = ¹ speed stirred- At · IVjststoff \ rir3 öi? eii «:% l mi-f water washed by being in sin em Miadisr gi! lii;? .-« v.'riä, and isolated; · by © r on a sr coarse-pored Nutsche abfiltriex't is. "The Polymeriast wi in a VaIaiuinofan at etvm '70 ⁰ G getroclmsto Itei * -rieh ' resulting solids (25 *, 0 g} v? ir-l in ο in er Yfile ^ H-IIVLö g "^ ~ grind until i * r a sieve with ai'ies, * _{passes through 0?} 84 mm (20 nesh). Then the 6 hours * wixd with hot Amei-aensänre ^ n *" The üliiua is through " Filter through ai-ie gi »obpori; i; ö Si.:^tev.:i-la;3--nutsche removed and the polyin u * isate with ^ eh ^^^ ott Shares in i oestilliortem water gowasohoiio Bas B \ 'i ^ crisat ifird dam. in a vaknumoi'en b © i Qtva 70 ⁰ C;

The polyamide yield is 20 _f 2 g (9S jl mm? The logarithmic viscosity - '. Ahli geaieossn nil c of 125 rag Pclymerisat in 25.0 al 95'Me 98 g * -tf _e -

- 90 "

0 09836/2187

SAD ORIGINAL

Q-1031-R

Sulfur acid » is 2 _r 88. '

Filisherat © llung %

Sine HißchuEg of 0.20 g of the above polymer and 8.0 ml of a solvent, prepared from 3.0 g of lithium chloride, 66 p / 3 ιοί Hxamethylphoephorainid and 35 1/3 ml of N-methyl-2- pyrrolidonj, tfird in a Veremchsrohr Stirred at Eaumteiaperatur with a spatula. Mixing is continued until a clear mass is obtained, which is then spread on a glass plate with a 0.0127 CBJ kakel. "The plate is then immersed in cold: water" During the coagulation of the Kasee dissolves the check resulting film from the glass plate, and is GETRO "LMET ₉ by wirfi pressed at 70 ⁰ G in a Vakiiuaiofen between abeorptionefähigen Papierhandtöchern. The dry film is clear, tough and flexible ο

Making a mass:

A mixture of 5.0 g of the above polymer and 45.0 g of 99.2% by weight sulfuric acid is mixed in a 200 ml round flask under anhydrous conditions with a Meolsaniscl: driven stirrer from Wi U / ieltyo , while with Qinem 33ia / V / a3ser "bath is cooled". The mixture is stirred overnight-The calibrating mass shows Rtihropales-3eni5-and oep ^ lförißiert linearly polarized light "

009836/2167

ßAD ORtQJNAL

Fadenher oteilung by Faßspinnent

The Spinnmasae prepared above is for the removal of trapped gases you centrifuged is then extruded by means of a mechanically driven by a Spritsse 0/064 cm thick Edelmetallapinndüse with 20 holes of 0.076 mm in diameter in an aqueous bath at 25 ⁰ C. The bath is about 5 * 1 cm wide and about 2.54 cm deep. After passing through a bath length of about 0.76 m, the yarn is at an angle of about 45 ° out of the water and si? The yarn is guided by an electrically driven winding device. The yarn is collected on a perforated bobbin at 13.7 m / min = » B & is then washed overnight in cold running water and dried in air at room temperature» The threads are amorphous and have an orientation angle of 38 °, determined from a wide-angle X-ray diagram. The threads show the following S / E / Mi / den ~ values: 6.0 / 9.6 / 192 / 3.66 (stretch rate 10 ji).

Heat handling of threads ;

The above yarn is passed at 7 * 63 m / min "through a ^{tube heated to 400 °} C. (device B) and collected at 8.54 m / min". The resulting threads show medium crystallinity and have an orientation angle of 14 °. The Fädcra show the following 2 / B / ^Mi / the ~ value 12.2 / 2.8 / 517 / 3.07; the speed of sound is 8.66 km / sec. .

- 92 -

009836/2187

Bas this example illustrates

(1) the production of a mixed polyamide, which consists of like » repeating units that are selected under

(relative molar ratio 1t1 «2: 1) -,

(2) an anisotropic mass of the mixed polyamides and

(3) Threads of mixed polyamides _{or similar}

The production of a film of the mixed polyamide from one H-methylpyrrolidone-2 / lithium chloride bulk is also illustratesο

Polyamide production ί

4.8 g (0.025 mol) of p-aminobensoyl chloride hydrochloride are placed in a polyethylene bag in an iroecene container, that is, a chamber which is kept under conditions free from asb * a 7.6 cm length composite eh »which has a 29/26 internal connection at one end. The bag and tube are removed from the drying vessel and connected by the connector to a 500 mm resin making vessel equipped with a stirrer and calcium chloride drying tube. The contents of the bag trl ^ d go quickly v / ie possible in

- 93 -

009836/2187

SAO ORIGINAL

JV 1929684

a solution of 5-40 g (0.050 mol) of p-phenylenediaiain in a mixture of 55 ml of HoscaffieiibyXghonphoramid ("distilled off from OaHg iraä at reduced pressure stored over 5A molecular sieves) and 55 ml of M-methyl-2-pyrrolidoB (distilled off at reduced pressure from CaEL and stored over 5A molecular sieves) emptied »Kaoh 5 ~ 2inutige * n Miselian • a mixture of 5» 08 g (0.025 mol) powdery) (derephthaloyl chloride and 6.43 g (0.025 mol) 2,6-NapiitlmlGyi «chloride added all at once, while bit is ^{cooled in a water bath with 20 0} O. «The mixture hardens in 2 minutes to a clear, rubber-like mass and is left to stand over fold at room temperature. It is then combined with water and poured into a 3 » 785 liter »mixer stirred at high speed "The solid is washed three times with water by stirring it in a mixer and isolated by filtering it on a coarse-pored sintered glass suction filter." nem vacuum oven dried at about 7O ⁰ C. The resulting pesticide (21.0 g) is ground in a Wiley mill until it passes through a 0.84 mm (20 mesh) sieve. The Peststoff is äann about 6 hours triturated with hot formic acid, Me Saur © is filtered snutsche through a coarse SintergX & away and the polymer is with mehyeren proportions of distilled water washed _o The polymer is dried in a vacuum oven at about 70 ⁰ G. The Polymerisatarsbeute is 15 _f 2 g (93 »7 $ of theory) of the _β logarithmic © Viskoaitätssahl measured on a solution of 125 mg of polymer in 25.0 ml of 95 to 98 wt .- ^ strength Sch \ / efelßäure, is 3 * “9O.

0 0 9836/2117

CM BAD ORIGINAL

rstelT ^ Kg:

i: -r: e MIrschiang - "" of 0.20 g of the above polymer and 8.0 ml of ci'ifis solvent »prepared from 4.0 g of imö 9 & ml of H-otethyl-S-pyrrolidone, is in a kit a spatula at room temperature. The hi sch en ^ -ir?} Continued (ie, 24 hours) until a clear, pourable TiSsssung is obtained. The solution is then spread on a glass plate with a Q _{for 0127 era Bakel, pie} The plate is then immersed in cold water. While the vessels are coagulating, the resulting glass plate becomes detached and is dried by being

Vacuum scuffing at TO ⁰ C for about 6 hours between absorbent paper towels is pressed. The dry I ¹ IlJn is clear, sawy, and flexible.

Making an anisotropic mass:

A mixture of 5 »0 g of the above polymer and 45» 0 99 g, 2 ^ gewo- Lger ml sulfuric acid under anhydrous conditions; a mechanically driven puddle-type stirrer mixed in a 200 ml dog-top flask while cooling with a JSis / Waaser bath. "The mixture is stirred over Kactit ?; _c The resulting flowable measure ae-a and depolarizes polarized light,

Kaßapis.nen produced threads:

lio hexagon above spinning masse is centrifuged to remove trapped gasses _c . It is then carried out by means of an eiper sicehan ^: ach driven syringe through an oven, 064 cm thick Esselraetallspinndüse with 20 holes of 0.0076 cm diameter.

- 95 -

009836/2187

BAD OBQMAL

saesser iti οίΏ aqueous Had mvfe 25 ⁰ G gxtruöiert ,, Dae Ba is about 5? "which wide miu about 2 * 54 ο ?: deep« T "aeh 3 ^ ure fen a Badotreolue τοη about G ₈ 76 m throw with yarn at an angle of about 45 ° from the water left and right there is no electric winder. The yarn is 9t on a perforleri-en Sptale 15 m / min but ₀ gesatiüneltc JSE wirä gut Ifecbt in water gewasolien IWA © in part for wirfi

_f u away viährend, ®T rest eui * wivü Oer getrockast in air at Rauisteinperatur * The tr threads aißd amorphous \ mu had "a Ori.entierv.iägfäV / inlcel τοη 38 °, determined sue a

Threads are as follows 5.5 / 7.8 / 222 / 5.64 ο

Grarnes

The wet (göwasclione) yarn produced above is sr it 7 1 63m / min. »Passed through a Rohx- (device B) bled to 51O ⁰ O and with 8.84 κ / ΜΙη, overall» The threads have an orientation angle of Ii ⁰ and the following tensile properties (yarn) s ϊ / E / Mi / öen: 8 , _{5/2 1} 3/480 / 73.8 «,

96 -

0 09836/2187

SAD OBIQlMAL

Q-1031-R

B ice ρ 1 e__l 11

The present example illustrates the manufacture a mixed polyamide made up of repeating units consists of that under

-NH -V ^ V

-CO-,

0- »-NH-

and

-CO-.

V /

00-

(relative McI ratio 1: 1 j2: 1) are selected, (2) a anisotropic mass of the mixed polyamide and (3) threads of the mixed polyamide. The production of a film of the mixed polyamides A as an N, N ~ dimethylacetamide is also illustrated.

Tsrpolymeriajatherst ^

4 * 8 g (0.025 mol) of p-aminobenzoyl chloride hydrochloride are placed in a polyethylene bag in a drying chamber, i.e. in a chamber which is kept under anhydrous conditions al weighed * That the open end of the bag is connected to a glass tube about 7.6 om in length, the has a 29/26 internal connection socket at one end. The bag and tube are removed from the dry comb mer removed and using the connector with a 500 ml Resin production tank connected to a stirrer and fitted with an Aalzium Chloride drying tube. Of the The contents of the sachet are then converted into a solution as quickly as possible of 5.4-0 g (0.050 mol) of p-phenylenediamine (sublimed

Q09335 / 2187

Q-1031-R 1929624

by Sillkagel) in a mixture of 55 ml hexahylphosphoramide (distilled off from CaH ₂ at reduced pressure and stored over 5A molecular sieves) and 53 a1 H-methyl-2-pyrrolidone (with reduced eruene. aMestilliart τοη CaH ₂ and stored over 5A Molecular sieves) emptied. After mixing for 5 minutes, _{6.3 g (0 sec} 025 Hol) 4,4'-3iboenzoyl chloride are added all at once. After a further 2 »Hj: lnüt ± according Mischen.werden 6.43 g (O ₉₀₂₅ mole) of 2, S-NaphtSialoyltthlerid added all at once, while with a cool water bath (ie 20 ³ C) is cooled * The mixture hardens in 7 minutes to a clear, rubber-like mass and is left over: seam at low temperature. It is then combined with water and stirred at high speed in a mixer, mixer. The solid is washed three times with water by adding it is stirred in a mixer, and isolated by filtering it off on a coarse-pored sintered glass suction filter. The polymer is overnight la a vacuum oven at about 70 ⁰ O dried "The yield betrögt 17.3 g (94.8 $> of theory) _f

PilmherBtellmg:

! ■■ ^ ■ WnWlllllWWlMIIIMI I! "Willi III I I '" WMiUMUM .- *

A mixture of 0 ₈ 20 g of its own polymer and 8 _p 0 ml of a solvent, prepared from 2.4 g of methylene chloride. and 100 ml!, ^ Bimethylacetaiaid, is stirred in a test tube with a spatula at room temperature. Mixing is continued (24 hours) until a'clear, flowable solution is obtained. is spread on a glass plate with an O ₉ 0127 cui squeegee »The plate is then immersed in cold water. .While the mass coagulates, the ez-Gebenda "Pllin eich τολ the glass plate and is dried * by pressing a-rfisohen adsorptioi capable papiarhan cloths at *? Ö ° C in a vacuum oven" The dry S. ¹ IIm is clear, saäh-uiia flexible

- 98 ~

009836/218?

BATH

Manufacture: an aniso tropic mass ;.

A mixture of 5-0 g of the above polymer and 45-0 g of 99s2% strength by weight sulfuric acid is mixed under anhydrous conditions with; a mechanically driven paddle-type stirrer in a 200 ml Eund flask while cooling with an ice / water bath. The mixture is frozen overnight. The resulting mass shows Hühropaleszenz w & ü depolarized polarized light.

j ^ adenhers-fcelliing by

The spinning slurry produced above is centrifuged to remove entrapped gases. It is then extruded by means of a mechanically driven syringe through a 0.064 cm thick Melme tall spinneret having 20 holes of 0.0076 cm IferchsLesser in an aqueous bath at 25 ⁰ C. The sow is about 5 _1/2 inches wide and about 2.54 inches deep. After passing through a bath length of about 0.76 m, the yarn is guided out of the water at an iron angle of about 45 ° and onto an electrically driven winder. -1Mb of gam is tied up on a perforated spool at 11.6 m / min. It is then washed in cool running water over lausiit washed and dried in air at room temperature. The loads are amorphous and have an orientation winch: ®! of 38 °, determined from a wide-angle X-ray trail diagram. The threads £ ilgen the following I / E / Mi / -the values: _ 5.5 / IOE _t 2 / L63 / 4.01 (Pdlmungsgcschwindigkeit 10 Jt)

j | er threads,; "

The above yarn is passed at 7.62 n / min, through a heated at 400 ⁰ C Mtikr (Device I) and 8.39 m / min.

sizing threads show mean ICri etallinitit and. have an orientation angle of 15 ° ■>

- 99

009838/2137

Q-1031-R ^m 1929684

The threads show the following I / E / Mi / den values: 10.3 / 2.3 / 567 / 2.46.

Example 12

The present example illustrates the manufacture of (l) a copolymer with random distribution, that is made up of repeating units below

-NH- (/ ^ -00-, -NH-f V) -NH- and -00- (' ^N ) ~ C0 ~

(relative molar ratio 1ϊ3ϊ3) are selected ?, (2) a anisotropic oleum mass of the mixed polyamide and (3) threads of mixed polyamides.

Polymer production:

4.8 g (0,0Σ! 5 moles) of p-Amlnobenaoylchloridhydrochlorid be "ir> weighed h _e in a chamber which is kept under anhydrous conditions a Polyäthyleiibeutel" in a drying chamber, a The open end dea bag is eiiem glass tube connected with about 7 _f 61 cm length having at one end a 29/26 S Innenverbindiingsanschluß = the bag with the tube is connected mer removed from the dry comb and by means of the 3 terminal to a 500 ml Haraherste] lung tank, equipped with a stirrer and is equipped with a potassium chloride drying tubec The contents of bag B are as quickly as possible in a solution of 8.10 g (0.075 mol) of p-phenylenediamine (sublimed by Silil; agel) in a mixture of 130 ml of hexaraethylphosphoram: .d ( at reduced pressure, distilled off from OaHg and stored over 5A molecular sieves) and 140 ml of K-methyl-2-pyrrolidone (at reduced pressure distilled off from OaHg and stored over 5A molecular sieves)

- 100 -

009836/2187

emptied, after 5 minutes of mixing, 15 * 23 g (0.075 mol) of powdered serephthaloyl chloride are added all at once with vigorous stirring. The !! temperature of the reaction mixture is moderate with a cool water bath (20 ⁰ C) in the mixture is 5 minutes, a kautsehukahnliehe mass and is allowed to stand at room temperature Bht. The mixture is then combined with water and stirred in a 3 _f 785 liter mixer at high speed. The solid is washed three times with water by stirring in a mixer and isolated by stirring on a coarse-pored Si & terglasnutsehe filtered off The solid is laughed over in a vacuum oven

dried at about 7O ^{0 O.} The resulting solid yellow pearls (25 »6 g) are ground in a Wiley = MtiMe until they pass through a sieve with a mesh size of ύοά 0.84 (20 mesh)»! Then they are heated for several hours with hot 9β $ hydrochloric IMEIs @ 2i8äure Terri layer "the acid is removed by! filtration and the solid washed with several portions W!". sser then washed About Haoht and dried at about 70 ⁰ C in vacuum oven eijiem. The polyamide yield is 19.0 g (91% of theory) ₉ Me logarithmic viscosity number, measured on an iron 125 solution ^. g Polymerisa-; in 25 jO ml 95 to 98 Gewo-5 $ lger Sohwefelsäux ©, amounts to 6.82,

A Mi-sohiing 7 ₉ 5 β ^ © ^β above polymer and 67.5 β fuming sulfuric acid (0.8 $ free SO ,,) is under v / aseerfreion conditions with a mechanically driven vane type Rührfjr in a 200 ml round-bottomed flask mixed while cooling with an ice / water bath · The mixture is stirred for several hours until visible. no more solid dents can be observed, the cooling bath at room temperature during this period

- 101 -

009836/2187

is allowed to warm up. The resulting mass shows Rühropaleezenz and depolarized linearly polarized Light.

ff by ad enherstellung, Naßs p i n n s?

The Spinnmaese prepared in the above manner is sur-removal of trapped gases sentrifugiert "It is then spinneret by means of a mechanically driven Spritse by a 0.064 cm thick extruded precious metal with the punch 20 of 0.005 cm diameter in a Wasserkoagulierungsbad with 27 ⁰ C. The water bath is about five and a half inches wide and about an inch deep. After running through a stretch of bath about 0.61 m, the yarn is led out of the water at an angle of about 45 ° and to an electrically driven winder. The yarn is perforated on a; Coil at 9 "45 m / min _o gesactmelto It is then washed for several (3) hours in cool running water and a rope is dried in air on a coil at temperature." Orieatlerungswinlcal of 28 ° _f determined from a wide angle Röntgenstrahlssidiagrpmme bis Päden show aie referred to as "T / e / Ml / the values :. 9 ^ 2 / 10.1 / 268 / 3.41 ,

_ii na, s sen ,, gaden:

The above wet (washed) yarn is fazse with 7 »62 ra / min _e '. a heated to 61O ⁰ C tube (device B) passed IMD geBaminelt 8.1 m / mln. " The faed ^ n sseigen high Kristallini SiOH resulting did and an orientation angle of 10 °, determined from a wide angle ~ Röntgenstrahlendl & gi? _E aEöß The threads show the following! I / E / Mi / den values at 20.1 / 2.0 / 1069 / 2.73.

- 102-

009836/2187

The present example illustrates the manufacture of (1) a mixed polyamide with random distribution, that consists of repeating units "below

and

(relative molar ratio 1: 1: 1) are selected, (2) one anisotropic oleum mass of the mixed polyamide and (3) threads of the mixed polyamide.

Polymer production:

14.4 g (0.075 mol) of p-aminobenzoyl chloride hydrochloride are placed in a drying chamber, i.e. in a chamber which is below is kept anhydrous conditions, weighed into a polyethylene bag. The open end of the pouch is with a glass tube about 3 inches long and 1 inch inside diameter connected, which has a 29/26 S internal connection terminal at one end. The bag and the tube are removed from the drying chamber and using the S Connections with a 1 iitr. Resin production tank connected, dei: with a Hührer and with a! Calciumchloridtrockenr-ab :? equipped, and it is cooled with an ice / water bath. The contents of the sachet will be released as quickly as possible (generally within 3 minutes) in a solution of 8.10 g (0.075 mol) of p-phenylenediamine (sublimed duroa silica gel) in a mixture of 160 ml hexaaethylph'jsphoramid (distilled from CaHp under reduced pressure and stored over 5A molecular sieves) and

- 103 -

009836/2187

1929684

100 ml of N-methyl-2-pyrrolidone (distilled off from CaH ₂ under reduced pressure and stored over 5A molecular sieves) emptied. After mixing the above ingredients for 5 minutes, 15 »23 g (0.075 mol) of powdered terephthaloylochloride are added all at once with vigorous stirring and βί3 is further cooled with an ice / water bath. After about 20 minutes a clear gel is obtained which is left to stand at room temperature overnight. The clear GaI is then combined with water and _{stirred at high speed in a 3 f} 785 Xitr mixer. The polymer is washed three times with water by stirring in a mixer and isolated by filtering it on a coarse-pored sintered glass groove. The polymer is dried in a vacuum oven at about 70 ^{° C. overnight.} The resulting yellow beads (37.1 g) are triturated with hot 93 # formic acid for several hours. The acid is removed by filtering through a coarse-pored sintered glass groove. The polymer is washed twice with water and finally with acetone in a mixer as described above. It is in a vacuum oven overnight at about 70 ⁰ O The dried Polymerisatausbaute is 24.0 g (90.8 #) · The logarithm - sohe viscosity number, measured on a solution of 125 mg of polymer in 25.0 ml of 95 to 98 Gew _e -? 6iger sulfuric acid, is 3.73.

Making a mass;

A mixture of 5> 0 g of the large polymer and 45.0 g of fuming sulfuric acid (0.8 # free SO ₅ ) is mixed under anhydrous conditions with a mechanically driven paddle-type stirrer in a 200 ml round bottom flask, while an ice / water Bathroom is cooled. The mixture is stirred for several hours, after which time no more solid particles can be observed. The resulting mass shows Rühropaleszena and

- 104 -

00983 6/2 187

depolarized linearly polarized light »

The spinning mass produced in the above process is centrifuged to remove enclosed oases. It is then extruded by means of a mechanically driven syringe through a 0.025 cm thick stainless steel spinneret with 20 holes 0.0076 cm in diameter into a water bath at 27 ^° C. The water bath is about 5.1 cm wide and about 2.54 cm deep. After passing through a bath length of about 0.61 m, the yarn is guided out of the water at an angle of about 45 ° and passed through an electrically driven winder. The yarn is collected on a perforated bobbin at 12.8 m / min. Eb is then washed for several (3) hours in cold running water and dried in air at room temperature ° and a speed of sound of 4.72 ksi / Selc. The threads have the following T / E / Mi / den values: 8.6 / 10.8 / 205 / 5.89.

Heat Treatment of l ung "threads ;.

The yarn / else produced in the above V is conducted with 7.63 m / min ·, through a heated at 600 ⁰ G tube (device A) and collected with 8.24 m / min. The threads custody resulting aeigen high crystallinity, a Orient! Erungswinkel of 10 °, an acoustic velocity of 9.29 km / sec "and the following ^r J? / E / Mi / the value 1O ₉ 7 / 1.2 / 821 / 5.39.

.Movie:

0.20 g of the above polymer are placed in a Versuohsrohr with 4 _B 0 ml of a solvent which is obtained by dissolving 3.0 g of lithium chloride in a mixture of 66 2/3 ml

- 105 -

00983372197

Q-1031-H-; / ^m 1929684

Hexamethylpfcosphoramid 1/2 and 33 ml li- = lfetkyX ~ 2 ~ pyrroliaori is prepared, and the mixture is m ± t a spatula stirred at room temperature until a liquid kis: ·: © solution is obtained. Is to be further 4 _S O eye give nl solvent and the resulting SiOH Klera Scssag is spread on the Oberfllsiie a glass plate by means of a C, 0127 cm doctor blade. The plat``; © is then placed in cold water. While the mass coagulates, Ii5st & es · 3Ιση. resulting FilB himself by swlselien adsorptive from the glass plate afc-τιβ-ϊ ^ ird dried at 70 ⁰ C in a vacuum oils ". Papi towels are pressed · dry PIj m is looked and has one leiciits feri

At s υ i e 1 14

The present example veraiscliEuliöIr ^ £ 1) allows the production of a mixed polyamide with accidental ^ ¥ ^ 2r ^r -eiluag ₉ that consists of repeating units; _a the under

-BH- ^ Y> ~ M. imd ■ = '! Qg ^X ) —CO «

(relative ratio 3: 1: 1) eu8gev? alslfe slsi-ϊ, (2) a axaisotrope Haoee clea Mischpol jramids unö. (,?)? "ds: a slss M:?, Schpolyaa: .ds ·

Polymerizate] lerBtellunfi; s ■

57s6 κ · t ° »3 ^{ -> mol). p-jUflinobenzoylchloriäkyclrooIiloriOl v / earth in a fe · Jokenkamiaer, fi, h. in a ΈίΜ ^ ΒΤ- the * mter wasBöivfrelen conditions, in eisism Polyäthylenebut jI ■ weighed in. The open en <ie äey bag is connected with Qi: iem glass tube with about 7 _t 6 ca I «SBg3 _f

- 106 -

009836/2187

bad original.

dae auxvfeißt a 29/26 \ InnenverMnaujigesaschluß at one end. The bag and the ear are enti'örat from the! Üroeken ™ lcamraer and by means of the connection with a 1 I »tr. HerslierütellmigBl'Eihalte ^ x · Terbunden, who imo with elnsm stirrer. advises -inern Kalslaniohloild-Trockenrolix is equipped «I ^! : r the inside of the bag we'd as soon as possible into a l'os mg of 10.8 g (0.10 mol) of p-phenylondlarain

by Silils & gel) in a mixture of 260 ml of iosphoresiid (distilled off from CaH ₂ uid at Tsrmindestein Drnok, stored over a 5-4 molecular sieve oil) and 280 ml of methyl, pyrrolidone (at -vsriaidertem I) distilled off τοπ CaII ₉ uiif ?. ar.f stored over 5A molecular sieves) emptied. After 3 hours of mixing, 20.30 g (0.10 mol) of powder are obtained. Shaped tcrepjitheloylolilorid (coated) with vigorous stirring. The temperature of the mixture is moderated with a y / aestv.rbafl at room temperature. The mixture is quickly lakoa and imierlia / .b of about 10 minutes, a firm cash is obtained. The solid mass is left to stand for 2 days The moist mass is then stirred with water in a 3 »785 3Jtr * mixer with a high degree of volatility, Dan P <: 3.2iaeriBat is mixed three times with water , iaaem es; in e: toeni mixer stirred \ fird _ff and isolated, in which * he filiriert on a gx'obporigen fSinterglasnutßßhe r-L. The PoIymer.Leat v ^ ix'd over Haoht in a y-acuum oven V, el otv / a 70 ⁰ C. The Polymerieataiiabeui; e amounts to ¹ JV ₉ Q g C9715 $> of the theory). I) Io logarithm! Aehe ^{c /} i ikoaitäi / OSCiilj £ ernes 13 en in a solution of 125 rag Polymeric acid in 2 _t about 95 "to 98% strength by weight sulfuric acid, amounts to 3.77.

MaasQ:

A Miechui: ^ τοη 40.0 g of the above polymer and 360 g 39% sulfuric acid is produced under anhydrous conditions rides a mechanically driven stirrer Steel in a 100 ml hardening container

- 107 -

Q 09836 / 21Θ7

E ψ 1929594

mixed »while cooling with an ice / water bath. The mixture is stirred overnight during this Time the cooling bath is allowed to warm to room temperature. The resulting mass shows agitated tropalescence and depolarized linearly polarized light

Thread production by wet spinning;

The spinning dope prepared above is centrifuged to remove entrapped gases and any solid particles. It is then passed through a 0.064 cm thick precious metal spinneret with 20 holes _{at the rate of about 0.8 ml / Hin o at a bridge of 26.6 kg / cm} of 0.005 cm diameter is extruded into an aqueous bath which is kept at 16 ^° C. The bath is about 40 cm wide, 14 cm deep and 94 om long and has rollers made of stainless steel »which are about 0.61 m apart. The yarn is drawn through the bath and around the rolls in such a way that it runs through the water bath three times. The yarn is collected on a perforated spool at 10.1 m / hin. It is washed in cold running water for several hours (i.e. for 3 hours) and dried in air at room temperature. The threads show medium crystallinity and an orientation angle of 28 °. The threads show the following T / E / Mi / den values: 10.2 / 7.8 / 264 / 2.13.

Heat treatment of the threads

The .hergestellte in the above manner, yarn is passed at 7.6 m / min, through a erhitstes to 586 ⁰ C tube (device B) and 7 »86 m / min, wound up. The calibrating threads show high crystallinity, an orientation angle of 10 ° and a speed of sound of; 11.51 km / sec. The threads show the following I / E / Mi / den values: 15.6 / 1.8 / 838 / 2.00.

- ICÖ -

009836/2187

. . SADORiQlNAL

Example 15 to 17 ^ld

The following m three examples illustrate the production "of anisotropic Oleummassen, the mixtures of poly-Cp bensamid) and poly (p-phenylene terephthalamide) contain, as well as the production of filaments from these compounds. The preparation of Polj- (p-benaaiaid ) and from poly-, (p-phenylenerephthalamide) is described separately,

Poly ° (p ~ ben samid) productioni

120 g (0.625 mol) of p-arainobensoylchloride hydrochloride are weighed into a polyethylene bag in a drying chamber, ie in a chamber which is kept under anhydrous conditions. The open end of the bag is connected to a glass pipe having about 7 »6 cm long" the on has at one end a 29/26 f inner connection terminal ₀ Dar bag and tube and means removed from the drying chamber of the ^ terminal to a 1 liter HarzleretelluBgsbehälier connected ₅ which is equipped with an air-driven stirrer and a calcium chloride dry pipe -Methyl-2-pyrrolidone (distilled off from GaH ₂ at reduced pressure and stored over 5A molecular sieves) emptied, stirring vigorously and cooling with an ice / water bath. The mixture becomes a solid mass within 13 minutes. It is left to stand over Haoht at room temperature. The solid mass is then combined with water and stirred in a 3.785 liter misoher at high speed. The polymer is washed three times with water? by stirring it in a mixer, and isolating it by filtering it off on a coarse-pored sintered glass tube. That

- 109 -

0Ö9838 / USf

BATH ORIGINAL

Polymer is dried overnight in a Vakuiimofen at about ⁰ C 7Q. The polymer yield is 70.0 g (94.3 $> the Sheorie). The logarithmic © viscosity rate, measured on a solution of 125 mg of polymer in 25.0 ml of 95 to 98% strength by weight sulfuric acid, is 2.83.

Poly- (p-phenylen / t er e. Phtha l aiaid) -Hers tellun / e ;;.

20.31 g (0.10 mol) of powdered lerephthaloyl chloride are added to a solution of 10.80 g (0.10 mol) of p-phenylenediamine and 60 ml of N-methyl-2-pyrrol.idone and it is in a 0.946 Ltr Mixer mixed at high speed. Within minutes a stiff hatred is obtained. After 20 minutes the mass is combined with water and stirred in a 0.946 liter mixer at high speed * The polymer is washed 4 times with water, once with alcohol and finally with acetone by stirring in a mixer, and filtered through isolated. The polymer is dried over Kacht in a vacuum oven at about 100 ⁰ C. The polymer yield is 23 »0 g (96% of theory). The inherent viscosity, measured on a solution of 125 mg of polymer in 25.0 ml of 95 to 98% by weight sulfuric acid, is 3.67.

Production of an anisotropic , mass;

Poly-1,4-benaamid and poly (p-phenyleneterephthalamide), prepared as described above, are in the amounts given in Table I together with 45 _f 0 g of fuming sulfuric acid (0.8 # free SO ») in a 200 ml Mixing round bottom flask equipped with a mechanically driven hill-type stirrer while cooling with an egg / water heater. The mixture is stirred overnight, during which time the cooling bath is allowed to warm to room temperature. The masses are flowable and aeigen Hühropaltaatna

- 110 «■. .,

0 08mm?

BATH ORIGINAL

Q-1031-B

Table 1

sssssssssssescssasascsss

Crowds

Haese: Example poly (p-benzamide) poly (p-phenylene / terephthalic)

amide)

15 2.5 g 2.5 g

16 1.25g 3.75g

17 3.75 g 1.25 g

Padenhereteil; by wet spinning i

Each spinning dope prepared in the above manner is centrifuged to remove entrapped gases and is then extruded by means of a mechanically driven piston through a 0.064 cm thick noble metal spinneret with 20 holes 0.0076 cm in diameter into a coagulating water bath at 25 ° C. The water bath is about 5 »! cm wide and approx. 2.54 cm deep. After passing through a bath section of approx. 0.76 m, the yarn is guided out of the water at an angle of approx. 45 ° and to an electrically driven winder at the rate given in Table II. It is then washed in cold running water for several (3) hours and part of it is removed for heat treatment. The best is dried in air at tree temperature. The threads show the orientation angles (O ₀ A ₆ ) given in Table II below, including T / E / Mi / den values (all with 10 # elongation speed).

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98 36/2137

Tables

Thread as if extruded

Dimensions:
example Thread collecting device
agility 5
7th
4th T E. Thread properties the O.A. 15th
16
17th 9.14 m / min.
IC, 7 rpm
10.7 m / min. ,8th
,1
"8th 9.6
10,
10, Wed 4.98
4.11
5.42 28 °
25 °
31 ° 165
0 220
8 161

W änaebeh aridl u nff of wet threads:

The obi ^ e nesse (washed) Ga :: n in the state as extruded is passed r-it 7.64 m / min ₀ through a ^{tube heated to 640 0} C (device B) and collected at the speeds given in Table III The resulting threads have the orientation angles and T / E / Mi / den values given in Table III. The cask of 15 (Table II) trcckene spun yarn is heated with 7.63 m / min through the _β at 600 °, directed 'getflllte with nitrogen tube structure and collected at 8.1 m / min _o. The calibrated threads show high crystallinity and an orientation angle of 12 °, especially from a tioitwinktl X-ray diagram. The loads see the following Oü / E / Mi / den values: 11.8 / 1, .3 / 889 / 4.8O.

Table III heat-treated thread

Thread out
'hfl α ηαο F, densaaimelge- T , 9
.3
a 1
1
1 Stringy leo sticks E. Wed the O.A. hwlnOl ^ eit 15th
11th
10 ,8th
, 4
»4 946
1056
805 5.98
3.76 8 °
9 °
10 ° 15th
16
17th 8th.
8th,
8th. 66 m / min c
23 m / min.
39 m / min

009836/2187

βΑΟ ORIGINAL

Β ,, β, i B, p.,! θ 1, 18

The present example illustrates the manufacture of (1) a mixed polyaraid with random distribution, which consists of sioh repeating units »the under

and

(relative molar ratio 9: 1: 1) are selected, (2) an anisotropic Haraatoffmasso of the mixed polyamides and (3) threads of the mixed polyamide _a

Polymerization division:

A 1 liter resin production container, equipped with an air-driven Soher-Saheibenrtihrer made of stainless steel Carpenter 20, nitrogen inlet tube and potassium chloride "Trooken tube, is flamed out with a Buneen burner and at the same time flushed with nitrogen." The container is closed and placed in a drying chamber, the " H. placed in a chamber which is kept under v / aaser-free conditions, 352 ml of tetraiethylurea are poured into an iSriemseyer flask in the drying chamber, which is then sealed and cooled in ice. 3.888 g (0.036 mol) of p-phenylenedlamine and 7.308 g (0.036 mol) of terephthaloyl chloride are weighed in the drying chamber, ground together with a pestle in a mortar and transferred to an Erlenmeyer flask, which is then sealed. 62.220 g (0.324 mol) of p-Junino- 'benzoylechloride hydrochloride are poured out in the drying chamber and transferred to the container. The container is removed from the drying chamber, reconnected to the stirrer motor and nitrogen line and cooled in an ice bath.

- 113 -

009836/2187

.- ^ <^. · -...; 8AD ORIGINAL

Tetramethylurea is quickly poured into the p-amin above: 3oylchloride hydrochloride, which is stirred at high speed, immediately afterwards the mixture of p-phenylenediamine and xerephthaloyl chloride is added to the above reaction solution. It is then placed in a bis-bath for 15 minutes with cooling and stirred at about 25 ⁰ G for 2.25 hours. The solution is combined in a mixer-nd ν _B water stirred for 5 minutes at high speed and the laiig sieJi resulting precipitate is sWMtriert. The precipitate is washed three times with water and washed with alcohol by stirring in a mixer (3 to 5 minutes) at 90 ⁰ C in a vacuum oven '; lm nitrogen atom getroclcneto Me Polymerisatauobut t carries 99.6 '; i,

Herstellun _t a: the mass:

30 g of the above polymer and 110 g of tetramethylbarnstoff / lithium chloride solution are placed in a 503 ml des Salaes contains _9. Introduced _α The resulting mixture is cooled for 2 hours in solid carbon dioxide and then for 2 hours at 125 ⁰ C (oil bait temperature). iserUlrt ₀ Disposal begins after 45 minutes. The M ^ aoliing v / ith 2 Stimden Xaiw _t in fa "stone liohlesxlicaiycl cooled and then for 15 hours at 125 ⁰ O (Ölbaltemperator) ?? ge iii: .rt _o iOrmmasse is again 2 hour 311 laiig in .fentorn KohXendioxya gerciihlt and then 5 hours: 1 year at 130 ⁰ O (oil bath temperature) for 15 hours at 12O ⁰ O. 13 weight, - ^ solid he »ssu form * the mass depolar- *

- 314 -

009836/2107

BAD ORiGtNAL

Yaws as a thin layer of linearly polarized light ]? aaei} jh.erstellimgdurG.b S

The composition produced in the above 4p Weiee is HO erlittst to about ⁰ C and at a rate of about 2.34 ml / min, at a pressure iron 5 »625 Ms 5» 976 kg / cm ² by a erhitste to 125 ⁰ C spinneret des 3? yps rait lead with? Holes with extruded O ₉ 01 cm diameter in a Troolmuugssäule whose walls are kept at a temperature in Beireich 198-207 ⁰ C, "the column with a rectified current (0.1344 nr / min"), vo: i dry Purged nitrogen which enters the column at 235 ° 2. The emerging threads are passed over a small guide roller carrying a size solution and wound on a spool at a speed of 139 m / min it is changed into water (25 ⁰ O) "are singe emerged to residues of solvent and salt to remove," the logarithmic Yiskositätösahl! LSATs polymer is of the Päden 1.48 »the leached with water in the air I ₅ dried (21.1 ⁰ FY 65 $ relative Peuo itigkeit!) Fsiden have average Krietallinität and a 1? ient.ierung8winke'J. from 27 ° »Cooked 3? aden sscigen the following T / E / MI / den-VJerte: 8 _f 5 / 2.8 / _{443/3 f} 01 ο

dling of threads:

Di α ht above? Geotellten 3? Aeden be clamped in a eins'tuflgen Ar) eitßgang under a nitrogen blanket over a gihaltene at 5-3O ° C 7 _t 62 passed cra Ilatte with their length by Hull increased to 1 i " will. The dwell time over the hot plate is about 2 seconds. The resulting fillings show high crystallinity and have an orientation angle of 12 °. The threads have the following

- 115 - * 009836/2187

Q-1031-R 71k

the T / E / Mi / den properties (cooked thread): 12.9 / 1.4 / 915 / 2.94.

Example 19

The present example corresponds to example 18, with the Exception that the mentioned repeating units of the mixed polyamide are present in a molar ratio of 2: 1: 1 and the specified differences "exist in apparatus and mode of operation ·

Polymer leather division:

The apparatus and the method of operation correspond, example with the following exceptions:

The intermediates are 8.110 g (0.075 mol) of p-phenylenediamine, 15.227 g (0.075 mole) terephthaloyl chloride, 28.805 g (0.150 mole) p-aminoben.zoyl chloride hydrochloride and 300 ml Hexamethylphosphoramide.

The reaction solution is stirred for 0.5 hour at about ^{0 0} O and 1.5 hours at about 25 ^{0 O.}

The polymer jsate yield is $ 99.4 and * f _inll - 1.16.

Making the mass:

In a 500 ml Harssherstellungsbehälter equipped with an air-driven shear-Soheibenrührer, condenser and calcium chloride drying tube, 30 g of the above polymer and 270 g iftramethylharnstof-f / Iiithiumchlorld-solution containing 6.54 wt. -4> of the salt, · Repeated cooling in solid carbon dioxide and stirring at 125 ⁰ O (oil bath temperature) does not cause complete dissolution of the solid material, but results in further cooling

- 116 -

009836/2187

BATH ORIGINAL

Q-1051-R ^Γ

# contains polymer - solid carbon dioxide for three hours and Rührbehandlungen tei 100 ⁰ C for four hours a mass 10 weight ".

Thread manufacture by dry spinning;

The mass produced in the above manner is ^{heated to 90 0} C and at the rate of about 3.5 oil / min. at a pressure of 9.843 kg / cm through a heated at 116 ⁰ C spinneret with 9 holes each O ₉ 0127 cm diameter in a drying column, extruded, whose walls are kept at a temperature in the range 197-207 ⁰ C »The column is purged by dry nitrogen, which enters the column at 264 ⁰ C with a rectified current (0.1274 irr / min). The emerging threads are passed over a small guide roller carrying a size solution and wound onto a spool at a speed of 139 m / min. This corresponds to a Spinnstreckfakior of 4,6 '· These extruded filaments (C 25 ^0), which is in water changed, dipped to best of solvents and salt leached to remove the "with water, air dried (21.1 ⁰ C , 65 1 » relative humidity) threads show average crystallinity and an orientation angle of 35 °« boiled threads have the following T / E / Ml / den values: 3.4 / 2.5 / 216 / 3.34.

of threads,:,

The equipment and the method of operation correspond to example 18 « The resulting filaments show high crystallinity and have an orientation angle of 15 ° <. The threads have that the following T / E / Mi / den properties (cooked thread): 7.2 / 0.7 / 886 / 1.68.

βΑΟ ORIGINAL - 117 -

0 0 9836/2187

. «■? O am

B ₁₁ el β ρ ie, 1 20

The present example Teraneohau is based on (1) MissclTioly-Cp-phenyien-p ₉ ρ ⁵ - »aiphenyiäl isophthalamid} (90:10), (2) an anisofcrspen of it and (3) Μα ©» from it »

Polymeri3athe:? 8 division:

A 500 ml container, equipped with a stainless steel ether of the .Schsetseyp., Nitrogen inlet tube and potassium chloride sock tube, is connected to a Bunsen burner :? ! aiisgeflamrat and equilateral purged with nitrogen "The behältsr is closed and in a chamber placed rocken- · _S 9 733 g (0.09 mol) of p-phenylenediamine in the Troclc @: 2lcammer GeV / ogen and ο brought into the Harztsehältar 192 m. HexamstliylpliOphoraiaid and 48 ml H ~ methyl- »2-pyrrolidone were measured in the srockenka liaier and poured into the container. The container is removed from the chamber and can be removed with the Hührmotox * ιοί d ii fuel line -rerlsunde-n .. the Misohung is gertihj.'t "until the resolution dea Mamina gtattfindöt, after which the;? uöhält © r * is jekilhlt in an ice bath _o.

■ I "827 g (0,0OJ. Mol) Isophthaloylohlorid IMD 22 ^ 09- g C0 _ä 06, J. Mol) 4 »4 ^e -'33ii} snzoylohlorid weräan in the TiOck-aakaiiaier succeed, combine'S and on oinmal to dex * DiaminlÖs ^ mg"; x Quick scrambled eggs and iceMiliiimg ^ srden 2 hours-I

Etv / a £ i this time the 'Aantatl hardens a gel ^! ; inöseä Maeoe., which is not melir Ruh ^ able :). £

This is left st-m for 64 hours at about 2Ti ⁰ C o ^ elicui «Di © si ilatinous Mas-tJo. is in a ^; a Mieoher .a; lt-Waife * 3r "vö3? elaigt, - the mixture wixd ia.it Ivohe-i ¹ Ges ^ lwia-äigkölt gorulated and: your resulting bodice is filtered off on a raittelporigen sinter-glass slide) et» The Uie-3. © r-

-lie -

0 09836/2187 bad original

blow is three times with Viasse :? and washed twice with alcohol, ii) .öem it is stirred in a mixer, and filtered after each VfescliTorgang "The product is 16 hours at 80 ⁰ C in a Vakuum.xfen the nitrogen atom dried <> The Polymerisatausb & ute is about 100 f * and

^ inn "^{2> 51} °

Division of a mass:

In a 3-centrifuge flask equipped with a stirrer, 25.812 g of the above polymer and 146.27 g of 100.72 liters of sulfuric acid (3.2 % free SO 2) are combined. The mixture is stirred at about 25 ⁰ C, to form an anisotropic composition containing 15 weight "- contains the copolymer #" The DDA-value of a 15 wt _o - # Kesseling strength in $ 100.81 sulfuric acid is 98.2 »

Fad enherst ellynjg, .durch, wet spinning;

The hergefstellte in the c-lived way mass is at 25 ⁰ C in a scarlet; brought frêle steel cell Carpenter 20 and through a spinneret having 20 holes of 0.076 lurchmeaser mm in 10 Ge w extrudievt .- # sulfuric acid at 25 ⁰ C · the koagulierteii filaments at a speed of 13 ra / min, Ri, f a coil is wound, said water cufgetropft v / IIDC These threads (25 ⁰ C), since ^ is changed, immersed b in Weßßer; not lo the Waeser more eauer lotο lie with water luftgetrockaeten (21.1 ⁰ C, 65 io relative humidity) yarns exhibit low crystalline ät ^ at oinem Orie leached ": atlerungswinkel of 28 ° and a sound velocity of 6.10 km / sec. Threads (in Eigönstearu.) Have the following T / E / Mi / den values: 5.2 / 4.7 / 273AO, 72.

- 119 i-

009836/2187

der, Fäjien.: _

The dry threads produced above are passed through a pipe at 600 ^° C. (device A) at a speed of 7.62 m / min. The threads drawn to 1.04 times show high crystallinity and have an orientation angle of 12 °. The threads have the following l / E / Mi / den Sigensohaften (cooked thread); 8.8 / 1.4 / 706 / 12.26.

Example 21

The present example illustrates the manufacture of (1) a mixed polyamide with random distribution, that is made up of repeating units below

-CO

¹¹²¹⁰ ~ ■ - ■ σο-

(relative ratio 95ϊ5: 95: 5) are selected, (2} one anisotropic * oleum mass of the mixed polyamide and (5) threads of the mixed polyamide.

Polymeri sai fiber division;

Mn 500 ml resin making tank equipped with a Rather made of stainless steel from SchJaeebesent3``p, nitrogen £ ~ inlet pipe and calcium chloride drain pipe, will rait one Bunsen-Breimer flamed out and at the same time with nitrogen flushed. The container is closed and placed in a Brought drying chamber. 9 »245 grams (0.0855 moles) of p-bienyleii diamine and 0.487 g (0.0045 moles) of m-phenylenediamine weighed in the drying chamber and placed in the resin container. : 92 ml hexamethylphosphoramide and 48 ml IST-Me-

'- 120 -.' ■■■ "

009836/2187

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Q-1031-R ^4Ί

thyl-2-pyrrolidone are measured in the drying chamber and poured into the container, the container is removed from the drying chamber and xdleather with the stirrer motor and connected to the nitrogen pipe «When the dissolution of the When diamine occurs, the container is cooled in an egg bath.

0.914 g (0.0045 mol) Isophthaloylohlorid and 22.865 g (0.0855 mol) 4 _P 4 ^l ~ Dibenzoylc2ilorid be weighed in the drying _chamber} combined and added all at once to the above solution, which is stirred rapidly. The reaction mixture is stirred while cooling for 18 hours. The viscous gel is combined with water, stirred in a mixer and the precipitate is filtered off. The bodice is washed three times with water and once with alcohol, each in one Mixer is stirred, and filtered off. V Dag product / ird 16 hours at 80 ⁰ C in a vacuum oven with a nitrogen stream dried <The yield is 100? S

In a centrifuge flask rüBtet with a stirrer be ~ _f 28.41 g of the above polymers and g 100 _f (Ί "free SO ₃ 5.2) 72 161.0 combined sulfuric acid sequence" The; The mixture is ^{stirred at about 25 0} O until a uniform anisotropic Maesö (which contains 15 wt .- ^ copolymer) is formed. The DDA value of a 15 weight mass in 100.81% sulfuric acid is 95.4o

The above nisotropic mass is placed in a Carpenter 20 stainless steel cell and extruded through a spinneret with 20 holes 0.076 mm in diameter into 10% strength by weight sulfuric acid at about 19.5 ^° C. The coagulated threads

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arrive at a speed of 11.4 m / min « over a guide: onto a take-up spool immersed in water. These threads are immersed in water (25 ⁰ C) ₁ that is changed; until the latter is no longer acidic α The leached with water, luftgetrookneten (21.1 ⁰ C, 65 $> relative humidity) filaments show little Kristallini "· tat at an orientation angle of 27 ° and a velocity of sound of 5.97 km / sec. Threads (self-made) have the following ϊ / E / Mi / den-Wertfi χ 5.6 / 5.3 / 297 / 8.98.

Heat treatment of thread

Dry and wet threads (which have not yet been dry) are passed through a pipe at 60O ⁰ O (device A) at a speed of 7.62 m / min *. Hasee threads, which are stretched 1.04 times, have a high crystal quality and an orientation angle of 9 °. Hie PU & on. (In. Elgenzustanc) have 3? / E / Mi / the values vcn 12.3 / 1.6 / 837 / 7.997 * ( Drockene threads which are stretched to 1.04 times _e have high crystallinity and a 0ri © ntie: rimgsv7lTfe> X vcn 9 ° and a speed of sound of 8.84 loa / Selc. The Pä ~ den have (in their own right) the following T / ü / Mi / den values: 12.8 / 1, 8/81} / 7.95.

B e iie 1 22

The present example verasiso illustrates the manufacturing process. vo »(1) a misoh polyainide with a random distribution, that consists of sioh repeating units below

(relative col ratio 9: ls9sl) are selected »(2) an anisotropic oleum composition of the mixed polyamides and (3) of

- "5 OO _"

009836/2187

\ ... i '.' '..:'. ⁸ AD ORIGINAL

Threads of kischpolyamide "

Pqlymerisatherstelliffli:

The equipment and operation are the same as in Example 21, with the following exceptions:

The intermediates are 8.760 g (0.081 mol) of p-phenylenediamine, 0.573 g (0.009 mol) of la-phenylenediamine, 1.92 ml of hexamethylphosphoramide, 48 ml of N-methyl-2-pyrrolidone, It827 g (0.009 mol) of terephthalic chloride and 22.609 g (0.081 mole) 4,4 * -dibenzoyl chloride ₀

The polymerization mixture is stirred for 2 hours and cooled in an ice bath. The polymer system forms gradually a viscous, non-stirrable gel. This mass is left to stand for 16 hours.

The product is dried for 16 hours at 90 ^° C. in a vacuum oven with a stream of nitrogen. The yield is IOC $> and the L _inh "2.26.

In a centrifuge flask equipped with a stirrer, 27.654 g of the above polymer and 157.90 g of 100.72% are added. Sulfuric acid (3 _t 2 % free SO-) combined. This miso !:, mg is passed a 25 ⁰ C ö hours at etv / to lüden to an anisotropic mass 15 Gre \ * c-fo Mischpolymerisa- !. contains. The DDA "value of a 15% by weight measure of BQ in 100 pounds ^; .: c Schwe.ieXsEure is 52.3.

Padenhersti.-llunir by Naßep.1 nnen s

The above egg isoti-ope mass is brewed with about 25 ⁰ C 1 & a Carpenter 20 spinning wool and passed through a spinneret with 20 holes. ^ rn of 0.076 mm I uraluaesser in 10 wt .-? oige

~ 123 009836/2187

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Sulfuric acid with 23 ⁰ C extruded. The threads are guided at a speed of 14 m / min via a guide onto a take-up spool (over which water drips). The extruded threads are ^{immersed in water (25 0} O), which is changed, until the latter is no longer acidic. The leached with water, air-dried (21.1 ⁰ C, 65 # RH) yarns show traces of crystallinity at an orientation angle of about 36 ° and a velocity of sound of 5 * 59 km / sec .. threads (in the eigenstate) have the following T / E / Mi / den values: 5.8 / 7 % 22/236/12, OO (stretch rate 60 #).

Heat treatment of the threads:

The troubled threads produced above are passed through a tube with 60O ⁰ C (device A) at 7.62 m / Hin. The threads drawn to 1.04 times show average crystallinity, an orientation angle of 14 ° and a speed of sound of 7.81 km / sec. The threads are as follows. I / E / Mi / den properties (thread in its own state): 10.3 / 2.2 / 596 / 8.85.

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Example 23

The present example illustrates the manufacture from ..

(1) mixed poly- (p-phenylene-p, ρ'-dipheriyldiearbOxaraid / -terephthalamid) (75:25 in Part A, 60:40 in "Part B),

(2) anisotropic oleum masses thereof and

(3) threads from it.

PART A · ....... -. ■ '- ■■

Polymer production : '- ■■■ -. ■■

A 1 liter resin production tank with a stirrer snow blow-type stainless steel, 'nitrogen inlet' tube and calcium chloride drying tube is equipped flamed out with a pumice burner and at the same time Purged with nitrogen. The container is sealed and placed in a drying chamber, 8.652 grams (0.08 moles) of p-phenylenediamine are weighed in the drying chamber and placed in the resin container. 171 ml of hexamethylphosphoramide and 43 ml of N-methyl-2-pyrrolidone are measured out in the drying chamber and put in the resin container. The resin container was removed from the drying chamber and again with the stirrer motor and connected to the nitrogen line. When the diamine has dissolved, the container is turned into a chilled ice cream,

16.7473 g (0.06) -MbI 4.4 "dibenzoyl chloride and 4.0604 g (0.02 mol) 2erephthaloyl chloride (both finely ground) \ rar-

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_{the y} weighed in the drying chamber are combined and added all at once to the rapidly stirred diamine solution. The reaction mixture is stirred for 1 hour and cooled with an ice bath. It solidifies to form a viscous gel, which is ^{stirred at 25 °} C. for τ β hours. That. Gel is combined with water, stirred in a mixer, and the resulting precipitate is filtered off. The product is washed three times with water and once with alcohol by stirring in a mixer, and is then filtered. _B It is dried for 16 hours at 80 ^° C. in a vacuum oven with a stream of nitrogen. The yield is 100 pounds and f) . ". Fe * 4.17, 4.13a

Making a, mass:

In a centrifuge flask equipped with a stirrer, "the 169.3 g of 100.70 # strength sulfuric acid (3" 1 $ free SO ₅ ) and 22.0 g of the above polymer are combined "This mixture is ^{stirred at about 25 °} C. until a uniform anisotropic mass, which contains 11.5 wt. ~ 5 pounds of polymer, is formed. The DDA value of a 11.5% strength by weight mass in 100.81% sulfuric acid is 97.2.

Thread production by wet spinning : i _f

The above anisotropic solution and is brought into a spin cell stainless steel Carpenter 20 extruded through a spinneret having 20 holes of 0.076 mm diameter in 10 weight ~ _e ^c / SiGe sulfuric acid at 25 ⁰ C. The threads reach a take-up bobbin at a speed of 20.4 m / min *. These extruded threads are ^{soaked in water (25 °} C.) that is changed until it is no longer acidic. The water-leached »air-

- T26 - ■ 0 0 9836/2187

dried (2i, 1 ° C _f 65 $ relative humidity) threads show traces of crystallinity at an orientation angle of "31 ° and a speed of sound of 5.14 kin / seco The threads (boiled sample) have the following T / E / Wed / den «fourth: 7.8 / 6.6 / 239 / 10.10.

Heat treatment of the threads :

Wet threads (which have not yet been dried) are passed through a pipe at 7.62 m / Hin, which has a temperature of 60O ⁰ C in the putty (device A). times have been drawn, show high crystallinity and an orientation angle of 11 ° as well as a speed of sound of 8.95 kra / sec »The threads (in their own state) have the following T / E / Mi / äen ~ fourth: 17.5 / 2, 2/744 / 7.57.

PART B poly merisatfter Btellung "

The equipment and mode of operation are the same as in Part A, with the following exceptions:

The resin production tank has a size of 500 ml » A shear disc stirrer is used.

The intermediates are 4.866 g (0.045 mol) of p-phenylenediamine, 75 ml hexamethylphosphoramide, 75 nl N-methyl »2 ~ pyrrolidone, 7.536 g (0.0270 mol) 4,4'-dibenzoyl chloride and

- 127 009836/2187

Q-1Q31-R

3.654 g (0.0180 mol) terephthaloyl chloride _β

The reaction mixture is stirred for 2 hours and cooled with an ice bath.

The polymer is dried for 18 hours at 80 ⁰ G in a vacuum oven with a nitrogen stream

The yield is 100 5 "and * \ _ίη ^ (concentration 0.1 $") = 5.71 ".

The dried polymer is stirred in a 5 Aung jSigen sodium bicarbonates and "soaked It is washed with water and 16 hours fstroir dried at 80 ⁰ C in a Vakuiuaofen with a Stickstof.

D © ^ rn ifWert (0.1 g polymer in 100 ml SehwefelsäurelÖ simgsmittel ait 95 to 98 i * Kc η sen stepped ion) is 5? 48 _β

Making a mass:

i 1.0 g of the above polymers are combined with 62.33 g 100.65 -feiger Sohwefelsäurs in a Zentril'ugenkolben which is equipped Htihrer "The mixture is stirred at etv / a 20 ⁰ O

eioh resulting at. isotropic mass (the 15th • it contains mixed polyamides) zoigt Rühropaleszenr. ,,

Faäentt first through

The above solution arisotrope w: .rd into a spinning cell made of stainless steel Carpenter 20 and brought by "ine spinneret having 20 holes of 0.076 mm diameter into a water bath Rait 23 ⁰ C extruded. The threads arrive with oiner

009836/2187

8AD OfiJGINAi.

speed of 14.5 m / min, on a guide on a take-up spool. These extruded threads are ^{soaked in water (25 °} C.), which is changed, until it is no longer acidic. The water-leached, air-dried (21.1 ⁰ C, 65 i> relative humidity) threads (in their own state) show low crystallinity at ^ an orientation angle of 29 ° and a speed of sound of 6.24 km / sec. The threads (in their own state) have the following! D / E / Mi / don value 11.9 / 6.4 / 274 / 8.45 *

Heat treatment of the threads?

The filaments contact with 7.62 m / min, passed through a tube in the M: .TTE a temperature of 55O ⁰ C comprises (device A). The threads drawn on the 1.06-fold3 show mean kriwtallinity at an orientation angle of 12 ° and a} · speed of sound of 7.18 km / sec. The threads (in the egg state) have the following I / B / Mi / den values: 16.5 / *, 4/639 / 7.64,

B_e _i β pi ΐ 1 24

The present example illustrates the manufacture of

{1) mixed poly ~ (p-phenylene-p, p ⁹ -diphenyldicarboxaraid / «terephthelaiaid) (55ϊ45),

(2) an anisotropic oleum lake thereof and

(3) by Fäder from it _o

009836/2187

Polymerisather position:

The equipment and the way of working are the same as in Example i? 3A, with the following exceptions!

The hardening container has a size of 500 idL

The intermediates are 9.733 g (0.09 mol) of p-phenylcmdiamine, 192 μl of hexaemethylphosphoramide, 48 ml of N-methyl-2-pyrrolidone, 13.817 g (0.0495 mol) of 4,4'-DIbOnJSOyIChIoX ¹ IcI vazä 8.223 g (0 , 0405 moles) terephthaloyl chloride.

The polymeric gel is stirred for 16 hours with cooling in tap water.

The yield is 100 ? * And rj _inll * 6.39.6 "54o production * in mass:

24.80 g of the above polymer are combined in a centrifuge flask equipped with a stirrer with 223 Ω 2- S 100.705% ßchv / eic acid. The mixture .wird at about 25 ⁰ C until an anisotropic mass results "the 10 GeWo-i" of the mixed polyamide. The older DDA value of a 10.0 gi-5Wp -

Pactenh first lung by wet spinning ϊ

The above anisotropic mass is brought and at about 25 ⁰ C in οine v free Stahlaille Carpenter nozzle 20 by spin-a- 20! Duehern of 0.076 mm diameter in 10 gewo- ^ lg Schwefölsäurj with 29 ⁰ C extruded "The Fiden reach Rait

■. . - 130 -

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at a speed of 30.5 m / min, via a! guide on a take-up spool «These extruded threads are soaked in V / ater (25 ⁰ C), which is changed until it is no longer acidic» The one with V / ater Leached, air-dried (21.1 ° C _S 65 tf ° relative humidity) threads are amorphous and have an orientation angle of about 4-0 °. The threads (in their own state) have the following Φ / E / Mi / den values; 9.7 / 6.7 / 256 / 3.42,

Heat treatment of the threads ;

The above dried fibers are passed at 7.62 m / min in a tube having in the middle a temperature of 600 ⁰ G (device A).

The threads drawn 1 "07-fold show little Crystallinity and an orientation angle of 18 ° »Die Threads (in the ESgen state) have the following 3? / E / Mi / den ~ Values: 22.5 / 3.2 / 668 / 2.77.

ΰ -3 i s ρ i β 1 25

Xte «present example illustrates the Heretellimg

sinein "föschpolyamid with random distribution, the auj eiob consists of repeating units that are selected; unite! under

-NH - ^ [Λ-CO-, -NH- (ζ \ -NH- and -CO- (e molar ratio " ¹ OtS),

009836/2187

Q.1051-H ^1it 19296S4

\ 2) an anisotropic oleum mass of the mixed polyamide and (3) threads of the mixed polyamide ₀

Polyxyny representation:

A 500 ml resin production container, equipped with a stainless steel blender, nitrogen inlet tube and calcium chloride drying tube, flamed with a Bunsen burner and flushed with nitrogen at the same time. The container is sealed and placed in a croquet kasnaer ", 7" 300 g (0.0675 mol) p-phenylenediamine are weighed in the drying chamber and placed in the container. The container is then dried out and connected again to the stirrer rotor and a nitrogen line. When the dissolution of the P: U> ss: iii has taken place, the container is cooled in a Bisbafi gi ^s «'-

■■!, 3> 21 s C0 | C? 25 mol) p-Aminobenzoylchloridhyörochic ^ ia imä 18.841 g (0 _? ) 675 I'tol) .4., 4 '-Dibenzoylchloride are in the Srookötikaiaiiie ? ab ^ i / ogew, -united and anf eiiroal? υ der ^ ascfn; /: öril-rir-; en biamin solution given _o The Eeaktiorexrii- «, cbung Yilrd for ΐ hour stirred and cooled in an'Eir bid and there in 16 hours stirred at about 25 ⁰ C-G el \ rirä IAIT V / Aoser combined, in a Miocher gsrCxhrt tm of Hie ü'll kill is filtered off. The Niederachlng il: cf; iFial τα it / ater and washed once with alcohol QT Ι «eiüein lisoher stirred and filtered \ fird _o l ^l na - ύιύ: \: is at L 8O ⁰ C for 16 hours in a: a stick. joi '£ ethern dried, Bie yield iGO? δ: and JJ _{1 ih} «4» 92 _? 4.81 »

«13Σ ■ ■ -009836 / 2187

8AD

Q-1031-H

Production he ain mass:

177 g 100.70 $ sulfuric acid and the like 23jO g & u above polymer are in a genteifwgenkol'ben with a stirrer of gerüstetem combined. The mixture was stirred at 25 ⁰ C wirfl j until a uniform mass anisotropic _t the 11.5 parts by weight-5 contains "copolymer, results in" The DBA value of a gewo- 11.5 ^ strength in mass 100.81 #iger S is 95 * 4 »

Thread production by wet spinning:

The above anisotropic mass is brought at 25 ⁰ C in one spin cell stainless steel Carpenter 20 d \ raw spinneret having 20 holes of 0.076 mm diameter in a HO wt _e - # extrudiertc sulfuric acid init 23 ⁰ C, the ropes are ei with sin ? Speed of 22. m / min <, wound slides © threads are in water (25 ⁰ C), the Geweehse! - X is »soaked _f until it is no longer acidic _o Me ν with water leached, air-treated (21.1 ⁰ C , 65 # relative © Feuchtigkeil ·) threads show traces of crystalliniti · '■; bsi an orientation angle of 32 ° and a sound ^ tiseto wind speed of 5.6? km / sec. The threads (cooked out) have the following T / E / Mj / den values: 8.3 / 7.1 / 183 / 4.86 »

Warmth! "And the thread '

The above dried threads are passed _through a tube at 7.62 m / min, which is heated to 600 ° in the middle (device A) - pads which have been stretched out 1.14 times show high crystallinity an orientation triangle voc 12 ° and a speed of sound of 8.80 km / sec "]) .. © threads (in Elgenzuatand) have the following 3? / E / Mi / the" Vfirtes 17.9 / 2, i / 8 ^f 5 3 / 4.58.

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1928694

At s P ₁₁ i el 26

The present example corresponds to the above example 25 "with the exception that the named repeating units of the mixed polyamide are present in the Mo! Ratio 2% 3i" 5 "

Polymerisath erstellupg '

The apparatus and the procedure are the same as in Example 25 »with the following exceptions:

The intermediates are 6.4 £> 9 g (Ο, Οβ mol) p-phenylsn ~ diamine, 214 ffll - hexamethylphoephorainld, 53 wl N-methyl-2-pyrrolidone, 7.682 g (0.04 mol] p-aminobensoylehloridhyclro · - Chloride and 16.747 g (0.06 mo .:) 4-, 4'-dibenzoylohlorld.

The polymer remains during the whole

in solution o A Filra is poured directly wet, * tier goll ».,

transparent, flexible and ssäli ioto

The polymer yield is 100% and f] _in ^ ss 4,8O ₉ 4 , BQ,

Manufacturing siner

In a centrifugal flask equipped with a stirrer, the 182.0 g of 100.70 g of sulfur ^; lure and 22.5 g dee obigea ■ polymer combined ■ ".'Diene Misühung.-wird- at 25 ⁰ C is stirred yew uniform aiilsotrope Kao;? ergxbt e, the 11 G-Sf _n -Mischpolymerisat contains ο Dor DM-VJeA ¹ "!; Airier 11» 0 in 100? 81 jSiger ■ Welding acid is 100 «

009836/2187

Thread-making aver oh hatred spin;

They above anisotropic mass is brought at 25 ⁰ C in a spin cell © stainless steel Carpenter 20 extruded through a spinneret having 20 holes of 0.076 mm in diameter in 10 gewo- ^ igs Sshwefelsäure mil 27 ⁰ C. The coagulated en Fiden be wound at a speed of 19 "8 m / Minoe on a bobbin., Which is immersed in water" These threads are soaked in water (25 ⁰ C), the wirJ changed BAES this is no longer acidic «. The ones leached out with water? air-dried (21.1 ° ö _$ 65 i "relative humidity) Fs to show traces of Cristal · = linität at sinem orientation angle of about 60 ° and a velocity of sound vcn 4 * 47 km / sec. The Fäöen have (boiled) the folgencen
3 * 5 / 9.6 / 194 / 5.31.

WJ-rjaebeliänä χ ^ ngder ^ threads:

Hanse threads (which had been dried yet niclit sine) ans to the above spinning process v / earth mine, 7.62 ra / min _e passed through a tube (device A) is in erhitsst üer center on 6OQ ⁰ C _{8 out;} ge on dao 1.08 ft.che verntreokten yarns show high Kriatallinität at er.nem Orientierungswiwkel of 9 ° and hate * E / E / Hi / n-V / _VO erte 12.7 / 2.0 / 622/4 , 45 (Päflen im Bigßrüsue * and), irockens J? Äf "© n rait of the same heat treatment, ^ <i3och a in era Steeok ^ er-hfilttiiß from 1, Q9 ~ faeh, K? N.gen l'obü Kri3tal3-iwitäfc ml "· an orientation angle VfjJi i? ^c min sinor Dchallg ^ sahvindlgkeli of 7 _s 08 krß / Sok _e 3) 3e threads (Iw Bigunsustanä) hf.ben T / E / Mi / den-Wertö of

009836/2187

8AD ORiGlNAL

Λ Q9 QR OΛ Q-1031-R * ^ΛΛ la ^^ DvjH

B eis ρ IeI. 27

The present example illustrates the manufacture of

(1) Poly-Cp «phenylene-p, ρ" -diphenyldicarboxamide),

(2) an anisotropic Oelumraasse thereof and

(3) threads

A 500 ml resin production container, equipped with a stainless steel stirrer of the snow blow type, nitrogen inlet tube and potassium chloride drying tube, is flamed out with a Bunsen burner and at the same time flushed with fc - *; liner "The container is sealed and placed in a roeksn chamber" β * 488 g (0 ₈ 06 mol) of p-phenylenedisricine are drawn off in the drying chamber and placed in the container. ¹ 128 ml of hexamethylphosphoramide and 32 ml of H-methyl-2-pyrrolidoE are measured in the iDroekenkamiBer. -and poured into the container ex. The container is removed from the dryness as soon as it is dry and again m; ', t <& ®m HÜhrsiotor and the stick * stoff lsi tune connected o When the slide is dissolved, the container is cooled in an exbath "

1-6-, 748 g (0.06 EoI) 4i4 ^e -dibeaaoylchloride (finely ground) are added all at once to the rapidly conducted dialup. Mixture is stirred for 1/2 hour and poured into an ice bath. Then etundon 16 is laug stirred at etwL 25 ⁰ C ". Bas gel-with combined water and gerühmt- in a mixer, after which the precipitate vrirdo filtered off This is three times with water for $ d once with alcohol washed" by a Mixer is set and filtered _o After the

..-.-. 136.009836 /2187

■ BAD OfilGtNAL

Q-1031-R ⁹¹

Washing with alcohol is poured over the polymer and filtered off. The polymer is ^{dried for 16 hours at 80 0} in a vacuum oven with a nitrogen atom. The yield is 100 ^c ß> and J] ^ _n J ₁ »2.28

A second similar preparation is 100 $ yield and ^a linh - ^{2 '00} °

Division of a mass:

In a centrifuge flask equipped with a stirrer, the approximately equal amounts (37t08 g in total) of the two above polymers and 303 g of 100.25% sulfuric acid combined »This mixture was stirred while cooling in a bis-bath until a uniform anisotropic mass was obtained results, the 10.9 Gew "- $ mixed polyamide contains and Rühropaleszeng shows·

Yarn production by cassette spinning?

The above anisotropic mass is brought at 25 ⁰ C in a stainless steel cell Carpenter 20 through a spinneret having 20 holes of 0.076 mm in Durohmesser 16.4 GEWO-jSige sulfuric acid at 19 ⁰ C The extruded Paden be at a rate of 16.8 m / sec «wound onto a spool which is immersed in water. The water-leached, air-dried (21.1 ⁰ O, 65 fi relative humidity) threads show low crystallinity at an orientation angle of 37 ° , 2 / 3.5 / 120 / 6.92? the speed of sound is 4.51 km / sec

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009836/2187

SADOflJGlNAL

Heat treatment of the threads:

The dried threads above are passed at 7.62 m / min through a tube, the center of which has a temperature of 60O ⁰ G (device A). The threads drawn to 1.05 times show average crystallinity at an orientation angle of 16 ° and a speed of sound of 8.19 kra / sec. The threads (cooked out) have T / E / Mi / den values of 3.2 / 0.8 / 293 / 6.46.

^ Determination 8

If a sample of poly ~ (p-phenylene-p, p »-diphenyldicarbo2C-amide) with a n _inh » 1.86 (prepared in a similar manner as above) is dissolved in 100.8% sulfuric acid to give anisotropic masses which contain 10 and 15% by weight of polymer, the DDA values determined for these materials are 30.4 and 100%, respectively.

Example 28

The present example illustrates the manufacture of

(1) Poly-ip ^ '- phenylenbenzaiaid),

(2) an anisotropic mass thereof and

(3) of threads from it.

The preparation of intermediate compounds is also described «

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009836/2187

Production of 4- (4 '-thion yla rainoph enyl) -benzoyl chlorine id

A solution of 48 g of 4 (4 ^(l- aaiinophenyl) -beneioic acid and 3 drops of ϊί, ^ dimethylformamide in 300 μl of thionyl chloride is refluxed on a steam bath for 1.5 hours. Excess thionyl chloride is kept under reduced pressure 50 ml of toluene are added to the flask and the suspension is concentrated under reduced pressure. This step is repeated with 100 ml of toluene * About 100 ml of toluene are added to the flask to suspend the yellow solid, άβτ / is filtered off under a nitrogen atmosphere to a SintergXasnuteche "The solid is washed with toluene, or petroleum ether (30 to 60 °) gewasohen and then dried in a Vakuußaxsiccator about Phoaphorpentoxyd and Paraffifisohnitzeln" The 4 ^ (4 ^(! = 5hioi) ^{.ylaminopheny>} l) ~ bE ⁱ iBoyl chloride has a P β 145 to 146.5 ⁰ C,

Production of 4- (4 "~ Aminop: @nyl) ~ benzoylchloridh3rärQ" chloride

24 g of 4- (4 ^r '~ Thionylaminophenyl) benzoyl chloride are suspended in 500 ml Met'iylench? I.orid in einjm flammgetroolraeten three-necked round bottom flask equipped with a mechanical stirrer and outlet tube is provided and öaseinlaß- ₀ The mixture we Saturated with hydrogen chloride for 2 hours. The solid is suspended in 250 ml of anhydrous ether and stirred for 1 hour with a magnetic stirrer. The substance is filtered off under nitrogen and then dried in a vacuum desiccator for 2 days. The yield of 4 "(4 ° -aminophenyl) - benzoylchloridhyd sOchlorid amounts to 68 $ "

009836/2197

ßAD ORIGINAL

1929684

Polymer production

A 1-liter resin ₀ manufacturing vessel equipped with a Schneebesenrübrer, nitrogen inlet tube and calcium chloride drying tube, is flamed with a burner and simultaneously purged with nitrogen. 210 ml hexamethyl phosphorus amide (calcium hydride distilled off at reduced pressure and stored over molecular sieves) and 210 ml IT-methylpyrrolidone-2 (calcium hydride distilled off under reduced pressure and stored over molecular sieves) are filtered in the drying chamber into a measuring cylinder . The cylinder is removed from the drying chamber and the contents poured into the resin container, which is cooled in an ice / water bath. 46.6 g (0.174 mol) of 4- (4 ^e ~ aminophenyl) -benzoylchloriähydroohlorid are weighed in the! Drying chamber in a polyethylene bag and then transferred rapidly at moderate stirring in the core container. The resulting mixture is stirred for 30 minutes after which the ice / water bath is removed. The reaction mixture is stirred for an additional 2 hours and 15 minutes. 12.9 g (0.175 mol) of lithium carbonate are added to the paint container and the mixture is stirred for a further 35 minutes. After standing overnight, the polymer mass is combined with water and stirred in a mixer, converting it into a fine powder. The polymer is washed three times with water and once with alcohol by stirring it in the mixer and filtering on a sintered glass suction filter will. The polymer is dried over fold at 6O ⁰ O in a vacuum oven. The yield of poly (p, p ^f -phenylenebenzamide) is 96.4 # (* H _K ij ^β 1 »99 in 99.8% sulfuric acid).

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Manufacture of a mass :

In a three-necked polymer bulk flask fitted with a Is equipped with a stirrer and is in an ice / Yiasser bath, 46 g of 99.83% sulfuric acid are introduced. 5 g of the polymer is introduced into the flask and the resulting mixture is stirred over freight while an anisotropic hatred is obtained. When stirred, the mass reveals its appearance and is spinnable »

thread production by wet spinning?

The spinning maize prepared above is placed in a stainless steel cylinder lined with "Teflon" ΪΡΑ © fluorocarbon and the whole is centrifuged to remove air bubbles. The Polymerisatmasse is then e.?cfcrudiert by a Platinspinndüse with 20 holes of 0.076 mm diameter into a water bath with a temperature of 20-30 ⁰ C by means of a mechanically driven syringe. The threads are wound up on a bobbin at a speed of about 7.93 m / min. Y / erts: 2.24 / 3.9 / 145.4 / 4.90 and a speed of sound of 4 * 06 km / sec.

Heat treatment of the pads t

The threads produced above are passed through a hot tube (device A) with a length of 81.3 cm, the inner wall temperature of which is 600 ^° C. in the middle. The Paden is by a factor of 1.1 times and stretched at a speed of 7.62 m / min ₀ in the hot tube led ©

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Q-1031-R 1U 1929634

The resulting threads show high crystallinity and have an orientation angle of 27 ° and a speed of sound from 5.82 km / sec, the threads have the following T / E / Mi / den values (thread not cooked out): 4.17 / 1.6 / 288.2 / 4.80.

Example 29

The present example illustrates the manufacture from

(T) a copolymer made from equimolar amounts of randomly repeating units of poly- (p, p'-phenylenebenzamide) and poly- (p-bensaraid),

(2) an anisotropic oleum mass thereof and

(3) of threads from it.

Polyme riaatherBte ˚:

A 1 ltr. Resin production tank equipped with a Whisk stirrer, nitrogen inlet tube and calcium chloride drying tube, is flamed out with a burner and at the same time flushed with nitrogen 200 ml hexamethylphoaphox - amide and 200 ml of ji-methylpyrrolidone-2 (each distilled off from calcium hydride at reduced pressure and stored through molecular sieves) are filtered into a measuring cylinder in the drying chamber. The cylinder comes out of the drying chamber removed and the contents are poured into the resin container * 22.6 g (0.0843 mol) 4- (4'-aminophenyl) -benzoyl-

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chloride hydrochloride and 17.04 g p-Aminobenzoylchloridhydro chloride (0.0843 mol monomer, wherein contain about 5 Ι "inert solvent impurity) are weighed into the Irockenkammer into a polyethylene bag. The solids are mixed together in the bag and then quickly transferred to the resin container with moderate agitation. Within 2 hours the contents of the flask form a "rubbery" mass. After standing over the weekend, 12.55 g (0.17 mol) of lithium carbonate in 100 ml of N-methylpyrrolidone-2 are added to the voluminous mass. The mixture is stirred for 10 minutes and then left to stand for 4 hours. The polymeric mass is combined with water and stirred in the mixer, where it is converted into rather fibrous glow. The polymer is washed five times with water and three times with alcohol by stirring it in the mixer and filtering it on a sintered glass filter. The polymer is dried in a vacuum oven at 60 ^{° C. overnight.} The yield of the copolymer is 98.2 # (Πχ ^ ■ 3 »03 in 99» 5 sulfuric acid) *

Making a mass?

In a three-necked polymer bulk flask equipped with a stirrer and located in an ice / water bath, 25 ml of 100.7% sulfuric acid are introduced. 6 g of the polymer are added to the flask and the resulting mixture is stirred overnight during which time an anisotropic mass is obtained, which shows Rühropaleszent.

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Paden therapy by NaQepinnen :

The spinning mass produced above is turned into a stainless steel

Steel cylinder lined with "Teflon" TEAvSJ fluorocarbon is placed and the whole is centrifuged to remove air bubbles. The mass is then se by means of a mechanically driven syringe through a Elatinspinndü- "with 20 holes of 0.076 mm diameter into a water bath with a temperature of 20-30 ⁰ C extruded * After passing through ₁ 61 m, the filaments having a a water route O Speed of about 7.93 m / min. wound on a wet spool and soaked in fresh water for about 4 hours before drying. Non-boiled threads show the following T / E / Mi / den values 416/7 »3/188 / 2.66 and a speed of sound of 3.45 km / sec.

Heat treatment of the threads :

The yarns prepared as above are passed through a hot tube (device A) with 81.3 cm long, having an inner wall tempera door is in the middle of the pipe 45O ⁰ O. The thread is stretched by a factor of 1.1 and guided into the pipe at a speed of 7.63 m / min. 37 km / sec. The threads have the following 3? / E / Mi / den values (not cooked threads): 6.9 / 1.5 / 530 / 6.95.

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EXAMPLE 30

The present example illustrates the manufacture from

(1) a copolymer that is made up of random white. se repeating units of Po Iy- (p> ρ "» phenylene · = benzamide) and poly (p-benzamide),

(2) an anisotropic mass thereof and

(3) from padsn from it.

Polymer preparation :

A 1 liter resin production vessel equipped with a whisk stirrer, nitrogen inlet tube and calcium chloride drying tube is flame-out with a burner and at the same time flushed with nitrogen. 230 ml of hexamethylphosphoramide and 230 ml of N-methylpyrrolidone-2 are filtered into a measuring cylinder in the drying chamber. The cylinder is removed from the drying chamber and the contents are poured into the resin container which ~ in an ice / water bath is chilled "15.7 g of 4- (4 ⁱ ~ aminophenyl) ~ benzoylhydrochlorid (0.0570 mol Konomeres wherein about 2.5 f ° inert solvent contamination are contained) and 34.9 g of p-aminobenzoyl chloride hydrochloride (0.01728 mol of monomores, which contains about 5 $ inert solvent contamination) are weighed in a polyethylene bag oil in the drying chamber. The solids are in the bag mixed together and then quickly transferred to the resin container with moderate stirring »Within 1 hour the contents of the flask form a" gum-like "mass. The polymeric substance is left to stand for 4 days and then combined with water and stirred in a mixer, in which it in rather fibrous

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Is converted particles ₀ The polymer is washed three times with water and twice with alcohol, by being stirred in deai mixer and filtered on a sintered glass funnel, "The polymer is ι dried in a vacuum oven at 7O ⁰ C pulverized in a ball mill and then again in the Brought a vacuum oven until it is dry. The polymer ^{yield is 91.4 # (^ inh β} 3.83 in 100.2% sulfuric acid).

Making a mass :

In a three-necked polymeric bulk flask fitted with a Stirrer is equipped and egg oh in an ice / water bath 45.0 g of 99.8% sulfuric acid are introduced. 5 g of the polymer are added and the mixture is stirred overnight, during which time a anisotropic mass is obtained, the ftühropaleszenz shows "

Thread production by wet spinning ;

The internal dimension made above is packed into a stainless steel cylinder with TEAMS '"Teflon" fluorocarbon lined. brought and daa whole is centrifuged to remove air bubbles "The mass is then exl by means of a mechanically driven syringe through" ine Platinspinndüse with 20 holes of 0.076 mm diameter into a water bath with a temperature 20-30 ⁰ C; rudiert "After passing through einor Water tri-fioke of 61 cm twist the threads at a speed of about 9.19 m / m: ln. wound on a spool · The spool is soaked in water overnight and then allowed to air dry. Unboiled threads show the following Τ / 3 / Mi / den values: 5.73 / 7.7 / 229 / 3.42 and

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009836/2117 _ßAD original

a speed of sound of 4.24 km / sec

Heat treatment of the threads t

The yarns prepared as above are passed through a hot tube (device A) with 81.3 cm long, whose inner wall temperature beträgtα in the middle of the pipe 400 ⁰ C, the yarn is stretched times by a factor of 1.1 "and will be at a rate of 7.62 m / min »in the pipe. The resulting threads show medium crystallinity and have an orientation angle of 19 ° and a speed of sound of 7.73 km / sec. Unboiled threads show the following T / E / Mi / den values 11.84 / 2.6 / 541 / 2.70.

DDA determination, Fadenher position ι

If the polymer described above (rj _{in} l} «3» 83) is dissolved in 100.2% sulfuric acid in order to form a 11 gev / _0-5 % mass, an anisotropic system is formed that has a DM - has a value of 100. A 7% mass of the same substances eats isotropically and the DDA value is zero. ! mi / the values of E, 58 / 9.1 / 183 / 2i85 "fold heat treatment at 45O ⁰ C (device A) are the I / J3 / ^mi / Den - values 11.9 / 2.4 / 614 / 4.92, the orientation angle is 15 °.

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a ns

Example 51 to 35

The following examples illustrate the preparation of

(1) ordered and semi-ordered p-oriented aromatic mixed polyamides made from p, p'-diaiainobenzanilide _t £ erephfrhaloylchlorid (X) and p, p'-bibenzoylchloride (Y),

(2) of anisotropic masses of the mixed polyamides and

(3) by Pädsn's mixed polyamides with high strength and high modulo

Mixed polymer production s

The copolymers given in Table IV below are prepared in an identical manner, using the appropriate ratio of diacid chlorides for the composition under consideration. All glassware are at least Asten dried for 2 hours in an oven at 120 ⁰ G, the weighing and dimensions are carried out in a drying chamber and the reactions are carried out under a nitrogen blanket.

The diamine "4 / is in a mixer in a 2j1 ~ volume odor of hexamethylphosphoramide and H-methylpyrrolidon-2 in an amount dissolved to a 10 to 13 weight percent concentration (based on the total weight) of final polymer zu ergeoeiic An equivalent amount of diacid chloride is given out very quickly, stirring as quickly as possible. The polymer solidifies in 1 minute a chewy gel that cannot be stirred. This is left undisturbed for at least 1 hour "! That

009836/2187

Polymerisat.wird is isolated in water, washed in the mixer four times with water and once each time with acetone and alcohol and ^{dried overnight at 100 0} O in a vacuum. The polymer can be further purified by first grinding it in a mill to reduce the particle size and then treating it with formic acid on the steam bath for 1 hour. After thorough washing with water, the polymer is dried again.

Polymers 32 through 35 in Table IV are prepared in this manner. Polymer 31 is made in hexamethylphosphoramide made alone, although similar results are obtained in a mixed solvent system should.

Making a mass :

The Spinnmaasen are made by appropriate quantities of polymer and solvent are combined and stirred at room temperature in a closed system. Anisotropic masses are obtained, the red thropalescence show., The masses are centrifuged before wet spinning

Hate spiders:

The hatred plan is carried out with a motor-driven hypodermic syringe, which is equipped with a large-area Spinneret m: .t 20 0.076 mm holes is provided. The strings are coagulated in water at room temperature. The immersion length is 60.0 to 81.3 cm. The threads are with wound at the highest possible speed (see Table IV), u while the coil rotates in a water

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_e advantage The thread is then soaked 16 Us 24 hours in distilled water ·

Heat treatment of the threads ;

The extracted wet threads are stretched and / or tempered through a hot drill (device A). The insertion speed is 3 »66 bin 7.62 ω / min. Stretching ratios, temperatures and thread properties are shown in Table IV. ¹

The mixed polyamides, the threads of which are described in Table IV, consist of repeating units, which are listed under

-TMGO-f \ -mG0 ~ £% -CQ- and -HHCO- are selected »

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TABEILE IY

Ul
I. Copolymers of
ρ, ρ ^β -dibenzoyl chloride * 1/0 linh ρ, ρ '-Siaininobenzanilide Weight -jS
Polymer with terephthaloyl and Heat treatment at ⁰ C 192 9694 Mixed polymer 0.75 / 0.25 Mass production be crazy ver
stretches JOC J »£ #, U ■ * · ίϊ« L «V / A ^^ V C» A ι HBh J ^ (ι ^ * ** 0.5 / 0.5 3.6 5 ^{s H} 2 ^S0 4 10 Winding
speed
age
while spinning
m / min. 597 O
O 0.25 / 0.75 4.5 10 8.7 1.16, 600
580 co
co
Ca) 31 * 0/1 3.7 100.7 10 12.5 1.08x
1.00x 600
550 i / 21 32 5.9 100.7 10 12.8 1.07x
1.01x 600 CD 33 2.4 99.2 11th 12.8 1.07x 600 34 99.2 13.1 1.08x - 35 99.2

Continuation! TABLE IY:

(D
H- KO TS
Η ·

3 thread properties

like extruded

Kristal O.A. line

jl 6.4 / 11/173 / 6.7 low

ω 4.9 / 12/145 / 5.4 tracks

, ζ 8.8 / 8/259 / 5.1 tracks

^ g 9.6 / 9.6 / 257 / 5.5 tracks «■ 5.6 / 9/216 / 7.2 low

S, V-. (km / sec.)

4.96 4.14 5.73 5 ₈ 88

5.55

heat treated

Crystal
line

10 / 1.2 / 827 / 4.2 high

14 / 2.4 / 622 / 5.1 medium

13 / 2.1 / 554 / 4.5 medium
18 / 2.5 / 800 / 5.8 high
13 / 2.4 / 707 / 6.6 high.

O.A.

14th
14th
12th
10
11th

S. V ο
Sec.)

7.47

9.21
8.19

* Tensile results as extruded, determined at 10 i> expansion rate «** Tensile results as extruded, determined at 60 f» expansion rate.

SM determination : If another sample of the polymer from Example 35 with 99.2

Seiger sulfuric acid is combined to form a mass that 11 6ew .- $ S contains polymer, the resulting Mass a DM- ¥ ert of 100 was observed.

Q-1031-R

Example 36

This example illustrates

(1) the production of a p-oriented aromatic Mixed polyamides with many components and more random Distribution,

(2) an anisotropic mass thereof and

(3) pads made therefrom with high strength and high modulus,

The mixed polyamide consists of equiaolar slopes of itself randomly repeating units »passing through the following structures are represented:

¹  £, -CO- ^ 3 ~ ⁰⁰ "· ^and

-CO- f \ -f% -CO-.

Polymer production;

A solution of 4.55 g (0.02 mol of p ^ -diaminobenzanilide and 2.16 g (0.02 mol) of p-PhenyLendiaaiin in a mixture of 90 ml of hexamethylphosphorawid and 45 ml of N-methylpyrrolidone-i is prepared in the drying chamber It is transferred to a mixer container, placed under nitrogen, and a mixture of 4.06 g (0.02 mol) of terephthaloyl chloride and 5.58 g (0.02 mol) of dibenzoyl chloride is added with very rapid stirring in 2 minutes to a kauteohukartigen gel "After 2.5 hours, the polymer is worked up in water. be is in Clem mixer with three times with water and once each

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SAD ORIGINAL

Washed acetone and alcohol and dried ^{at 100 0 O in a vacuum oven.} The yield is quantitative and the inherent viscosity is 5.4.

Making a mass s

An anisotropic Hasse is produced from the above polymer »irdem 5» 5 g polymer at room temperature * 45 g of 100.7% sulfuric acid and 5.0 g of 20% fuming Sulfuric acid are combined. Initially, the result is a stiff G * l, which after 6 days of standing becomes a flowable, however, viscous hats that show agitated rheumatism.

Spider-properties and properties in the state as extruilert _m ^^ _nmmmmaaM ^^^^^ _XM ^ _m

Sas Mspinnen takes place mrvt a motor-driven hypodermic syringe, which is provided with a thick spinneret with 20 loosen of 0.076 mm diameter. You threads are coagulated in water at a room temperature. The Eintavchli.nge is 71.3 cm »You will thread with 13.1 m / Hin, wound while the coil rotivrt in a water tank. The thread is then distilled for 16 hours Soaked in water, you pad properties in the state How ejctruded are I / s / m / äen * 6.3 / 13.1 / 149At04. Bas Yarn has a trace of crystalline alignment and an angle of orientation of approximately 45 ° and a speed of sound of 4.42 km / sec.

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Thread heat treatment and properties

The above na3se yarn is stretched with an introduction rate of 3.81 m / min through a hot tube (device. A) with 55O ⁰ C 1.1-fold. The drawn yarn had the following T / E / Mi / den value of 12.4 / 2.3 / 629 / 67.8 ", It had low crystallinity with low perfection, an orientation angle of 17 ° and an optical speed of 7.84 km / 3eko

Examples 37 through 39 below illustrate the Production of mixed (polyamide) ureas with random distribution, which consist of repeating units, the under

-CO ^^ - CO- and ~

are selected, as well as masses and threads of these copolymers with random distribution. It is noted _$ that the anisotropic compositions of Example 37 and 38 tighter Päden (for example, higher strength and higher Mcdnl own) - yield than the isotropic composition of Example 39 "Until relative proportions of the repeating units (described above in a random manner in the order given above) are given for each of Examples 37 to 39 "

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SAD OfUOiNAL

Q-1031-R **

B ei s ρ i β 1 37 polymer isatin division ι

A 946 ml glass blender container is dried, heated iriäem the inner surface with hot air at 15O ⁰ G. The mixer container is allowed to cool to room temperature inside a drying chamber, ie in a chamber that is kept under anhydrous conditions. Kethylpyrrolidon (under reduced pressure distilled from KalsiuBhydrid and stored in the Qrockenkainmer over molecular sieves) and 7 * 5 g L: lthiumchlorid (dried in a Vakiruxnofen at 20Q ⁰ C ut kept d in aar drying chamber) turn in the mixer vessel transferred "Am plastic cover for the mixer container is wrapped in aluminum foil and placed on the mixer. The mixer container is removed from the drying chamber. A stream of dried nitrogen gas is introduced into the mixer vessel through a hole in the plastic lid and the aluminum foil. The mixture is stirred wildly at a moderate speed until all the lithium chloride is dissolved. 16.22 g (0.150 mol) subliated: p-phenylenediamine are weighed in the drying chamber wA transferred to the mixer container · organic mixture is stirred at moderate speed until all p-phenylenediamine is dissolved »

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Γ'b SAD ORIGINAL

2.40 g (0.015 mol) of p-phenylene diisocyanate are weighed in the drying chamber and transferred to the mixer vessel. The mixture is stirred at a moderate speed for 12 minutes. Weigh out 27.41 g (0.135 mol) of sublimed 'j? E:? Ephthaioyl chloride in the drying chamber. The solution in the mixing vessel is stirred very rapidly while the terephthaloyl chloride is added. The solution gels to a solid mass in less than 10 seconds after the addition of the tirephthaloyichloride. This gel was left to stand for 5 hours and then added to Waneer in a 3.79 liter mixer and stirred at high speed. The precipitated polymer is filtered off using a coarse sintered glass suction filter. The polymer is washed three times with water and once waxed rule with acetone, "wherein the polymer is filtered after each washing program, the Polpaerisat is dried in a vacuum oven at 80 to 100 ⁰ G. The polymer yield is 35.9 g (99 #). The polymer has an inherent viscosity of 1.83. The ratio of the units is 9: 9: 1 »

Manufacture of a mass

A 500 ml resin kettle equipped with a stainless steel stirrer from the whisk type, en dried uad ir a drying chamber cool to room temperature & clas & er · In in a vacuum oven the resin tank 34 g of polymer and 145 ml of concentrated sulfuric acid (100.54 ° / o lurch Titration) »The Hara container is removed from the drying chamber and connected to an air-driven Eühriaotor. The mixture is stirred overnight with the temperature being moderated ^{by a room temperature 1 water bath.} Et ¹ a uniform, cloudy mass is formed which contains 13 (hw.-JÄ polymerizate., Me Hasse depolarizes light, when it is viewed as a thin layer of crossed polarizers *

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BATH ORIGINAL

Q-1031-R ° 192969Λ

Jade manufacture and thread reefs such as ext rudlert;

The Polymerisatmasse prepared above is placed in a spin cell of stainless steel and diert at a pressure of 28.12 kg / cm through a Platinspinndüse with 20 holes of 0.076 mm Durohmesser in a water bath at 10 to 20 ⁰ C extru ". The loads are led out of the water bath and the yarn is fed at a speed of 3.66 m / min. wound up ο The bobbins containing the thread are left to stand in distilled water overnight and then air-dried. The inherent viscosity of the polymer in the yarn is 1.75, determined in concentrated sulfuric acid. The threads have low crystallinity, an orientation angle of about 45 ° and a speed of sound of 4 "40 km / sec". The average eye properties are T / E / Mi / den ^ "3.52 / 16.5 / 119 / 4.01 .

Fad en wärmebe handluna; and - properties :

The yarn is heat-treated ₉ by feeding the yarn (20 filaments) is passed through a heated tube (device A) "The wall of the Rotreß is held in the center at 599 ⁰ C. The Fadeneinfuhrungsgeschwindigke.it is 7.62 m / min, and the length of the yarn is increased by $ 10 as it passes through the tube. The resulting gas has high crystallinity, an orientation angle of 14 °, a speed of sound of 8, <7 kiü / sec. and the following average adrenal properties T / 3 / i: ii / aeii. «8.41 / 1.5 / 531 / 3.47»

B eia ρ i e 1 38

Polymeric ether division

A 946 ml chemical vessel is dried by keeping the surface of the hot air with 15H ⁰ C

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8AD ORfQINAL

Q-1031-R

Allowed to cool to room temperature. 120 ml of hexamethylphosphoramide (calcium hydride distilled off under reduced pressure and stored in the drying chamber over molecular sieves), 60 ml of N-methylpyrrolidone (distilled off from potassium hydroxide under reduced pressure and stored in the drying chamber over molecular sieves), 5.0 g Lithium chloride (dried in a vacuum oven at 200 ^° C. and stored in the drying chamber) and 10.81 g (0.10 mol) of sublimed p-phenylenediamine are transferred into the mixer vessel. A plastic lid for the mixer vessel is wrapped in aluminum foil and placed on the Mixing vessel brought. The mixing vessel is removed from the drying chamber. A stream of dried nitrogen gas is introduced into the blender jar through a hole in the plastic lid and in the aluminum foil. The mixture is stirred at a moderate speed until all solids are dissolved.

80 g (0.005 mol) of p-phenylene diisocyanate are weighed in the drying chamber and transferred to the blender. stir at a moderate speed for 5 minutes. 19.29 grams (0.095 moles) of sublimed terephthalcyl chloride are weighed into the dry box. The solution in the blender is stirred very rapidly while the uerephlüaloylchloride is added. The solution gels to a stiff mass in about 15 seconds. The gelled Losing is left to stand overnight, after which it is Ln a 3, ' ^? 9 Str. Mixer added to Wabser and stirred with high speed. The polymer is filtered off on a coarse sintered glass suction filter. The polymer is washed 3 more times with water and once with acetone in the mixer and filtered after each washing process. Fac.i the final filtration, the Polyrasricat iinem in vacuum oven at 80 to 100 ⁰ C is dried. The polymer .satauebeiite is 25 »! g (92 # yield). The polymer has an inherent viscosity of 2.87. The ratio of the units is 95-95: 5.

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BAD OßiÜINAL

Manufacturing ; “A he crowd;

A 100 ml round bottom flask is dried in a vacuum oven and cooled to tree temperature in a drying chamber (the flask is equipped with an iron Teflon® TFÄ fluorocarbon stirrer). To the flask 15 g of the polymer 'and 65 ml of concentrated sulfuric acid are brought (100,44 ⁰ A by titration). The mixture is stirred, the temperature being moderated with the aid of a water bath with tree temperature. Stirring soon becomes difficult and another 10 ml of acid are added. Cooling with an EisAeser bath also supports the preparation of the mass. After stirring for the necessary amount of time, the mixture becomes a uniform, cloudy mass. This mass depolarizes light "if it is observed as a thin layer between crossed polarizers".

Fadenherstellun g juad Faden Eigenensehaft en_wie_ extrudedj.

The polymer mass produced above is placed in a mechanically driven stainless steel syringe with Teflon® TFÄ fluorocarbon coating and extruded through a platinum spinning nozzle with 20 holes 0.076 mm in diameter into a water bath at 10 to 20 ^° C. The threads are led out of the water bath and wound up at a speed of 3 2 m / min. The coils containing the fadan are left to stand overnight in distilled water and then dried in air. The logarithmic viscosity of the polymer in the thread is 2.04 «The average length of the threads is i 21, I ⁰ C, 65 # relative humidity) T / B / Mi / den.« 5.55 / 10.7 / 131/3, 00. The threads have an average crystallinity, an orientation angle of 45 ° and a speed of 4.44 km / sec.

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Q-1031-R

Padenwärmebej iandlunfl; and passions:

Yarn from a second spille of the above spinning process with average yarn tensile properties T / E / Mi / deEo »5f24 / 14.8 / 16iJ / 8.55 is heat-treated by passing the yarns through a heated tube (device A). The wall of the tube is held in the center at 599 G ⁰ The Padeneinirührungsgeschv / indigkeit is 7 "62 m / min" and the Fadenlän.je is increased while passing through the pipe 10 i>. The resulting thread has high crystallinity! - tat, an orientation angle of 11 °, a speed of sound of 13.98 km / sec, and the following average thread drafts T / E / Mi / den "" 9.96 / 1 , 1/847/4 »6O ₀

Be ₁ Js ρ 1; jJL_33.

Pol ymer isath-? R position %

A 946 ml Güasmischergefäß is ι dried _s by the In "nenoberflach3 with hot IUFD heated at 150 ⁰ C * The mixer vessel is within a Irockenkammer, that is, in a chamber" which is maintained under anhydrous conditions, .imtemperatur Ra to cool transmitted 90 ml hexamethylphosphoramide (distilled off from potassium hydride under reduced pressure and stored in the drying chamber over molecular sieves), 45 al N-methylpyrrolidone (distilled off from potassium hydride under reduced pressure and stored in the drying chamber over molecular sieves), 3.75 g lithium chloride (dried λη a Valcuumofen at 2OU ⁰ O and in the drying chamber stor / AHRT) and 4.05 g (0.0375 mol) sublimiertee p-Phenylöndi imine can be converted into the mixer vessel "a Kunststoffdeikel for the mixing vessel is in iUumiaiumfolie elngewic celt and the Kdschergefäß brought. The failure vessel is numbered outside the drying chamber. Mn flow of getroctoi item nitrogen gas v / irö through a! »Och in the Kunötoffde ikel and in the aluminum foil in the

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barrel introduced. The mixture is made at a moderate rate stirred until the pests have dissolved.

1.20 g ₍₉ O 0075 mole) of p-phenylene diisocyanate are weighed in the dry box and transferred to the mixing vessel. The mixture is stirred at a moderate speed for 5 minutes. 6 »09 g (0.030 mol) sublimed terephthaloylchloride are weighed in the drying chamber» The solution in the mixer vessel is stirred very quickly while the Terephthaloylchloride is added «The solution gels to a stiff mass in 30 seconds. The gel is overnight 'and then allowed to stand au water in a 3 _S 79% Itx mixer and added »stirred at high speed the niedergesclilagene polymer is on a coarse -Sinter-' glasxmtschü filtered off. The polymer is washed three times with water and once with acetone, wherein the polymer is filtered off after feathers washing operation "After the final filtration, the polymer is in a Va ~ kuumofen nit 80 to 10O ⁰ C dried. The polymer yield is 9.2 g (100 #) _o The polymer has an inherent viscosity number of 2.82. The "ratio of the units is 4 ^ -si ·

HgrjBtelljanf : e, lner Massei

In a 100 ml round-bottomed flask equipped with a Teflon vS / TFA-fluorocarbon * j stoff-Flugelrtihre c , 5.0 g of polyamide and 35 »1,100.7% (by titration) sulfuric acid are placed. The mixture is stirred, the Teiaperi'.tur being moderated by means of a water bath at room temperature. The polymer dissolves into a clear, very iscous solution. Another 15 ml of acid are added, so I ate a clear, viscous, spirable liquid after the miso hair; is formed. This mass depolarizes non-linearly polarized light.

- 162. BATH ORIGINAL

0 098 36/2 187

lit

Fadenherstollung and thread properties as extruded:

The PolymerisatmaBse prepared above is placed in a "eohänisch driven stainless steel tip with Teflon v- / TFÄ-Flüorkohlenstoff liner and extrucliert by a Platinspinndüse with 20 holes of 0.076 mm diameter in a water bath at 10 to 20 ⁰ Q. The threads are led out of the water bath and wound up at a speed of 3.96 m / min. The bobbins containing the thread are left to stand in distilled water overnight and then air-dried. The threads have a trace of crystallinity, an orientation angle of 65 °, a speed of sound of 3.21 km / sex *, and the following average threads = - train properties. * 2 _f 40 / 41.1 / 79/4 »85.

Filament heat treatment and properties, see chap

The threads produced above are heat-treated by passing the thread through a heated pipe (device A), increasing the length of the thread by 10% . The thread insertion speed is 8.2 m / min in the vicinity of the:. · In the middle of the longitudinal extension of the pipe at 554 ⁰ C. The resulting thread has high crystallinity, an orientation angle of 18 ° and average thread tensile properties T / E / Mi / den. »3.93 / 1.3 / 300 / 4.34.

Examples 40-48 below illustrate these Production of both anisotropic and isotropic hydrofluoric hydrofluoric (HF) compounds, the poly (p-benzamide), poly (p-phenylene terephthalamide) and a mixed poly fCp ^ ea »- amide) / (p ~ pienylene terephthal © mid)]. It will be tends to make the anisotropic HF masses stronger threads in the state v / ie aactruded (for example with higher strength and higher modulus) than comparable isotropic Masses "

- 163 -

0 098 36/2187 bad

Example- 40

This example illustrates this

an anisotropic HF mass containing poly- (p ~ benz £ iaiid).

20 g of poly-Cii-benzamide) (η, _1η1ι - 3.04, manufactured in, MjH-BJ, - = methylaoetanide aiit lithium carbonate as an acid acceptor according to the general procedures described here) and 105 ml of anhydrous HF are in a polyethylene -Scfcraubd @ ekelila · - srche (180 ml. Volume) and stirred for 2 to 4 times with a Haste * JLoy stirrer, the v / el protrudes through a hole in the bottle lid. .Bath is cooled from the outside. An anisotropic mass showing R-l'iropele & ssns is formed which contains IS G-ew _u - = »# PoX.-ymerisat (a similar 18 # mass is cloppa" (. Turr; che »u _f vfQim sie 3w..sahen crossed polarizers entered; lit et v'ii'ä) _c The 16 ^ igö mass _f which is about the viscosity of glycerin Lat _t is poured into a ^3rd externally cooled (to about 10 ⁰ C) Ie and on A flask above the Löniing Druok is used to expel a pad from a pi & tinspinalüsenlech with 0.0152 cm diameter and 0.0076 cm length ± ώ a 0.9 d long "Lucite V ^" -t column with 15.2 .what ' mi the through a was sweet stick »uGff strom, dfei ^: dem

Padenlaiif eat is directed in the opposite direction, to about 70 ° 0

© we rhitiT-t U The pressure applied amounts to about 1.3 ima Au £ / ickelgeschwindigkeit is 140 m / min _o boiled The Reel "with the ge" anmelten thread wild 15 to 30 minutes in water, after which samples of the threads removed and dried before the teat. The dry sample shows the following properties: 4.7 / 2.8 / 276-2.2 A thread of 1 to 2 seconds of successive treatment over elieoi hot ice. Staff (55O ⁰ O, Luftatmoephär «, punished: · ?,

- 164 -

SAD

009836/2187

1929684

1 j, 008 = f © oh 3 TerstreeknBg) tmd in. Eiaem hot Mohr (T © 3? «Rioirteag A ₃ no Ter.vteecäkimg) bsi 54O ⁰ C nratervmriesi ims dsii i & tj, lie fol ^ adä Pacem-SugeigeascliaftiiS Tors ϊ /ftiiS S / Hi s 5e 6/19 7/396 «lbs Ps.dea has high Ss = Ietaliiaits ^

B -s I a 9 i @ I 41

®lIg @ si © Iiä3B A ^ baite ^ eisea) werdea

in example 40 with 90 mi waoser celebrations ΓΈ v <s '£ ®lia.gt _β vm eiae viekcse isotropic mass au form _p ' li © 14 Ge-Wo · =? ^ asa polyamide contains "piping dimensions" © © © r ia example he&Ghst@hf.nen Sp & aaseli® esi ^ rudiert _s woboi eiB Dsuek "on the Kolber vob 5» 5 Isg / osi wid eiBe Aufwictelgeßchiifiadigkeit veil S3 m / Miss, verv / eiads ^ be _o Danaoa will d © r Faasu grl & d : «Ioh ia water extracted \ m & gdried and a®.ig the folgezdea J? Aä» 2Tigeige; jeohafte »: Γ / Β / ΜΙ ^ '2 _ρ 1/27 /? 3 _Λ Dar Faden violates low feißtallinität us iron Qriantieruagewiakel νο ; υ 50 ^D _e This Paäezi is raachei & asider by a Rote 'device A) ₆ the center of which ^{is heated to 300 0} G (l _f 3 ~: * aöhe? eratrecku, Bg ₃ touchiaeit etv / κ. 2 Sekusa «

A similar a lio> hv _f daa is heated to 535 ⁰ C {1 ρ 05 «= tae I -Yes ferst ^ eckuaig ₈ Bortihrtmgszeit 2 Sekimäea) ₉ guided ZiHCh this treatment the? adsn shows the following fegeli: eaBchaft © ßs ϊ / ι ? ΛΤΙ β 4 _S 6/2 _S 3/283 «The thread has medium hriatalliBity and an orientation.3ViinlEel T 33 °.

The -vQzlX Agende example illustrates this

one? isoiropeB HF «> Ma © g @ ₉ die (

3.69

Q-1031-R

amide).

1929624

10 g lfoi ^ C ^^ fe atallt% küu fiis! Lies Dm) ; / sMs: i vis is Is

it 85 Ms 90 rO,, -ϊ ^ i: "ι- λ

ί _ο 5 "to 4c> ä

O ₅ OlS

Q iea In water «ad feoekasB di © £ oX ^ ssiAsii eye characteristics ϊ / E / Mi a 3 ₉ 4 / 5ί / 79 *" Jtessciib. Wlsd di ^ asr j? A. ^. I "with the Cres.ilMincligkeit ¥ osi 3,7 a / MiiSc ämreli sin Böhx '(V ^: direction A) -, which in aeinem 5 oaa middle part au.? 535 ^ 0 heated iat, stretched on the 2,0-faolie, lios-iiiih cisi? Fad * ^ dis following suction properties a »/ E / Mi w 11/1 ^ 0/6 ^ 3 S3.ig1; I * at high crystallinity and a Gj / ieiitle-g. *!? ^^ 'of 13 ° t during loading in the state like ezcl £ · α ^ .: 1 low crystallinity and only traces vge Gria: "ti; rang has «. - ..- - ■ .; ' - ^.

The last example illustrates this

an isotropic HMSasae »di«; Poly-Cp-phenylene terephtliaX

amide) contains.

10 g poly-fp-phenylenetereiphthalajöid) ( H. ^ · ^ ** 5 »6»
represents by the general ^ s described here
However, it is a different sample than in example 42) ν are combined with 120 ial w & eser & ra ^ eS HF as in example 40 in order to form an isotropic mass, the 7 ^ 7
of the polymer contains. Diaae Masee v / ird in the in both

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BATH ORIGINAL

Q-1031-R

The cell described in game 40 is brought and truded through a nickel spinneret, which is connected to the cell via a spinning nozzle made of stainless steel that is bent at 90 °, so that the mass is horizontal and at an angle of 90 ° the axis of the spinning cell is ejected. The spinneret has about 175 round holes each with a diameter of O ₉ O25 mm. Me Pä (s be a distance of about 70 meters eizies water bath (cooled to O to 4 ⁰ G) is extruded, after which they are wound up at about 7.3 m / IIin.. The pressure on your piston in the Zello is 21 kg / om. After the threads have been boiled twice in a row for 15 minutes in distilled wasuer and dried, they show the following thread attributes T / E / Mi * 3.2 / 63/77. The speed of sound is 2.59 km / After 1.6-fold drawing mi ;, 15 m / min, through a heated tube (device D) where the 5 »08 cm central part has a temperature of 705 ° C., these threads show the following thread tensile properties T / E / Mi / den. «8.0 / 1.2 / 800 / 0.55» The legs have a high crystallinity and an orientation angle of 13 °.

B e i β ρ .1 e 1 4.4;

The present example illustrates wet spinning an anisotropic HF mass, the poly ^ Cp-phenylene terephthalamide) contains.

28 g of poly-Ci! -Phenyl ent er ephthalamid) i ^ X ^ j ^ ** 4 »0, prepared by the general procedures described here) are combined as in Example 40 with 110 ml of anhydrous HF, in an anisotropic, stirring tropalescence showing To form a mass * which contains 20 wt .- # of the polymer. This compound is placed in the cell described in Example 40 and extruded through a 100-hole spinneret as in Example 43, each hole having a diameter of 0.063 mm

. - 137 -

008836 / 2H7 W »« «w * l

Q-1031-R

Threads are passed through a water bath (6 ^° C.) for a distance of 210 cm, after which they are wound up at 71 m / min. The pressure on the piston in the cell is 9.1 to 9.6 "fcg / pm. After washing overnight in running water and drying, the threads show the following thread tensile properties T / E / Mi / den - 8.7 / 5 4/260 / 1.72. The threads show average crystallinity and a Orientierungswin · "angle of 21 °. The sound velocity is 6.35 km / S.ek" After the 1.05-feehen stretching to 15 m / min _a through a nitrogen-filled, heated tube (device C) ₉ in which the 5 at the middle part has a temperature of 562 ^° C., these threads show the following thread tensile properties T / E / Mi * 17.1 / 2.2 / 817. The threads have high crystallinity and an orientation angle of 11 °

B e i a ρ 1

The present example illustrates wet spinning an anisotropic HF mass containing poly (p-benzamide),

28 g of poly (ρ-benzamide) ( ¹ ZiUh ^β ^ »9» produced by the general procedures described here) are combined as in Example 4-0 old 110 ml of anhydrous HF to form an anisotropic box, see below, which shows Rühropaleszenz * this mass is brought ia described in example 40 _t cell which is modified to Naßepinnen as in example 43rd Dis mass is passed through a 100 hole Spiandüse, wherein ^ edes hole 0.063 I & HAS Duiohmesser aufweistj in a water bath (6 ⁰ O) ex "trudiei-t. The threads are guided through the Bsi over a distance of 210 am and "wound up" at 80.8 m / min. The pressure on the piston in the spinning cell is 7.03 kg / cm. Naoh wash *! Over the weekend in running water and dry them, these threads show the following thread sizes T / E / Wed: 6.2 / 4 _f 7/304 ·. ^ ie threads & .ei.gen. mean ki'iatallinity, an orientation angle of 20 ° xxni

- 168 -

-AV) I ^ oAe 0 09836/2117

as

a sound velocity of 6.57 km / sec _"o These threads are dan.i immersed in water and stretched (0 device) ver * with the speed of 15 m / min through a pipe _o, slide on its 5.08 cm in the middle part a temperature of 58D ⁰ C is heated, the stretching ratio being 1.06 times. The threads show the following tensile properties T / E / Mi * 14> 2/2 _# 4 / 802o The threads have high crystallinity and an orientation angle of 11 ° and the speed of sound is 9.32 km / sec. _O

Example 46

The present example illustrates wet spinning an anisotropic HF mass containing poly (p ~ benzamide),

28 g of poly-Cp-benzamide) (^ _iDil ^Ä 3.7, prepared by the general procedures described here) v / ground as in Example 40 combined with 110 ml of anhydrous HF to give an anisotropic mass showing RUhropalescence _s the 20th Weight .- ^ polymer contains * This solution is placed in the cell described in Example 40, which is modified for spinning as in Example 43. The mass is extruded as in Example 45 and the resulting threads are 91.4 m / Min, wound up. The pressure on the piston in the spinning cell is about 9.7 kg / cm. Haoh wash over after? in running water and drying, the filaments show the following thread ZugelgenBchaften T / E / Mi / the "7.2 / 3.2 / 3 0 / 1,45ο The threads show mid © Krlstallinität and a Orientierungewinkel of 27 ^0« The yarns with iS;, 2 m / Mi »;, through a heated Bohr (device C) ₀ vorin of 5 cm central part eist a temperature of 56o ^ O ⁰ to ν, 1.03-fold projecting stretches _e the filaments show the following Tensile properties iü / E / Mi » 14.0 / 2.4 / 626, high crystallinity and an orientation angle of 17 °»

009338/2117

R.
Example, $ χ

The present example illustrates that wet spinning an anisotropic HF mass, the Mlschpoly-ECp-benzamidJ / p- = · phenylene terephthalamide)] (90:10) contains *

30.0 g of the mixed polyamide described above ('^ Ji _n J ₁ ^κ 3 * 7 »produced by the general working methods described here) are: - combined with 110 ml of anhydrous EF to form an anisotropic, hemropalescence-showing hatred, the 21 Contains wt. = # Of the mixed polyamide. This mass is as in Example 4. $ (the water bath is ^{cooled to 2 0} C and contains 0.05 wt .- ^ Detergent) extruded, the extruded threads guided on a compensation guide and in a. Distance of 7.6: 1 cm from the spinneret by 90 ° with respect to _β The pressure on the spin cell is 6.75 kg 'cm ² and the filaments of the yarn "directional rerdreht with 80.8 to 96 m / Mn. wound up "After washing and drying, these threads show the following tensile properties T / E / Mi / den" 11.6 / 3.0 / 410 / 1.24 ". The threads show medium crystallinity and an angle of νm 22 °. After 1.03 * fan verse refraction at the speed of 4.33 m / min, through a erhitates Bohr (ιJ device) whose central part 5 cm demonstration of a temperature of 544 ⁰ O: show serve threads "transactions the following Zugeigen T / E / iii ■ 12.2 / 2.0 / 600, high crystallinity and an orientation angle of 12 °.

IL & X & JßJL & I. , 4.3

The present Belapiel causes ahaulicht the Kaßsp lines an isotropic HF mass containing poly (p-benaaoiia)!,

10 g of poly (p-benzamide) (1 / J ₁₁ J ₁ ^B 2 _P 9 # produced by the general procedures described here) are combined as in Example 40 with 90 ml of anhydrous HF to obtain a vis

- 170 -

BATHROOM QRiGINAL

009836/2117

form-viscosity, clear, isotropic composition containing 10 wt. ~ $> polymer This mass is brought the cell described in Example 40 and having such mm in Example 43 by a 60 Lqch-Platinspinndüse, wherein ^ edes hole 0.076 diameter, ex trudiert through a water bath (0 to 6 ° C). The thread run is guided around rollers in such a way that the path length in the bath is 210 cm. The pressure on the piston in the line © is 15 »5 kg / cm and the yarn is wound up at 13.4 m / Hin. After rinsing for 1 hour in running water and drying, the yarn shows the following tensile properties T / E / Mi / den β 2.8 / 28/83 / 2.4 and a speed of sound of 3.33 km / sec. After drawing a sample the rinsed wet yarn in the state as extruded at the rate of 14.6 m / min, through a heated Bohr (device C), the 5.08 cm center portion has a temperature of 593 ⁰ C (^ reinforcing eckverhältnis 1.37 Faeh ) the yarn has the following thread draw characteristics T / 33 / Mi ■ 8.8 / 1.8 / 621. The threads are highly crystalline and show an orientation angle of 17 °

Example 49

The present example illustrates the preparation of poly (p, p'-diphenylene terephthalamide) and one anisotropic Oleuro mass thereof.

Polvaterisathera division %

25 ml of hexamethylpnoB-phoramid, 25 ml of N-methylpyrrolidone-2 and 1.84 g of benzidine are placed in a flared 100 ml flask (equipped with a stirrer:? And openings? To flush with nitrogen and to introduce substances) is stirred to form a solution. The solution is then cooled with solid carbon dioxide and 2.03 g of terephthaloylochloride, dissolved in 10 ml of dry tetrahydrofuran, are rapidly added with stirring.

o. 171 -

^Wt ' ^:: ' ^f """00983S / 21I7

Q-IO ₃₁ -E

give. The mixture becomes very viscous within 1 minute and unmovable. The mixture is left at tap temperature for 16 hours left to stand, after which the polymer is precipitated by stirring it with water in a mixer is alternately filtered and then washed once with alcohol and ether. The polymer, dried in vacuo, weighs 2.96 g and is logarithmic Viscosity steel of 1.45.

Hers tellung a crowd:

1.9 g of the polymer are mechanically stirred in a closed Yersuche tube with 7.0 ml of 100.95 Seiger sulfuric acid. The egg-dissolving polymer first forms a clear, viscous mass, which, however, becomes cloudy and uniform as the dissolution proceeds. The crowd shows BühropalesH-zens and depolarized as a thin layer under a cover slip on a microscope slide, linearly polarized Light.

Example 50 '

The present example illustrates the manufacture of Poly (1,5-ne-phthyleneterephthalamide) and an anisotropic * Oleum mass c.avon "

10.15 6 (0.05 mol) terephthaloyl chloride are added to a warm slurry (with 35 ⁰ C) of 7.90 & (0 ₃ 05 mol) 1,5-Najhthalindiamine (sublimed) in a half of 60 ml Hiocamethylphosphoraiaid and Add 30 ml of N-methyX-2-pyrrolidone, which is contained in a 500 ml resin production container, which is provided with an air-driven fan and an Eclziumchlorid-Trookenrohr. In 45 fc a stiff mass is obtained, which is left to stand over heclite at room temperature. The mass is ricxm

- 172 -

00983672117 bathroom original

Q-1031-R ⁱ

Purified with water and generally stirred 3 * 785 L tr. mixer with high speed. The polymer is collected., 3 ~ Bal washed with water by gerthrt in a mixer and by filtration on a coarse-pored S ± nterg3asnut8ohe isolier ", and dried over Geesthacht in a Vakuun.ofen having about JO ⁰ Ii" The .Polymerisatausbeute is 13 »60 β (94» 5% of the (theory). The logarithmic viscosity number _f gomeesen in a solution of 125 mg of polymer in 25 »C ml of 95 to 98 weight percent sulfuric acid is 2.22.

Production of an anisotropic musa ;

A mixture of 2.5 g of the above polymer and 22.5 g of fuming sulfuric acid (1.3% free S0 _y ) is obtained from knowledge-free Bt conditions with a hill-type stirrer in a 200 ml deep flask mixed while chilling with an ice / waaser 'load. The mixture is stirred for several (4) hours, during which time the cooling bath is allowed to warm to partial temperature. The resulting:? Negligible mass aeigt stirring rheumatism ναό. depolarizes linearly polarized light.

173 -

009838/2187 bad original

Example 51

The present example illustrates

(1) the production of a mixed polyamide with a random distribution, which consists of equimolar amounts of due to repeating units that are under

-KH-, D 3 ^, -HH

• CO- ^ J ^ -OO-, -C0 ~ \ ^} - t (Jg -CO- and

are selected,

(2) an anisotropic mass of the mixed polyamide and

(3) threads of 3 mixed polyamides.,

Polymerisath -y position;

A solution of 1.08 g (0.01 col) of p-phenylenediamine, 1 _f i5B β (0.01 mol) of 1,5-naphthalenediamine and. 2.27 g (0.01 mol) of p, p ⁰ -Diarainooenaanilid in a mixture of 60 ml of hexamethylphosphyramide and 30 ml of F-methylpyrrolidone-2 is prepared in a misoher container in a drying chamber. A mixture of 2.03 g (0 * 01 mol) terephthaloyl ^{chloride, 2.79 g (0.01 mol) 4.4 5} -bibenzcyl dichloride and 2.53 s (0.01 mol) 2,6-haphthoyl dichloride is described under aahr admitted to his quick soneil. The resulting very viscous, clear solution is stirred for 15 minutes and then left undisturbed for 16 hours. The polymer is in water

- 174 -

It is worked up in a mixer four times with water, each time washed with acetone and alcohol and dried ^{in a vacuum at 10O 0 O.} The yield is 9.5 g (94 Ji), η _1η1ι = 2.93o

Making jiner mass:

A spin mass is produced from the above polymer by combining 4 g of the polymer and 56 g of 99t2% ΕρΛΟμ at room temperature. The result is a very viscous rabbit that depolarizes linearly polarized light.

Spider properties and properties in the as- extruded state

The wet spinning takes place from a motor-driven syringe, which is provided with a * spinneret. Due to the high viscosity of the mass, a specially designed, thick-planar spinneret with 20 holes with a diameter of 0.1 mm each is used. The pads are placed in water at room temperature , r-'as contained in a metal trough, coagulated. The immersion length is 83.8 times. The threads are _{wound at 14 »3 m / M: .n o} , while the bobbin with the lower plate rotates in a water container. The yarn is then soaked in water for 16 hours and dried. The cooking properties in the as-extruded state are l '/ E / Mi / den «3.2 / 9.7 / 132/97. The yarn is amorphous and has an orientation angle of about 50 ° and a speed of sound of 3f82 km / sec.

-175 ~

0 09 83 _{6/2117 ßAD} original

Q-1031-H

Thread heat treatment and properties

-J * "-—" TT-- · »ι Ii .Wi! ■! ι— i 'iii * iMw. I ι Μ ι ■>! ii I ^- IWPM "ι ι

Bas nass® Gern is drawn 1.1 times through a hot tube (Yorrie-lr ^ rag Aj at 38O ⁰ C at an insertion speed of Ιή8 · π »/ min«. The drawn yarn has the following properties T / E / Hi / den ■ »6.9 / 2.1 / 413/7 * - So has traces of crystallinity and a GrientienuK ^ swwinkel of 24 ° as well as a sound velocity of 6.37 km / sec

Example 52 This example illustrates

(1) the production of a mixed polyamide with susceptibleϊγ Distribution, the equimolar amounts of sieve in sufälligsr V / also contains repeating units, öie

™ co » ^J

are selected

(2) an aniactropic mass © des

(3) threads d.a miachpolyainidso

Polymerisat!?, First ι

Bine · Lösurig ψοη 1.62 g (0.015 mol) p-4henylei; 3ini-t ^: -T 3.35 g (0.015 mol) 4 »4 ⁹ -DIaiait obeuaanilHI In« inc.r

- 176

009836/2117 bad original

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from 60 ml of hexamethylphosphoroid and 30 ml of N-methylpyrrolionone is borgestslit in a mixer vessel in a rockeiakaiu3ier, a mixture of 3.045 B (0.015 mol) iearephthalo; 'lchlo3? id and 3.79 ^ g (0.015 mol) 2, 6-Faphthaloyl chloride is quickly dispensed with very rapid stirring. In 2 minutes you get :; A clear, stir = »ba:? es GeIo Kach for 2 hours at S-ehen the polymer is worked up in water, it w: .rd in a mixer four times with water, once ai-i each time; Acetone and alcohol and washed ii5 a Vakuuaiofen 100 ⁰ C dried "The yield is 9.5 g (99 Ά), (\ _inh." 2 "77th

Making a mass:

A base is produced from the above polymer by adding 2 g of polymer and IB g of 99.2 HpSO. to be united. After 6 hours of intermittent stirring, it results in a viscous anisotropic M which shows stirring tropalescence.

Spinning properties and properties in the state like extruded

The wet spinning takes place from a motor-driven syringe which is provided with a spinneret with 20 holes, each 0.076 min in diameter. The threads are coagulated in v / asijer at room temperature, as they are contained in a metal trough. The immersion length is 81 em. The threads are 21.7 m / I'in. wound up while the bobbin with the lower surface rotates in a water container <> The Fade »is then soaked in barrels for 16 hours and dried. The yarn is amorphous and has an orientation

0 0S836 / 21S7 BADORIGJNAt

Q-1031-E

angle of eSwa 60 °. You yarn properties in iia condition! how extruded see inds T / E / Mi / den = 2.14 / 17.3 / 78/176.

Thread bait annealing and properties;

The above thread is made through a hot morning

device A) with 475 ° C with a Binfufenrngsgescliwiiiiiskr-ait of

3 »81 m / min, stretched forward 1.1 times. Bas ^ - Yarn has the following properties: /// 6.8 / 0.9 / 698 / 72.7. It has more crystallinity, one Orientation angle of 12 ° and one of 8.84 km / liek.

B e i_s ρ i * 1 53

This example illustrates

(1) the production of a mixed ipolyaajid osaiiia ice cream) rji conspicuous distribution, because they get out of themselves

Units that are under

-Mi- / Λ-HH-, -CO- ^ TVCC and -Btt - ^^ - cT \ -f ~ \ -IiIl- V = / \ = / V = / «μ Vr /

JT-H

are selected (relative ratio 3: 4: ϊ) «

(2) an aniiotropic oleum race of the mixed (poi ^ aiiiil-oxa ~ diazole) and

(3) Mixed (polyaraid-oxadiasols) threads.

- 176 ■ -

BATH ORIGINAL

0Q8836 / 21I7

Polymerisathe rst RECOVERY;

A solution of 3.24 g (0.03 mol) of p-phenylenediamine and 2.52 g (0.01 mol) of 2,5-bis (p »aminophenyl) -1,3,4-oxadiaaol in a mixture of 90 ml of hexamethylphosphoramide and 45 ml of N-methylpyrrolidone are prepared in a mixer container in a drying chamber. 8.12 g (0.04 mol) of terephthaloyl chloride are added all at once with rapid stirring. The result is a very viscous, clear solution which becomes undetectable in 2 minutes. It is left undisturbed for 16 hours. The polymer is worked up in water and washed in the mixer four times with V / AS 8 and once each time with acetone and alcohol and ^{dried in a vacuum oven at 100 °} C., ¹ L _n ^ ₁ ™ 3.28 "

H creation giner Masset

A mass is produced from the above polymer, by combining 6 g of polymer, 44 g of 100.7% HgSO, and 10 g of fuming sulfuric acid (20 ^ -free SO ^) « The mixture is stirred until a very stiff gel results. This is left undisturbed for 2 weeks »Me Checkout may appear to be a breakable gel, but it can be poured into the spinning shaft only slowly. the Mass depolarized linearly polarized light »

[jpinnöigensciaften and properties like extruded

Bio the above mass is transferred into the spinning cell and a Centrifuged for hour. Wet pinning is done from a motor-driven syringe with a thick The diameter of the lineal diameter has to be 20 holes of ^ evieils 0.076 is provided * The threads are in water with

»179 - ■ ■

o8834 / 2117-, sad

1 SO

Q-1031-R

which is contained in a metal trough, coagulates «The immersion length is 83.8 cm. The threads are run at 8.1 m / min, wound while the bobbin rotates in a water tank., The yarn is then soaked in distilled water for 16 hours and dried th in the state as extruded are T / E / Mi / den 2.4 / 14.4 / 94.3 / 103 (Expansion rate 10 Ji). The yarn has a trace degree of crystallinity, an orientation angle of 50 ° and a speed of sound of 3.35 km / sec

Wjigm ebehandl mg and properties s

The above wet yarn is drawn through a hot tube (device A) at % 15 ° 0 with an introduction speed of 3.81 m / min. den = 3.8 / 0.9 / 500/57. It has medium crystallinity and an orientation angle of 15 ° and a speed of sound of 6.80 km / sec.

ρ ^ i t? _l 54

The present example illustrates the preparation of poly - (2- {5hlor-p-phenylene terephthalamide) -Fäöen high modulus of-an optically anisotropic material which about 20 Gete ^r <, · by weight of the polyamides.

To a stirred solution of 35 g (0.245 mol) 2 ~ chlorine-p « phenylenediamine, dissolved in 425 * nl Hsxamethylphosphoraniid and cooled in a bath of egg and water, it becomes 49.7 g

■ - 180 -

9836/2117 _{eAD OT1QINAL}

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(0.245 moles)! Perephthaloyl chloride added. A precipitate in the form of a wet paste forms almost immediately. The mixture of raactons is left to stand overnight, after which the polymer is collected and stirred with water in a mixer. The polymer is dried for several days at 78 ^° C. in a vacuum oven. 60 g of poly (2-chloro-p-phenylenetarephthalamide) with a _{value of} 1.13 were obtained

A mass, lie 17.2 GeW ₀ - ^ polymer and 2.7 wt .- $ j sais contains, we prepared <l by adding 5 g of the above prepared poly (2-jhlor-p-phenylene terephthalamide) with 25 ml of a Solution obtained by mixing 100 ml of Ν, Ν-Dlmethylacetamid and 3.1 g of idthium chloride :.}. The mass is left to stand at room temperature for a week or longer, during which time it is divided into an isotropic upper layer and an anisotropic lower layer (i.e., for the lower layer, T> TÖ, determined according to the procedure described here) The layers are isolated and the anisotropic lower layer is extruded at room temperature through a spinneret with five holes, each 0.076 ram diameter, into a water bath which is kept at 21 ^° C. . The yarn produced are wound up at 17.4 m / min _o. After soaking in water and drying, the threads show the following properties: T / E / Mi (boiled sample) »3.5 /, 8/234» the angle of orientation is 39.2 ° (method three). When this yarn is gel.eitet via a rod 425 ⁰ C, the yarn properties T / E / Mi (ausgukooht · sample) take the value 2.4 / 0 * 7/318 and the Orlentierungiiwinkel is 28 ° (Method three ) »

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Physical properties and details of the composition of each of the layers described above are compiled in Table V below. Unless otherwise stated, the determinations were carried out at 25 to 25 ^{° C.}

TABLE V g / ml O ₉ 0260 Lower class upper layer 1.01 Density, g / rough 0.97 1.4676 Refractive inc ex, njp 1.4725 0.179 Polymer ^; content * g / ml 0.112 1.44 ¹ UnIi ^des ^ ⁰³ ymerisata 0.43 0.023.8 ' Mole content,

The present example illustrates the manufacture an optically anisotropic spin mass, which is about 10 Gevr »- ^ ]? oly ~ (2-ehlc »r ~ p-phenyleneterephthalamide) contains, and the Manufacture of threads with a high modulus from it.

A mass which contains 9 »5% by weight of polymer and 1.5% by weight of SaIa» is prepared by combining 5 g of poly (2-chloro-pphenylenteruphthalide), prepared in Example 54, with 50 ml of a solution the ml by miachen 100 Ν, Ν-Dimethylaoetainid and 1.6 g Iiithiumohlorid are obtained wi :: d, Di 'mass is used for a Rauatemperatur

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Week or longer, during which time it separates into two flowable layers or phases of approximately equal volume, the upper layer being isotropic and the lower layer being anisotropic (i.e., for the lower layer, T> 70, determined according to the working method described here). The layers are isolated and the lower layer is anisotropic at room temperature through a spinneret having a hole of 0.127 DurOhmes "SQT mm extruded into a bath maintained at 21 ⁰ C water bath. The resulting thread is wound at 22 m / min, soaked in water and drying, the thread shows the following properties T / E / Mi (cooked sample) 4.6 / 4.8 / 198, the orientation angle is 43 »9 ° (method three) ο If this thread is passed over a rod at 425 ° C, the properties T / E / Mi (boiled sample) take on the value 3.1 / 1.3 / 274, the orientation angle is 28 ° (method three).

Physical properties and information on the composition of each of the layers described above are compiled in Table VI below. Unless otherwise specified, the determinations are carried out ^{at 25 to 26 ° C.}

- 183

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TABELIE Dense g / ml VI layer lower
o _s 99 25th
Refractive index, ^Vi j \ upper certainly 1r 4544 Polymerization content, g / ml not , 4584 0 _f • 398 " ^]. r. dos PoXrmerisats 1 »080 1, 01 LiGl content _s g / ml 0 , 74 0, 0146 0 , 0120 0

Bine other r »pinmnasse is similar vfie above prepared DOH" with 5 g of the polymer in 50 ml exerts ijDid / salsa Mincliungo The mass ¥ ith etvra one week lföii £ säteL 'left ¥ oii (.ch shaken; ₉ van die Schi ;; Ii-ij © ri su a-cloudy mass to unite the n: urtet oj ^ tis *: ¹ *! it is clear that " f. eats larger than 50, determined -according to eggs here bs ~. written. · work _t sifeise _o This ifesse is tsrnsittsliST at Xiauioteinp-iratur through awei holes with each O. _f O127 c-Burchmenaer, the spinneret held at 23 ^{O |} v-es? V / water bath eir.rudiert. Bie .fäde.i are rait one f; -3acbvrii> öigkelt sw in. hen 9? Ö and 13.5 η / Κ ± η _ο wound up _s liach E: Uiweiehcm! ■. Water and dryness aeden the loads the following on properties ÜJ / B / Wed (Auskotihte sample) - 4, »/ 2.7 / ^ 23r the orientation. ' _{Angle is 3 ^ s} 9 ^L three) ο

184 ~

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8AD ORIGINAL

41S

B a ^ .. JL JiLJL . LrL = ^ - ^ 6

The present example illustrates the manufacturing process oilier double "refractive spinnutus from Paly" (p "-phenylentersphthalara-.d), which contains a mixture of anisotropic and ifjotropic phases "

2u of a sol * mg of 31 * 08 g (C, 28? Hol);? in a mia jtmng of 360 ml EexajEethylphoaphoraiaid and 180 ml Ü - M8t "iylpyrrolidon - 2 weeder. 3 $ 36 _t j p ~ Jüa: Lnobensoesäl ⁾ . ° re given» - / if V / aoserbwdkUhlung is branded, Zw this cooled solution v / ground 60 ^ 90 g (0 ^ 300 MoIj Ssrephthaloy .chlorid given the? Eeaktionsiaiischuag over Haelit g, -stirm and then in a Xiijoher with water in igt j U'i to precipitate the polymerisate <> The product is yesit V / an ier washed and dried in a vacuum oven to 65 ° C. The product is then usually a mixer with acetone ν, -purified, the mixture is filtered, then the product is mixed and h & i 65 ⁰ G in -är ' .Dried in a vacuum oven, 1! ε we ^ ä a quantitative® yield of poly- (pphenylenter "* _: .'hthalamidi (n. * V" 32) obtained ;. _o

A liasse, ie * 7.96 parts by weight polymer and jS 1 _S 24 G-eWe »# bellows contains is manufactured; zuorst by 18 g of poly (p '^ phenylentere hthalamid) (mountains is as above) _s 160 ml Heicamethylph-'sphorsaaicl, 40 ml f "methyl p; are combined yirroliclon-2 nnü 2.8 g Lithiu-.ichlorid ,, Pie Ground the constituents with a shear disk stirrer and put them in a bath; Sis und Wasesr gskühlt «, After placing the components and cooling them over laughs, a uniform» free-flowing ci-; homogeneous paste © is formed »Theeae is ^{heated to 60 0} O in order to ensure that it is fluid and is somewhat cloudy if it is not hit ": Let athen -fird) to generate," said Ellhropaleazenz ssidgt.

" 185 - '

09836/2187 © ad original

This mass iepolarisiert when ρ to be flowable is heated to about 35 ⁰ C, linearly polarized light ,, when viewed with a microscope polarisiereaden, DOH, with the microscope * IIRD a salvation Fold observed "'

The device Paden be prepared using the aas this mass comprises a I8sungs3elle _s is connected to the S-shaped tube "that contains in its lower end a spinneret having 20 holes of 0.01 cm diameter when the hot (60 ⁰ C) The mass has been poured into the solution cell, the cell and the S-shaped tube are heated with a heat gun until the mass begins to flow out of the spinneret openings. The bio device is positioned in such a way that the spinneret is horizontal Direction in a v / aaserbaä, which is held at 60 ⁰ G «The S-shaped tube is partially immersed in the bath * to help keep the mass warm before extrusion. The mass is extruded with a pressure of 0 »14 kg / cm and the resulting threads are at 22 m / min. wound on reels with care; it is ensured that the thread is kept taut at the tip nozzle surface. The bobbins are washed in cold water for several hours before they are all dried in air at room temperature. Threads from one of the bobbins show the following properties ΐ / E / Mi / den (boiled sample.): 3.7 / 4 »0/194/3» 7 »the orientation angle is 39 ° (method three).

! If the Arbaitsweisa above-described _s is repeated, except that the spinning nozzle © "rather have 0.076 MRA diameter respectively, so are poly ~ (p ~ ~ -phenylene törephthalara; d) filaments having the following properties

"■ 183" -

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T / E / Mi / den (cooked sample): 3.2 / 3 »2/219 / 2.54 obtained

and the opening angle is 37-3 ° (method three).

Example 57

The present example illustrates dimensional spinning an optically anisotropic masre to form poly <= (pphenylene terephthalamide) threads, their properties

© in the following © heat treatment significantly improved wardenο

18 g of poly (p -phenyl ent er ephtheJLamid) (rL ^ «i!> 32 _s prepared in Example 56), 134 ml of hexaraethylphosphoramide, 66 ml of N-methylpyrxolidon-2 and 2.8 g of lithium chloride are combined and in - 1O ⁰ O stirred for 2 to 3 hours »

to create a plank movable pasto that

on Eaumteinparatiir eMrasii galasseii becomes ο Bins flowable The mass is made »ine" esa the material 3 days long is continuously stirred ο 3as material shows Ettbropaleszens, ϊ = 46 »as measured by the present invention«

Bie mass, c'ie 7 $ 95 Gew "- $ Po'.ymerisat irad 1.24 Gew ₀ " ^ SeXa srsthäli "is with 0.14] q; / em" through a spinneret with 20 holes of 0 * each 076 κ & α Biirchiaoseer in a Wit ^e > s @ rba «ä extruded to the resulting threads are wound at 11 n / min» on a bobbin _p the 3 hours l * -ng in cold W®. «Js« ir washed weriäö ^ ,, feovor them in air at Raurateinperatu: · getroo ^ xet wordon »G-arn from a bobbin shows c ^; ie the following Eigennohtifte T / E / Mi / den (auageTcocht« sample} s 1.93 / 2 " 3/140 / 45.7 »aor orieutlor uneven angle is 42« 5 ° (ifethodo ijce :.) ": -; ine prob« this

009838/2187

which has been passed at 6.1 m / min through a nitrogen-filled tube with a length of 0.5 m, which ^{is heated in the middle to 56O 0} C, shows the following properties T / l / Mi / den (boiled Sample): 3.94 / 1/414 / 38.4, <3 orientation angle is 24 ° (method three).

Example 1_ 58

The present example illustrates the preparation of an anisotropic mass of poly-ip-lsenzamide) in U ^ Ui ₅ Ii ⁰ _? N ^t; -Tetramethylurea in situ ₀

400 g of p-Aminabenzoylchloridhydrochlorid be below 2 l. H, N, ⁰ N, N '^ fefcramethylharnstofi wherein 2 g of p-Amiiiobensoesäure are included, given that .v maintained at 5 ⁰ C? Earth The Reaktionsmisehung is about unier Auseenkühlung gsrUhrt for 15 minutes, then b © i Eigenteraperabur is stirred about 1.75 hours, after which 90 g Lithiumhydrosyd werderu fated give the ReaktionsmiEchung vrird for 3 minutes at 125 ⁰ C and then stirred at eriitzt Eigenteinperatur 2 hours, au form a mass » Which contains 10.8% polymer (a polymer sample isolated from the mass has a logarithmic viscosity range of 1» 40) ° This mass κ, which now contains about 6 ^c / a lithium chlorid, shows a weight value (T) of 57p like here

Poly ~ (p-benrimide) that from a similarly prepared isolated vrorlen solder »but using only 0.35 g of p-Aai-iob «n« oesäur ©. is available logarithmic viscosity number of 1.65. Until the mass increases a reference (i) of Figure 5B, as here

~ 188 "-

009836 / 2T87 · »« * »« *

B gj L. ⁸ pi e 1 59

The present example illustrates the production of a non-neutralized anisotropic spinning mass, which contains poly ~ (p-benz <unid), in situ _o In the finished mass there are 2 moles of hydrogen chloride for every mole of p-aminobensoylchloride hydrochloride used as monomer c

To 2 l "Μρ'.ί, ΙΡ, N" -Tetrainethy urea, where 0 ₉ 92 g of p-Aminobenzossäure added and that are cooled to ice temperature!, 256 g of p-Aminobenzoylchloridbydroöhlorid given the Reaktionemiecbung is eiv in the bath temperature / a Stirred for 55 minutes "in order to create a viscous mass. Stirring is stopped and the mass, which contains about 11 GeWo per polymer, is left to stand in a nitrogen atmosphere at room temperature before it is extruded in the form of threads" A poly (p-Benzßiaid) sample, which has been isolated from the mass, has an inherent viscosity of 1.10 Me Mas; ie shows a permeability value (T) of 55s. v / ie measured here.

⁶⁰

The present example illustrates the manufacture an anisotropic mass, which has a random distribution Copolymer of poly ~ (p- * bani3ainid / m-benzamiä) (95: 5) in a 95/5 mixture of N, N «dimethyl acetamide and Lithium Chlorild contains "

150 ml of H, U ₉ W , IT * -! Etramethy! Urea, which are stirred and cooled in an ice bath, are added in the course of 15 minutes.

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009836/2187

ute a mixture of 28.5 g of p-aminobenzoyl chloride hydrochloride and 1.5 g of m-aminobenzoyl chloride hydrochloride added "The reaction mixture is cooled on ice and stirred for 1 hour and then stirred for 1.5 hours at room temperature to give its stirrable mass" After 20 hours at room temperature a clear gel is obtained. "The GaI is combined with water in a mixer to precipitate the copolymer. The product is isolated, washed and dried, giving 15.5 g of poly" (p ~ benzainide / ~ m-benzamide) (95: 5) with a tj _inll - 1.12 results in »

A composition containing about 10% by weight of copolymer is prepared by adding a sufficient amount of the above-prepared copolymer to a 95/5 weight mixture of N, N-dimebhylaeetamide and lithium chloride. The ingredients are left for 10 to 15 minutes stirred and heated to 100 ⁰ G and then stirred at room temperature, is formed to a polymer of undissolved free mass "The composition exhibits a transmittance value (T) of 11, measured at room temperature as described herein

B e 1 S ₁ p _M i

The present example illustrates the manufacture of anisotropic spinning masses made of poly ~ (p-benzamide) in situ, using lithium carbonate to neutralize the mass will.

To 200 g of p-aulnobenzoyl chloride hydrochloride, 1,310 g of NiNSH ⁹ -letramethylurea ^{are added at about 7 0 O.} This reaction mixture is stirred for about 15 minutes at room temperature. After a total of about 80 minutes (with stirring)

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the temperature of the reaction mixture 4O reaches ⁰ G. The mixture is further 28 minutes stirred at 40 ⁰ C and then stirred rapidly during which time the clearness decreases and lithium carbonate in two portions (50 g, 28 g) is added, and the mixture is stored at 85 ^° C. »Then 2 g of p-aminobenzoic acid in 30 ml of N, N, NSN ^e -tetramethylurea are added, followed by further HO g Ν, Ν, ΪΓ, N'-tetraraethylurea <, the reaction mixture is passed through an oil bath heated with 1JO ⁰ C to about 80 to 9O ⁰ C., and about 225 g of liquid removed by passing the heated mixture is subjected to vacuum "There are an additional 72 g N, N, N ^0, N ° -Tetramethylharnstoff added and the reaction mixture is 4 days heated at 12O ⁰ C and removing unreacted LIgCO centrifuged. The reaction mixture is concentrated to form a mass containing about 9-5 wt. Poly (p-benzamide) since it has an inherent viscosity of 1.74. This Mass® shows a permeability value (T) of 21, measured at room temperature *, like hi © 5? described »

Example 62 _t

The present example further illustrates working methods

(1) for the preparation of poly (p-benzamide) _r which is useful in the formation of the compositions according to the invention, and

(2) for the division of related masses.

191 -

009836/2187

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horny A

450 g of p-arainobenzoylchloride hydrochloride are added to © innsa! Add 200 ml of dry Ν, Ν, Ν ', JP-Tetramethylurstcff, which are pre-cooled on ice, a solution immediately forms. the solution is stirred for a further 2 hours =, during this time the solution becomes warm and slowly forms a solid gel The gel is left to stand overnight * after which it is washed in a mixer twice with tap water --xmä once with 2B alcohol (the gel is divided into three parts for these washing processes) The isolated polyamide is dried at 80 ° in a vacuum oven under a nitrogen atmosphere, n _in ^ ~ 1f83 ° The sample is comminuted by grinding it for 3 days in the ball mill.

If this Härstellungsweise repeated gutted ti that the gel formation of laughing only 2 hours left standing for \ FIRD ₅ so the insulated polyamide shows a logarrrf. !! - mix Viskasitätszahl of 1.74. A similar manufacture wise supplies; a polymer which has a logarithmic viscosity number of 1.53 and a peak height ratio of 0 _P 7i> »

"In a mixture of 250 ml of N / K-Dimethylacetariiss and 1 ^{liter of} lithium chloride, 30 g of poly- (p ~ benza \ uid) are prepared - in Part A, about half of it is geluated by treatment in the ball mill: i. Di ^! Mi.oeMni _t i contains 10.8 GeWo ~ $ of the polyamide and 5Λ G «λΌ > iee SalKss,! Js immediately finds swelling equip IKe iia

-. 192 -. .

0 09836/2187 bad original

1929RQ ^

ifeijse is ^{heated to 10O 0} C in order to produce a suitable Masae ga.

feil σ ■ -

Mixture of 200 ml NsH-DimethylisobutyrsniM and 13g Lithiumechloricl at room temperature 20 g PolyCpbenKaaid) ii | _in jj - ^ »39» made according to the general

"Given operation of cable A) The combined Bestandteile- that 9.4 wt _o - # of the polyamide and 6.1 6 © ^ '· = $ of Sal = ses included are geriüwt at its own temperature, bia © in © pronounced An increase in viscosity is noticed, after which they are left in a bath of solid carbon dioxide and acetone frozen raid while standing over laughs on skin tissue. The components are ü & wn on

IiO erhitEt ⁰ G and about 2 hours, held there to form sine very viscous composition. The statutes will be frozen as before and heated and left to stand over the weekend. The ingredients are "heated closing vnter stirring in a bath maintained at IQO ⁰ O" to uic a thick, viscous mass to picture en _o

TsIl D

A spin measurement is made by adding 15 g of poly-Cp-bonaamid) (lj _inll ~ 1t20, comminuted by treatment in the Rugöliflühle, prepared according to the general procedure of rope A) at guarantee temperature to a mixture of 148 ml Ii - methyl cap: ο Iac tarn and 7 g of Ii: .thium chloride are given. This mixture, which contains 8.8% by weight of the polyamide and 4 »1% by weight of the salt, is stirred at low temperature until swelling takes place. The swollen mass is then cooled with a mixture of solid carbon dioxide and acetone aui, heated to 11O ⁰ C, ma create a mass au ,.

~ 193 0 0 9838 / 21®?

Q-1031-R 1SH

Ieil E

10 g Lithiunchlorid be bet 55 ⁰ C in 200 ml troakasem H- ~ Methylpyr: i; ~ solved Olidon. 2 20 g Poly-Cp-bemsamid) ^ linh ^s ^ · ^ρ ^ » ^her S ^es * ^e ll * according to the general Ji?] 33lts ™ manner of Toil A) are added at LOO ⁰ O with a lot of scrambled ice, the mixture contains 8 , 9 ~ # of Polysoaiao weight and 4 * 4 Gevr, _r -. $ of the salt, "In about 1 hour ergiöt Sidi a viscous ^ composition. Piping is overnight hei 100 ⁰ C stirred to erssugsn to a free-flowing Hasse. ■

Part ,, F

40 g of p-AmlniäbenaoylchloridhyäiOchlorid will »teaJ. Ice temperature au 200 ml lisli'-dimethylithylenurea, in order to form a clear solution. The cooling bath is removed after 20 minutes, after which a thick corn forms, sting, 1 hour is given 10 g of Mthiuaüi / droxyd and the Mixture is ^{heated to HO 0} G to turn a clear, slightly; A sample of the polymer precipitated by the addition of water has a logarithmic viscosity number of 1.36. This general statement contains something. 9.7 wt .- ^ of the polyamide and etv / s. 6 _} 9 Sew «.- ^ Lithimichloj.id.

Each of the homopolymeric poly (p-benzamld ^ iP ^ olien ύοώ part A to eiiisohli eßlioh i ¹ illustrates the; b ^ previous SuaaiK set-up for use in the inventive masses and / odea 'threads, ie,; ) ed3S polymer has a peak height ratio below about 0.86 and consists of. SeciiiiisntationsteBt «

For Qi β 1 b3

In the following Table 711 results are shown - ' the work patterns described above for var-

'- 194 -

. ORIGINAL BATHROOM

>; 0 09836/2187

Q-1031-R

different anisotropic compositions according to the invention, the
(p-bensamid-) contain, have been obtained. With
'"Quelle e ^a ü.0 written column gives either the spessiel len! Part of: i Example 62, in which the mass is produced
has been, or else a rope of Example 62 as "de Ben general procedure for preparing the cash ve spent, we-1, Bas Symbol ^R T" is used for the · value of ₉ from the expression

f / I ^ß '~ I?' / I ^o1 ) xlOO
is obtained.

- 195

009836/2187 "ad" hqinal

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I a b θ 1 1 β; ΠΙ

source
in at
game 62 • AüGißOillTQ pie of the masses ■ or
Ear-
- EtOff Liöi ia
the 2512. « - ^, JJr. * Ϊ Poly-Cp "» Bemsamid) a 4.9 - 42 3D Göw. «^ In
de £ * '/cMBBIBIU.&Tl
setzimg b 2.5 68 1 0 1.28 8.2 C. 6 ₉ i 64 2 B * 1.26 8 ₃ 7 d 4.6 4.2 3 ■. B * - 1.39 9A d 4.6 29 4th E. 1.18 7.4 e 6.0 21 5- E. 1.18 8, ₇ 2 Θ 4.0 47 6th E. -1.10 8 ₉ 0 d 5.1 68 7th B * 1.10 8.0 d 5.0 68 8th B * ■ 1.18 12.7 a 4.3 78 9 1.18 16.7 ! Footnotes: 10 1.18 13.8

b = s IJ-Me thy :, c apr oleo tarn

N, N-Djjca (> thylacetajaid N-Me fhf .. pyrrolidon- 2

* At room temperature ¹ it dissolves pol jmerieat,

* · * All lAeammc ^ M ?.: Ir. ··:. made,

B ö i

^. e 1 64

D «3 present Brisplf * X versiiBchauliohi a Γ ^ οπ ^ -οΛλη-granim far e .ne NiN-Dimcthylacatajjiid-LiWi.tuinchj.crl'i- Mi · .SiSe,

lr ^ iNity -; «■ *)? , from -X, 1S becomes-ge-no.H dei: in r © ifiu: -. el GZ A l) i ·

t? i \ lt iWlko c.en

009836/2187

BATH ORIGINAL

The general procedures given above are produced by mixing the polyamide, N ^ K-dimethylacetamide (contains about 0.2 to 2% of war-ser) and lithium chloride in different! Let room temperature go through. EUhren high Gteeehwlndigl eit (3000 to 4000 Upa) having a spiral wing geeslmten with O _s 635 cm Mröhaiesser are combined in a 2 wl tube with 0.952 om venting area se · sr without external Erhitaeß. Kle: .ne quantities of 'light _p dls resist the dissolution, _s wü-lk jiotivendigp were examined by hand serloit aelt = ^ Lassenproba-.s with vazcscMedsDasi Koasentr-ationen v / ext at ₅ inüam jeds sample sv / i'schen ainem MÜEroßkop ^ lbjektträger üüd e..ner Abdeetoing Is a thin layer gej. will tear. Meaä object carrier willia swischan

ess Polariaatoran with üiid without magnification betraoh "f & i dews whether di-> Maasea a 'eiiaaelne isotropic phase, a ·, one anisotropic Phaos ODAZ; an emulsion containing Ph &; - en ». You presence ^ on etvaigsüA fe »steiD parts; .- enf öntigem Polyaia. This white is also determined in the mass sample.

The result of such a provision was iö dem .l? Hassndiagrajji ·; voa Pigiir 1 gesse'.gt »Eb are given for areas. B rich (1) is completely isotropic, with the polymer being completely dissolved. Area (2) partially isotropic, v / obei microscopic areas linearly poj.ariBier'.eß Lioht depolarize. Area (3) is completely anl; ot; rop. Area (4) is also completely anisotropic, but contains solid, particulate matter. Polyamide. Me linio, wi & chen area (5) and area (4) represent the inaxlmalen · ■ 'olyeal content .that is, when the polyamide content goes above this point, the mas3β is over-saturated,' v / when solid polyamide is in it. Bareich (5) is completely isotropic, but contains solid particles in the form of polyamide ».

- 197, 6AD OHiGiNAi.

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The phase diagram is based on the appearance of the Mass samples determined as follows:

The beseiehneteii be isotropic (Area 1) masses are clear and transparent and erscheiner, when viewed with or without V ergröBexamg swißchen gekreius "" th polarizers (as described above) as structureless "dimlclea field <>

The Hassan referred to as partially anisotropic (area 2) are emulsions of isotropic and anisotropic phases. At lower Polyajaidkonsentrationen the continuous phase is isotropic, while at higher Polyamicikoiiaentrationen the continuous phase _o is anifotrop These masses appear cloudy, often show bite; Stir Opalesaens and can be obtained by centrifugation (or in some cases by gravity). If the continuous phase is isotropic, the microscopic, double-refractive parts of these masses appear against a dark field as a multitude of bright areas of varying size and shape, when under magnification (for example 400 times) they appear as similar polarizers ( as described above). When the continuous phase is anisotropic ;? so the isotropic parts of these masses appear against a light background as a multitude of small dark areas when they are viewed under magnification (e.g. 400-faoh) between true Poiari ejators (as described above) ",

Dis as completely anisotropic (area 3) mass Ben designated erßcheiren "if they zwistihen gekreuss th polarizers (as above bc; wrote) (beispj.alswelsö 400) under Vergrbflerurtg be considered ula a hellfau field with varying Joppelbi'echimgBriclitung. Often, thread-like lines, which are thin for nematic mesophases, can be seen KU. The eeild becomes low or oboe

- 198 009836 / 2H7 '

Q-X05I-R

Magnification depolarized. When standing undisturbed the mass is often transparent and only becomes transparent when it flows translucent.

The masses in area (4) and area (5) are similar to the masses in area (3) and in area (1), but also contain solid, particulate polyamide Area (2) are indistinguishable »At high magnification; (e.g. 790x), however, the particulate material appears angularly in these masses and does not eat. Its non-flowable nature results from the fact that this material does not flow _t when pressure is applied to the cover slip.

Ranges (2) and (3) are highly preferred masses. the Properties of generated from these anisotropic masses Jades in the state like extrudie.et are generally the Characteristic? η covered by threads? the a.us otherwise the same; Masses are produced "dJ.5 are isotropic or less anisotropic, as illustrated in the following example

3 e i s ώ 1 e 1 65

Iiii vorlxegfi. '. The example the thread properties are shown in. State i * io extruded one from a high kass aniso tropic mesir < made ϊa lens with the properties of elnc-E thread; compared to that of a crowd ii; t, al- · g ^ i.'ing is anisotropic «

Hung poly (': - beng ^| ? ADid) mass in KiU-Dimethylacetaiaid wire. & - ~ ι. * Χύ iV..B o'dgeif general laborBweJ.i3er>auc; p-Airiiiobei ζ i / l «hl iridhy & rochlorid imt-er use: us ^ ^: όϊι liithiumcsrbo ■ ην'ύ ¹ I .-. C:? eB"'cί111; » ΙΛβ Bid erg evening e 'Maar: -ε ( η, - »2.56)

009836/2187 bad original

is centrifuged in a Beokman "L" ultracentrifuge at 50,000 rpm for 21.5 hours using a Ti 50 rotor: d. The two layers are separated and separately flüsaigen lurch a 0.01 cm single-hole spinneret into a 75 ⁰ O kept at 60 Koagulierungswasserbad _t extruded to prepare filaments which exhibit, after drying, the following Zugeigenseha'ten:

From the upper "" somewhat anisotropic layer: T / E / Mi / den * 1.2 / 9.0 / 64 / 22.5.

From the lower, very anisotropic layer: T / E / Mi / den * 7.2 / 8.1 / 283 / 4.8.

At s ρ 1 3 1 66

The present example (Table VIII) is illustrated (l) the influence of the special amide or harassoff molecules and (2) contrasts effectiveness of Lithium and potassium chloride in the production of the invention anisotropic poly (p-benaamid) meshes, each have the maximum polymer content for the Specially evaluated systems have been found to be possible c The table also shows the relative resolving power of Kai « siumolalorid systems versus lithium chloride systems The Sabslle It can be seen that Lithiumchlori.d in general bes'se.c is.

Isolated B3ly- (p ~ benaaraid) with a logarithmic viscosity number of about 0.7 is prepared according to the general procedures described in Example 62. There are masses a ?, with each of the amide or urea media horge- · provides "which contain at about 4 to 9 wt .- ^ lithium chloride or ^% calcium chloride, vfobel polyamide is added until the maximum polya.aldgehal" fe is obtained. The salt is in the

■ - ί? 00 - 'Q09836 / 2tt7

Q-1031-R

Amount added representing the polyamide content for the special Amide or urea medium makes optimal. These results are given in Table YIXI.

a b β 1 1 e VIII

asssssssssasssssss

cool 1

Amide or urea medium

acyclic amides

N ι N-Diinethyl acetamide NιN-dimethylpropionamide N, N-dimethylbutyramide N, N-dimethylisobutyramide N, IT-dimethyl methoxyacetamide N, N-diethyl cetamide

cyclic aci de

N-methylpyriolidone-2 Ii-methylpipe ridon-2 N-methylcapj clactam N-ethyl pyramid-2

ac ethylated cyclic amines

2Ϊ- acetyl pyrrolidine N-acetylpiperiaine

oyclic brain matter

N ₁ N'-Dimethyläthylenharaetof £ N ₁ N * -Dimethy! Propylenurea

maximum poly
merizatkonzen
tration
(Weight-50 Lithium chlo
ridconcentra
tion
~ (Weight ~ jO 20th 5.3 28 5.1 30th 6.5 21 9.2 11th 5.1 22nd 5.0 U 5.2 11th 5.4 13th 5.2 25th 5.3 17th 5.4 14th 3.8 19th 5.0 18th 5.1

- 2Ql -

Q-1031-R

Table VIII

Part 2 *

Polymeri Amines Amide or ham satconzen 17th material medium tration 15th acyclic amides 11.4 N, N-dimethyl acetamide cyclic amides 19th N-methylpyxrolidone-2 14th N-methylpiperidone-2 17th N-lthylpyr3, ⁱ olidon-2 acetylated to oyolisohe H-Ao etylpyD? Rolidine N-Aoetylpi] »eridln

Potassium ClilO " Ride Concentrate Chloride

- tration

8.0

7.6 3.7 6.4

5.1 7.7

system in good condition Lithima GhIoridsystem *

D C

* Gaining explanations

A little effective, difference 410 #,> 5 %

B equally effective within 3 % of each other

C somewhat more effective, difference <5%,> 3 $>

D, effective, difference <10%,> 5 #.

B el s T) te 1 67

The present example illustrates the manufacture of copolymers of poly (p-phenylene terephthalamia) and poly- (p-phenyienleoplithalaaid), from masses thereof and from threads thereof, öegensätae bei Padeneigenscha ^ - ten ewisohan products from anieotropic cash registers and from ii3o tropan measurements are also settled.

00993S / 21I7

Q-1031-R

Mia chpolvmerisat production s

Isophthaloyl chloride (sublimated) is added all at once to a solution of 5.40 g (0.050 mol) of p-phenylenediamine in a mixture of 65 ml of hexamethylphosphoramide and 35 ml of N-methyl-2-pyrrolidone, which are contained in a 500 ml Harsher container equipped with an air-driven stirrer and a potassium chloride drying oven. The Hischung is stirred for 2 minutes and powdered Terephthaloylefalorid is (eublimiert) was added at once with vigorous stirring * The temperature of the reaction mixture with a cold (20 ⁰ C) water bath moderate · Ss is stirred Welter, is obtained until an unstirrable mass. The mixture is left to stand overnight at room temperature and is then combined with water in a 3.785 liter mixer and stirred at high speed. The polymer is washed three times with water by stirring it in a mixer and isolated by filtering it off on a coarse-pored sintered glass groove. The polymer is dried in a vacuum oven at about 70 ° C. overnight. The Polymeris.atausbeuten and logarithmieohen Sahlen viscosity, measured on a solution of 125 r n * g polymer in 25.0 ml of 95 bie 93 GAW .- # sulfuric acid, are samiaengestellt in Table IX. " *

Table IX

Missch- Is jphthaloylchlo- iPerephthaloyl- Ausbeu- mm / r polymeri-1 (I) chloride (Ϊ) te (inh ^{i / x}

risat '- _{| t [i M ||| ti} - "

[A] 0.51 g, 0.0025 9.65 g. 0.0475 11.5 g 4.48 95/5

MoL Mol -,.

[B] 1.32 g, 0.005 9.14 g * 0.045 11.2 g 5.84 90/10 Mole mole

[C] 1.53 g, 0.0075 8.63 g, 0.0425 11.4 g 3.22 85/15 Mole mole

[D] 2.34 g, 0 _f 010 mole 8.12 g, 0.0400 11.7 g 1.69 80/20

Mole

Production of an anisotropic mass from polymer [A]

A mixture of 5.0 g of polymer A (from Table IX) and 45 »0 g of fuming sulfuric acid (0.8 # free SO») is poured under anhydrous conditions with a mechanically driven stirrer of the Plügel type in a 200 ml round. · flask mixed while geklOli.t with an ice / water bath "the mixture is stirred overnight gel & soeii * during which time the cooling bath to room temperature Warming <is left · the resulting very viscous © Mao'se sselgt Rühropales ^ enz and linearly depolarize light.

Thread production from polymer [A] by

The spinning maize produced above is centrifuged with Eßfe ^ rmag ν closed gases. It is darts salt «tele a mechanically driven syringe dura aixe 0 _s 025 cm d; .cke noble metal spinneret with 20 holes _r - from 0 r 00 to 6 cm j) in diameter in an aqueous bath with 2:> ^c 0.rytruded . The water bath is about 5 »! om broad and etv ^f i 2 _s 54 chi ti'Sf »After going through a bathing table τ: γ. ei; vi 0.75 m we <i of the yarn with an angle of et \? a. ij ° tua out of the water and out of an electrically driven Axifwioicslv erection “The G-arn is with 7 _f 2? m / ri; t'.u collected on a perforated fcpule »Is will Φ * νη fA'y luebxere 'Sfc mden. (3 Stmiiden) in cold, flowing-u / v & vts & r gev / aschen mä dried in air at room temperature » Wv, Mden iseigni succeeds in crystallinity & t uad one. O ^ itntlt—

i. from '55, bebtimn ί; from a Vieiwi / i.mi-e "] - '> iöir ^; " i: e ..-; - igraimt' »Die Fädea aeigen dio following ? / l / lU. ^f cl. '\ values: 7.7'11.3 /

204 -

0 09836/2187

^ BATH ORIGINAL

Production of an isotropic mass from polymer [D]

E.Lne misclusion of 5 _f 0 g aes of polymer D (compare ¹ Sa. " belle IX) and 45.0 g ra.UGhend2r sulfuric acid (0.8 % free SO ,.) is iii.ter anhydrous conditions with a

^£ -.driven mixer of the wing type in »only 200 ml Hmic! 1: ols mixed _? while the @iaea ice / water bath is used for cooling. The mixture is allowed to stir overnight, during which time the cooling bath is left to warm up in the water. The resulting Masisa is viscous, clear WiA isotropic .

Pad ice production from polymer [Dj by Naßspianea

The Spinnraasse prepared above is centrifuged sur removing eiügaschloßä.enen gases. It is daam by means of a syringe through a nechanisch angetriabeneü O ₉₀₂₅ cm ^{d;! I} L k3 Edelmetallspimidüee 20 Lööhera 0.0076 QH diameter in an aqueous bath silt 25 ⁰ Q exfcr-u diert. The water bath is about 5 _f l csm wide and about 2 _B 54 esa deep ο After going through a bathing route of otv / a O _s 76 m , the Gara huv; an angle of approximately 45 out of the water and n & iiner electrically driven winder rf-ei'üm. ";. Tjb.3 yarn is 5.9 m / min, on a per» fori & Rtan S) gnaammelt molecules. It is then Soaked for several hours (3 hours) in cold, flowing water and dried in the air at Eaumteznparatur /i23kel-R8ntgenBtrahleiiö.iagraamu The threads show the following T / ß / Mi / den-V / erte: 2.4 / 25.1 / 82 / 5.68.

B e i a ρ 1 el 68

The present example illustrates the manufacture of threads αιβ an anisotropic mass that

- 2Q5 -

009131/2117

BATH ORIGINAL

nylenbenzanid) and fluorosulionic acid.

A total of 28 g of poly-CPJP ^ ptenylenbenaainid) with a ^ inh ^{V03Q in} 99 ₁ 8 £ ^about ^ »0 (ew ~ # sulfuric Sehwefelsäure ₉ c - 0.5%) are dissolved in 102 ml of commercial FLuoreulfonsäure wherein eite. Dark gray _s opaque anisotropic mass forms, which shows pronounced Rühropales- ZQJiZ. This wire Hasse, poured up to about 5 ml in an "Inconel" -Spinnzelle 4 "'5 on inner diameter and 11.7 cm deep. The mass is geBpoimen through a platinum spinning nozzle with 100 holes each with a _{diameter of 0 8} 0635 ram, a mechanical pressure of 13 _s 4 to 23.2 kg / cm being exerted on a piston above the spinning mass. Vev thread is extruded; .n water with 5 to 10 ⁰ O and, after passing through a bath track, is wound up about 140 cm at a speed of 14.7 to 22.6 m / mine. The thread is washed on the bobbin with running water while it is being wound up and for 16 stitches afterwards. The yarn is then placed on the coil in the air for 1.5 hours and dried with AEMR Geschwin speed ve η 8.2 m / min, in e: .nem to 635 ⁰ C erhitaten tube (device C) to 1.14 -fold stretched. The yarn strings for T / B / Wed are 3.70 / 1.2 / 402, the orientation angle is 21 °.

That the present Böisplel reveals the hex ^% position of FHden from an anisotropic mass, the poly-Cp-phenylene ~ p _l i) ⁱ -diphonyldioarboxaiuid), fluurulfonic acids and halves. contains *

Sine Isotrope Hasse is made by adding 13 g of poly ~

^β 2 _r 2) bsi

O ⁰ C in 40 ml of anhydrous H ″ to be dissolved. This mass

- 206 -.

009136/2187

8AD ORIGINAL

Q-1031-R

is about Ii; .ent to -80 ⁰ C gtvkihltc It is back to 0 ° heated and there are sugegebeiu 20 jal Commercial fluorosulfonic The mass is heated "evaporate the most λ HP to were reading under nitrogen to Räumtenperiitur" in the next '* Say!; a further 5 are given, fluorosulfom-irjii-o ssugs «, the result is a viscous» anisotropic MaSOo ₅ , which sseigt rühropaleasännz «. It consists of about 25 ml fluorosulfonic acid, "5 inl HP and 13 g of polymer. I3is 25 au. Viskü the" sen opaque Hasse. Beige RUhropaXeszeziz "The mass v ^T .ird imter using animal in the previous .Example Vorrioh" ti3 described Bg in iTom vojs Fäden extrud.ieit ».v.'with an isechanical pressure of 30 * 5 to 35» 2 kg / cm * "atf a piston above the mass" is applied to H ⁰ O verspo3s <nen u? id after a? Buichlaufstracke of 140 om in water wA about 5 om in egg ^ wasaur (in which the paefi ^ a are fixed by means of a smoothing, which is by 90 °

Padenlanfri <httmg is twisted) salt siner of 19 »7 m / lHn. wound up. The! Pälaa are βλχ £ the le \ m & 4 table long afterwards with Flussei'.dejiä V / aessr

The! "Eden v / <- rden with the Gesc" iwinäigk? Ä.t of B ₂ 2 m / min, so that 1.12 times -vez-sti-eokt _? Ib ies? di © jf-eaexi Mdsn cnx'oh ο in

to 55O ° C e: · hits5t <5ß Eohr (Vor; ^ ichtuag Ί); The 3? Aden h ,! ^; ben the following Duraisch / iittl to T / E / Mi / cen: 3.2 / 7.2 / 141/2 before the 5 ε4 / 1.2 / 508 after stretching.

Example 70

The present example Tera.iBGhaiil.tfiht vie production of poly- (3 _; 3 ⁵ -dimethyl-4,4 ^f - ■ »iphenyleii-to.rephthislsdcid}, P ^r --- j '·" (5 r 3 ^f - r. imetho% y ~ 4 ₈ 4 ^B -dip-lenylenter &p'h"hol-'iiaj! -r?) mid poly- (3 r 3 '- * ^f " £ sietaoxy ^ 4 _g 4 ^β -dip: ₄ enylene - »ii- ₁ 4 ⁸ ■» <■ iphanyl coraaiid) sowio tojj ani sctrop & n OlearomiiieeK divon.

207

BAD OHiGlNAL

polymer

It is used by the operation of Example 49!, Are used with the exception of 2.12 g of 3,5 ^I -Dimethylbenjsidin than the Dismia ,. The cooling with solid carbon dioxide is removed after 15 misery and iiaah 30 minutes is formed. a precipitate. After 2 hours the stirring is stopped and the mixture is allowed to stand for an additional 16 hours. The vaporized and dried polymer weighs 3.39 g and has a logarithmic viscosity steel of 2 * 11 »

2.0 g of the polymer are under anhydrous conditions dissolved in 8.0 ml of 100.95% sulfuric acid, meanwhile 48 hours which is stirred for a long time to create an anisotropic mass form, which shows Hühropaleszenz.

q? eil a polymer production ;:

The procedure of Part A above is used, except that 2.44 g of 3,3 ^I -dimethoxybenaidine is used as the diamine *, stirring is continued for 2 hours, during which time the system becomes very viscous and sioh then forms a precipitate. The mixture is left to stand for 16 hours at room temperature. The washed and dried polymer weighs 3.9 g and has a lo ^ arithmic viscosity number of O _P 99 *

Production _ί a Mas se;, ,, ·.

2.0 g of the Pilymerisats are under anhydrous conditions dissolved in 8.0; al 100.95% sulfuric acid, iadem Stirring slowly for 24 hours, Bs forms one

009836/2187

BATH ORIGINAL

clear, isotropic solution. The addition of 0.2 g of polymer and its dissolution provides a uniform, viscous one. anisotropic mass that has a high degree of agitation rheumatism shows.

Part Q

The procedure of Part A is used with the following exceptions: 2.44 g of 3,3'-i-methoxybenzain are used as the diamine and 2.79 g of 4,4'-i-sn25oyl chloride are used as a finely ground solid admitted. Hie cooling with solid carbon dioxide is removed after 15 minutes and after 20 minutes the mixture is viscous, however _s milky. After 2 hours the stirring is stopped and the mixture is left to stand for an additional 3 48 hours. The washed and dried polymer weighs 4.4 g and has a logarithinic discosity number of 1.43.

Making .a mass?

2.0 g of the polymer are under anhydrous conditions Dissolved in 8.0 .nl 100.95 # solv oleic acid by adding 24 Hours is slowly stirred. It forms a velar Isotropic solution. The addition of 0.2 g of the polymer and its dissolution provides a uniform, viscous, anisotropic Maase, which has a high degree of Rühropalescence.

In the case of mass production, a similarly prepared film sample (2.0 g # ^ _iMh »1.67) is mixed with 18 ml of technical metharine sulfonic acid (water content 0.3 ° 5fe, Breohung index n _D ²⁰ » 1, under anhydrous conditions for 24 hours at room temperature) 4293) stirred. The resulting viscous mass is anisotropic, shows Eühropalegzenz and depolarized when viewed through crossed polarizers linearly polarized light.

- 20.9 -

006836/2197

B ei, a ρ ie 1 fl

The present example illustrates the manufacture of poly (3'-methyl-p-benzamide) and anisotropic oleum masses of which * the DDA values are given for the masses.

Pplymerisatiierstellun ^ t

A 500 ml resin production container, which is equipped with a Rillxrer of the snow base type, calcium chloride drying tube and nitrogen tube, is ignited with a Bunsen burner and at the same time flushed with nitrogen. The container is sealed and placed in an Eroekexifcamiaer. 24.728 g (0.12 mol) of 3-methyl ~ 4 ^ aminobenzoylehlor ± d ~ hydrochlorld be weighed in the drying chamber and leads tiber In deri container. This is removed from the irooking chamber, reconnected to the stirrer motor and the nitrogen line and cooled in an ice bath.

140 ml of cold tetramethylurea are quickly poured into the 3-methyl-4-i3iainobenzoyl chloride hydrochloride, which is stirred at high speed. The resulting solution, which provides shortly thereafter a precipitate, is stirred for 1 hour at about 5 laiig O ⁰ and 4 hours at about 25 ^C 0th The mixture is then cooled in solid carbon dioxide and 8.868 g (0.12 wood) lithium carbonate are added. "Mused is 1/2 hour while, geküiilt in solid carbon dioxide and stirred for 1 prior at about 25 ° C. The mixture is stirred at about 25 ⁰ C 63 hours allowed to stand. The mixture is combined with water, stirred in a mixer and filtered. The precipitate is washed three times with water and each oinmal with acetone and alcohol by stirring in a mixer and after each washing procedure from "filtered vlrd" The polymer 16 hours is at SO ⁰ O in einom vacuum oven with ainem nitrogen stream ge -

- 210 -

009836/211?

YiA

Q-1031-R

19296 ^C1 4

dries. The yield is 100 7 _inh 0.88.

Hate t

IjO g of the above polymer are combined in a test tube with 5.66 g of 100.81% sulfuric acid (3.6% free SO ₃ ) and stirred with cooling until a solution is obtained. This anisotropic mass contains 15% by weight of polymer, DDA = 80.6 *.

1.0 g of the abigen polymer are combined with 5566 g of 100.14% sulfuric acid (Q _f S5 i> free SO ^) in a test tube and stirred while cooling until a solution results. This anisotropic mass contains 15% by weight of polymer, DDA β 92.2.

10.0 g of the above polymer are combined in a test tube with 48.82.5% 100.95% sulfuric acid (4.25 1 " free SO ₃ ) and stirred with cooling until a solution is obtained." -% polymer.

B e; i, B, p, 1 e 1, 72

The present example illustrates the preparation of poly (p-plienylene terephthalainide), as well as of anisotropic oleum compounds and compounds thereof. Mr the mass is the DDA value aagegebeö.

To a L3simg of 43.2 g (0.4 mol) of p-phenylenediamine, dissolved in 48 ml of dry hexamethylphosphoramide and 240 ml of dry tf-methylpyrrolidoii-2, which is contained in a mixer, _{s are} 0.11 with stirring g (0.4 mol) of finely ground Tarep & t & aloyl chloride added. The egg forms a gel in about 20 seconds. After 20 minutes the gel is broken and it is oiled with water, twice with alcohol and

- 211 -

009636/2117

BAD ÜHiGuMAL

Q-1031-R

washed twice with acetone to give 93 g of air-dried polymer having a T ^ _n J ₁ ~ 3 »13. Different batches of polymer with a slightly higher and etv / aa lower inherent viscosity are also prepared as above and combined to give a polymer with a ßieh j ^ J _{11 1} ~ 3 "16 is obtained.

30 g of the mixed polymer are dissolved in 27 ° C. g of 100.4% sulfuric acid at room temperature to give a composition capable of being used which contains 10% by weight of polymer. The mass is, determined by means of its depolarization axiisotropy value B (DDA value) of 93.6, anisotropic.

The mass at room temperature is · kg / cm pressure extruded with 60.7 through a spinneret having 60 holes, each with diameter 0.0635 aim in a bath maintained at 4 ⁰ C water bath, the filaments are wound up at 6.8 m / min. After drying, they show the following thread tensile properties ι T / E / Mi / den '* 7.0 / 10.7 / 197 / 4.9. ■ '

Β ^ Β, .ί, Β ,, ρ, i e,, 1 7.3 ■

The present example illustrates determinations of anisotropic and isotropic phase relationships for HF, 3TSO-H and GlSO-H materials that are made up of different materials according to the invention Usable polymers and copolymers are produced. Purely one system becomes an exact determination given, while for the other systems summary results (which are similar but without Viscosity determined to be obtained in a table are compiled. ·

~ 212 -

_Λ '^ _{Ä Λ} 8AO

009836/2117

Q-1031-B

horny A

It can be seen from the results given below and from FIG. 1 that there is a discontinuity in the slope of a curve for mass viscosity versus polymer concentration for "exemplary compositions according to the invention which contain poly (p-benzamide) in HJ?". The slope of the curve changes when the polymer concentration in the masses is about 14% by weight (ie _e , at the critical concentration). At lower polymer concentrations, the mass is clear and isotropic second phase is formed, which is _{visible at 15 + O 9} 5 #, has a lower viscosity, is opaque and shows agitation rheumatism. This anisotropic phase separates from the original clear phase with a high degree of viscosity "

The results relating to the above observations are summarized below. Two poly (p- »lfeenzaißid) <- masses in HP are produced" by combining samples of the polymer with HF, either in a polyallomer test tube with a diameter of 3ι82 cm and a depth of 10.2 cm, which is almost transparent and is equipped with a Teflon vy TFiUPluorico il ens t off cap through which a viscometer spindle extends into the mass, or in a polyafchylene bottle with a durometer of about 4.45 and 10.8 cm 5, which is capped through which a viscometer spindle extends »By using an external ice / water bath, a constant oil temperature of ⁰ ° C is maintained» The viscosity of the stirred mass is obtained from a Brookfield Synchro-Lectric ter (model EV, manufactured by Brookfield Engineering Laboratories, Inc., Staughton, Mase.), With the No. ₀ 4

009335/2117

JiH

and No. 6 «The viscosity measurements are carried out at different concentrations by correlating the spindle indicator readings (obtained with different spindle settings, the spindle assembly speeds and thus the amount of shear) with the sabelle values in the Brookfield Factor Finder« If more Polymer is added, aaiiaiat the viscosity of the solution until a maximum value of about 3600 poise is measured when 13.4 £ rew _a - # Polpaerisat are present in the tube «, when 20 + 1.0 wt .- fo polymer in the Tube are present, the initially clear phase disappears completely and only the anisotropic phase is visible high degree of Rühropaleszenz and (3) is thixotropic «.

Specific results from these determinations are in the Table X-A below.

Table X-A

g polymer / - spindle setting / calculated M & bsgk— GeWo -> ^ Polyneri- Spindelanzeiger-Able «viscosity in poise saiL__i; ■ aung.

Mass Ν;? · 1 (using 58 πΰ. Anhydrous )

3 / 4.9 56 50 * / ll, 5 5 / 7.9 1> 10 * / 55.5 7 / 10.8 i> 0.5 * / 21f5 9 / 13.4 i> l ** / 36 $ 14 / $ 19.4> l ** / 2.0

46 13.0

3600 200

SADORiGJNAL

008836/211?

Q-1031-H

Φ a b e 1 1 e X-A (continued)

g polymer / spindle setting / weight "~ $ Pol.-nneri- spindle indicator display eat sung

calculated bulk viscosity in poise

Mass No. 2 (using 10OVlO ₅ 5 90 ml of anhydrous HF, 2.1 same polymer as in bulk 5Ü * / 48 Number 1) 19th 4 / 4.2; i 2OV9C 90 '. . 6 / 6.2: « 1 * / 51- 1020 8 / 8.1 'ß O _s 5 * / 44 1760 10 / 10.0 % 2.5WaO "3200 12/11, S # l ** / 28 2800 14 / 13.5 % 1 ** / 17 1700 $ 16 / 15.1> l ** / 8 800 19 / 17.5 % l ** / 4 400 £ 21 / 18.9 l ** / 3 300 22 / 19.6 36 $ 24 / $ 21.0

* Spindle RV No. A is used. ** It wiri spindle RV Mr. 6 used.

If- in Fi3. 2 the viscosity is plotted against the polymerization concentration (both results are plotted in a corve, iforin X represents the results with mass Mr. 1 and the results with mass No. ₀ 2 are shown by dots), see below. that the critical point occurs at around 14 Gaw _o - # polymer. The final viscosity of 200 to 400 poise is about 4 to 6 # of the highest mass viscosity measured or determined from Fig. 2 from the viscosity at the discontinuity in the curve. "

- 215

009836/2117

BAD OBiGiNAL

1 Q? QR ca Q-1031-R - * - ^iaZybwH

(The above viscosity guidelines are with an uncalibrated Yisfe osimeter-Spindelsj-system was carried out in containers that did not have optimal dimensions So are the relative viscosity determinations for the mass Although rough, the absolute values are not necessarily correct.)

Tell B

By applying the above-described modes of operation, the sorbiniase given in Table XB below will be obtained for the given systems. In the systems in Table-B, decreases in viscosity (similar to those shown above) are qualitatively observed; if any given hatred changes from isotropic to anisotropic as the polymer concentration of hatred is increased. The anisotropic masses seigtn above visual Rühropalessens and depolarl * Sieren at cer viewing lii a microscope you;? Ch gekreuiste PoIi roide the plane of polarized Idcat "In Table 1 ^ B is in the tiherschrlebenen with" polymer of ™ gap "· Example given _{t the} general method of operation can be used to produce the given polymer or mixed polymer _t whose mfiss is assessed by the working methods of the present example

- 2: 6 -

ORIGINAL BATHROOM

009836/2107

Q-1031-R

1 (η _{± η1ι} » bell Solution with
tel isotropic masses B ^a 21 62-A (tj _inh HF A ^a . 20 to 13th 0? a ⁶² - ^A < Λ inh L e X-B ISO ₅ H. " 13% 12 to 19th ⁶² ~ ^{A (r} Linh HF 9 $> 19th Live relationships of anisotropic and HF 15 + 0.5 # 18 to 10 Polymer of ²⁶ (linh- ² PSO ₅ H 17 % 15th example ^{2 / c 7} UnIi "- ¹ 4.0) I ¹ SO ₅ H Q ü £
O /? 14 to b example ^{1 (7} linh ^Ä * 2.86) FSO ₅ H 11 to
12 % 15 % 10 example 6S-A (^ _inh = 3.9) PSO ₅ H 9 i> 9 to 10 example == 2.86) 0ISO ₅ H 7 to
8th % 9 example ² f C η inn ~ «3.9) GlSO ₅ H $ 8 example ² ^ ^ 'linh ^s , 0) 0ISO ₅ H 7 ^ - 11th example 23 ίη inh * ³ .35) Ii ¹ SO ₅ H 9 i> 10 example ²¹ ^ inh = ¹³ 3.4) Ji ¹ SO ₅ H 9 ^ 10 example 23 ( γι ι, ~ 3 = 2.86) , 0ISO ₅ H 8 "A 10 example Explanations: 3.4) GlSO ₅ H 9 $> example 2.0) 8? Ί example 3.2)
c-1 example , 5) c-2 example , 2) c ~ l example , 5) c-2

(a) A: Polymer concentrate Lon in the mass in which the second phase (anisotropic) is visible for opalescence or opalescence.

Bj Pol j merisat concentrate.lon, in which only one phase (anisotropic) is visible »

(b) Seheini to form two anisotropic phases, one at about

15 Gev.-ji and one at 19 to 20 wt.-56.

- 217

BATH ORIGINAL

009836/2187

(e-l) molar ratio of

-CO

entered 50:50.
(e «2) molar ratio of

-CO-i / ^ -CO - / - CO - ^. * S - </ ^ -0O- is 90:10.

Example 74

The present example illustrates the influence of Parweter (X) Acid Strength and Polymeric Consentratioxi, (2) the logarithmic viscosity number of Γν> 1 «χ a .: icitr · and (3) added salts to the suitably siii8otropeii uoiiwäfeleäure- and OleoMiiaasen, the? oly "- (p-benzanide) and poly (p-phenylene terephthalamide) contain,

SMWMM ^ l & fe ^ 3id Pol ^ r merisatkcnzentratlor »

The results of investigations into solubility in poly (benzeneid) The acid and oleum are given in Table XI mid Χ1Ϊ BueaKämengefasst. The solubility results will be The following terms are obtained: An excess of polymer v; ird ^ u the acid or oleum is placed in a round-bottomed flask, the one with a stirring device; Glass hole lift storage provide i & t, at the end of which a Teflon 09 'IFA-Fluorkohleiistofi' paddle stirrer is attached. The temperature of the flask: "J" is held with a water bath with room temperature moderate. Shares of acid or oleum are after long (for example 2 to 2: lo-stuidigen) helper periods isugegebsri and the maximum Lonaontrationtm become visual

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determined as the point at which no solid material builds up ßelien is. Further proportions of acid or oleum are added the liquid, anisotropic ones exhibiting Rühropaleszenz Masses given until the mass becomes visibly clear * The Polymer concentration present when the mass becomes visibly clear is called the critical point of consensus taken. The results shown relate to poly (p-benzamide) samples with logarithmic viscosity numbers of 2.72 and 1.53.

Tabel

Solubility of poly (p-bensamide) (Tl

rock acid ^l

β. 2.72) ^a in Sweden

maximum! solubility

H ₂ SO ₄ , % 4.5 96.3 7.14 97.3 10.3 99.2 ■ 12.7 100.5 14.4 102.3 14.5 104.5

critical point

none none 8.67 8.67 8.55 8.76

(a) Made in H ^ i-dimethylacetainide and neutralized with i

(b) Is determined visually as a concentration (wt .- ^ polymer) ι in which no fairy part particles are observed.

4- £ polymer in bulk

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Table XII

Solubility of poly-ip-bensamid) ( ^/ * lt _ri v, ~ 1.53) in sulfuric acid

^H 2 SO ₄ , * maximum Solubility ⁰ critical point ^D 68 95 , 9 6, 7 % 60 99 , 2 11th 9 _f 100 , 5 15, 5 9,

(e) Determined visually as concentration (wt .- ^ polymer), in which no fixed parts are observed.

Weight "io polymer in the mass.,

Using the results from the tables above, you can Phase diagrams are drawn as shown in 'Fig. 4 shown iSt ρ

Results from similar determinations on a poly (p-phenylene ^tereph: 5halamid) sample with an logarithmic viscosity steel mn 3.32 are summarized in Table XIII. A phase diagram derived from these results is shown in FIG.

Table XIII

Solubility of poly (p-phenylene terephthalamide) (tj ^ "~ 3υ32) in ^order Sch'wefeli3äure

> ¥ maximum solubility ⁰ ' critical point * 97 4.6 99 _p 7.8 100, 11.7 ---. .-- · --.- .'-. λ; ·
• r -. 'V ^; ·! · --'- - £ 20 - 8AOOfUGiNAL 009836/2187 JO _4;. $ , 3 , 2 , 5 * - ■■, · -: - ...

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a) Visually determined all concentration (6 wt .- # polymer), in which no solid particles are observed "

b) Weight "- $ polymer in the mass",

Eb is expected to be the critical concentration for a given polymer in a given acid with the Molecular weight (or the logarithmic Viscosity number) of the polymer varies * results for poly (p-phenyleaterephthalaiBid) samples with various inherent viscosity numbers are given in the table XIV shown «The following procedure is used to achieve these results! A sufficient and well-known one The amount of polymer is completely dissolved. The resulting anisotropic masses are then (during mixed with a spatula) titrated with the same acid or with oleum until the masses are visually clear, if they are subject to stress. This way of working Due to the very high mass viscosity, it may take several days to several weeks to dissolve the polymer. In general, this procedure is more satisfactory for polymers whose logarithmic viscosity number is below 3.5 lies.

Table XIV

Critical points (or concentrations) vqjj poly (p-phenylene terepithalamides) in ICO, 2 # sulfuric acid

Polymsrisat, t £ _inh kritiecle concentration

L, 24 10.61 # 2.23 9.4'i

2.64 9.52

2.70 9.13

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Table XIV (Forts eteuag)

1829694

Critical points (or concentrations) ύοώ PcIy- \ p -phsnyXenterephfhalamidea) in 10O ₃ 2 ^ iger sulfuric acid

Polymer, * tj _n k critical cons

2 * 76 3.92

2 ₅ 80 8.95

3.06. 8 ₉ 77

3 _S 37 8.39

a) & ew * -% Pciymerieat in the mass.

Ib Table JV are similar Ib results for
The results given in this table mean that the critical constraints are ₃ too low. Vißkc sitätsss ^ il des Polymerisate suiiiiPöt « Die 3Drg <? B 33isse eier TebelleiJ XIV and XV are in Pig» 6 bav /. schaulielit »

• Room XV

Critical effects (dull concentrations) of
in sulfuric acid

- ^ t --'- t -rr * T-Tnrnrr ^ .: f ^ - ^ «ΐ-ftiTrMi 'rrtf ^ ttr-ariTr ^ -iiiw w ι wiiniw hiiimihiii ii U iji m iiiw iwO« fcMHii> ni u ι ι wi in 'nr η -τ-

Polymer j Ij ₁ ^ _n J ₁ HpSO ,, # critical KosisentraiLon

1.67 99.5 9.88

It 67 100.3; "9 ₅ 55

1.75 99.7-9.74

1.75 / 100.5 8.57

1.75 100.5 ^ 10.00 2.16 100.2 9.67 2.66 '100.2 9.22 2 _S 76 100.2 9.30

2.76 100.3 9.69

a) Weight .- $ Polyiaeriaat in the checkout.

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Added salt

The addition salts tob has the consequence that _s Oleiaomasseii

(I) Poly ~ (pi ^ eayXeBterephtlialaiaid) (^, _- = 2.80) wiä

(II) Poly-C P = berasa »M) C ^ _infc - 2.72) in each case go into a solid pulp after a given saline liquid has been added. The agile SalsiE ^ ige for the formation is shown in the following table SVI for cash registers.

Easse / 3a3Lg ~ yggfeatljguja ggb, egigjmgggn

Polymer Iss the _{ς 1r} Salsmeüge the door lu: Ctre

Mass of a Ptfbi

0 _f 6 g

ΪΙ Ha ₂ HPO, 0 _? 8 g

I potassium acetate 0.6 g

XI Sa ₂ ^S0 4 ^{0 $ 8 g} -

Pie salts feaxöea added in parts of 0.2 g «, the masses ■ foleibsß fllsSfüriLg- uuä seigei? Eühropalefsseasj werai lclisinsre Mesgeii an SaIs as given in the Takeile _p in jedei? present ο

B ₁ e I ₁₁₁ S, ρ, i p. I.

The present noble example illustrates the influence of. To-iAperatur onfi & e? Sie3itsproser.tffleiige & n Polymexfieat on the critical tcniisuzitxatloBa points -for PpIy-C p-b-anfc-smid) ian <l " Toly- (p

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Poly-Cp-bens-amid) 'with. a logarithmic YiskOKi iätas VOB about 2 j 7 2 is produced in a similar way v / i © above 'bescliric-b ο There are masses with different EorasMtr-tionen _f nSmlleh- 9.2, 10.0 and 12.0 # · HpSO prepared at Bsumtemperatur: in 99, 5 parts by weight & Jmg i. Each of these pillows eats aniaotrap at this temperature. When the 2? Ea; pe.Tature is gradually increased * the ave ± tifeijs. ^ V samples change at
Mass lim.

Samples at 29 ⁰ C, 53 ⁰ C and 77 ° ü in essence

Polj ~ (p «=> pheryleBtsrephthalaiaici) with a logari.tiimis'afc.es viscosity number of about 3.1.6 is described in afealicher Weä.s® v / i-3-alien. There are masses with a tertiary concentration, namely 9.2, 10.0 and 12 + Q ^ in 100-3; HgSO ^ produced at raiim temperature & .. JsI *: - dd.eser masses. If at this temperature anisotropic is _t % Βηη ifc temperature slliaäM.ich increased v / ird _p . become «ils clr.el MagiBe: ·: -» rehearsals at 41 ⁰ IGS ₁ , 67 ⁰ C baw. 109 ° C in essentially isot;. * C? - pe

The! Points at which | ede de :. "above Praben merges into an essentially, isotropic mass, and the critical voltage ratio points for each sample are shown: Example shows that this point is for a special polynt - 3, 'iaat / FXüss.i gkeitsmediiua on the temperature of the mass around! The 6-ev / ichti pross? Jt amount of polymer because ^ ir ^ depends.

Example 76

The present example illustrates the hertmvllmsg of poly- (£ - clilor-1,4-phenyle: iterephtkalfisjnid) «an an.tsa trojoei? Hpi.üisaaesa in NjK-Bime '.- hylacet / vmä voa Passes with a high module from it.

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95jO g (O., 4 ^ 8 mol) of powdery TerepIithaLoylchlorid are at once to a felt solution (with about 3 C) of 71/4 g 0.502 mol) 2-chloro ~ 1,4 ~ phenyleadXaiiLiB in 2000 ml ijM -Mmetiiylacetsjnid given. My disapproval is stirred with greater speed, while it is chilled s & it with ice / water -> ». 3ad. The mixture appears to be about 1 to 2 billion. 10 minutes after the addition of the outer;) hthalcsylchloride, 37 _s O, g (0 _f 501 mol) of LithimaGarboaat are added to eiaiaal

Give chilling to keep the temperature below about 10 G hai tea. Hao.idsm has been continued for about 5 minutes j p'ilver-shaped xerephthaloyl chloride is added in small amounts. ""until the mixture is very thick _o Tm B Kuhl" - bad is to ifeint and dia mass on Baustemp ^ ratür warm geiaisen ₉ i ^ Onach you in Yerlauf few minutes (ie, _e 5 minutes) jaehr pulverföroiiges l'ereplithaloylohlorid small. Aritsilen is added, until a total of 0.500 moles of t ^ rephthaloyl chloride is added or until the mass no longer flows. Usually a smaller amount (ie 0.490 moles) is used to maintain a flowable mass at all times. The Maas © is then at Hamata / The temperature stands for a few hours (i.e. 12 hours), during which time it becomes somewhat more fluid. A small portion of the mass is combined with water and agitated in a high-speed mixer. The polymer lsate is filtered through a suction filter with a coarse Porosity ge & ammelto 23aa wet is dried in a vacuum oven at about 70 ⁰ C »Me Iqgarithmißciie Viakoeitätozahl ,, measured & ÖB on an O ₉ 5 (weight / YoLumen) solution in S5 at 98 & 8w "- $ 1 £ Qr sulfuric acid, amounting to 2.79. The mast is mixed with another mass produced in the same way and used directly in the manufacture of yam. The Maast- shows RüluOpaleazenz and D-3-

polarized polarized Mc-ht.

· Ίϊ ·, ΥΰΖ \ ί \ β tjA £ - .. 225 -

zn

by Nassapinnen;

The spinning mass produced above is extnidated at a rate of about 41 ml / min * through a noble metal spiral nozzle with 580 holes 0.0076 cm in diameter in an ^{aqueous coagulant bath kept at about 15 0} O. The bath is about 30.48 cm wide, 10 , 8 cm deep, and I ₁₁ 676m long. The thread bundle is sucked through the bath and guided out of the bath at an angle of about 45 to an electrically driven winding device. The yarn is collected with 43j89 m / min, a few hours (d _o h _o 3 hours) washed in cold running water and then in air at liaumtemperatur dried * The dry fibers exhibit low crystallinity and a Orientierrnigswinkel of 30 ° "determined from a Wide angle X-ray diagram. A Sarti twisted with three turns per 2.54 cm has the following T / B / Mi / doa values: 11.4 / 5.6 / 379/555.

The yarn prepared above is passed at 4.572 m / Hin "by sin heated to 45O ⁰ O, filled with nitrogen Eolirgefüge (device B) and 4,801 m / min, which eigebenden yarns show high Kristalliuität i a Oriextierungswlnkel of 12 °, determined from a white angle X-ray diagram ^ o. A 25 »4 cm long piece of yarn, twisted three turns per 2.54 cm bit, shows the following T / E / Mi / dan values: 11.9 / 1.4 / 875/493 and the gain shows One sha! '»! speed 7.84 km / Selu.

At s Di el 77

i> ii ι ι mn Mi min um μ imtiiwi m <! ... ι mum ΐι.ιιΐιΜιιιι>Aw>.

The present example illustrates the OteretaXlung of poly (2-ethyl-1,4-phenylene terephthalainide), an anisotropic lEpinmaasse in Hexailethylphoephoramid / li-Mathyl-S-

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pyrrolidon / Iiitisiiisaclilorid and of threads with high modulus from it.

PcIvEerisat heratelliings

10.15 g (O 05 ₉ mol) of powdered terephthaloyl chloride to be einyial ssu an ice / water-cooled slurry of 9 »75 g (0.05 Hol) 2-methyl-l, 4-phenjlendiamiMihydrO" ~ chloride in [16 BLL Hessmethylphosphoraiaid and 112 ml of H-methyl-2-pyrrolidone are added and the mixture is stirred at high speed. The mixture becomes clear within 1 minute and slowly becomes more viscous. After about 2.5 hours, 7 _{tons of} 4g Li ₂ O, Bugegeben, wherein after vigorous MIsaht, -α else anisotropic mass to the consistent state of a heavy Fe; tes ergxbt "the mass depolarizes polarized light in a small part of the mass is removed and siit water worked up and in a vacuum oven" at 70 ^0th! C dried. D; -Q logarithmic viscosity steel is 4 _S 46 in 95 to 9t> wt. Used spiders.

FadeBherBte'- JLiiBg äxtroh Kaßspitinen:

The SpinnTa '.' * Se is nit the Gsschwiudigkeit of about 2.0 ml / Kin _o extruded through a Metallspinndüse with 100 holes of 0.0064 --m Surcüameseer in a bath maintained at 17 ⁰ C wäseeriges KoaguJierungsbad. The bathroom is about 40 or wide, 14 and deep and 94 cm long. The thread bundle is pulled through the cooling device and then at an angle of about 1 °. 45 ° out of the bath and led to an electrically driven winding device »The threads are wound with 7» 015 e / MIji. collected "several (cage long washed in cold water and dried in air at room temperature. The dry threads show low levels of crystalline!"

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did and determined an orientation angle of about 50 ° » from a wide angle x-ray diagram. Me threads show the following I / E / Mi / den values: 9.74 / 10.2 / 287 / 1.64.

Another 3peil of the mass wii? D at the rate of about 0. £ ml / min, through a noble metal spiandüee with 20 holes of 0.0051 cm diameter in an Ißoprc panolbad extrudie maintained ^{at 24 0 G;: t.} The bathroom is about 5 »! om wide, about 2.54 cm deep and about 0.61 m long, "Das Sara. is pulled through cas coagulant and dana with. out of the bath at an angle of about 45 ° and fed into an electrically driven winding device. The yarn is collected at 10.68 m / min ", a plurality (Cage long washed uad in air at Hauiatem- 'temperature getiocknet kaitea in running water. The dry fibers exhibit low Eristallinität and a Orientiarungswinkel of about 40 ° _r ■ determined aui < A wide angle X-ray beam diagrams. The Mdeii show the following T / S / Ml / den value 9.0 / 8-, 6/265 / 1.82,

The Sara prepared above (aas the isopropanol Koagulieiiuigsmittel) is passed at 7.62 m / min, a lurch 4SO heated to ⁰ C with Stickstisff filled tube ^ efüge (Vorrichtuxig B) and collected with 8.02 m / min, , where the draw ratio is: .05 times. The resulting threads tend to have an average height of usd an orientation guide. 20 °, determined from a wide-angle X-ray diagram. The pedestrians have the following 5D / E / Ki / den values ϊ 8.5: 5 / 2.1 / 44 * 3/1 f809 and a sound speed of 7.27 km / sec.

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B ₁₁₁ Jg ₁ JL ₁ el 78

The present example illustrates the preparation of an anisotropic mass of poly (2-nitro-1,4-phenylenteraphthalaatiii) in a mixture of HsDcamethylphoBphoraniid _s F-methyl ~ 2 - »; 3yrrolidon uad lithium chloride»

Heratelluag one

6.09 g (0.010 mol) of powdered terephthaloyl chloride are added all at once to a solution of 4.59 g (0.030 mol) of 2-hi tro ~ l ₉ 4 ~ phe: .iylenediamine in 45 ml of IT ~ methyl ~ 2- pyrrolldon and 25 ffil hexam'5thylphosphoramid and it is stirred rapidly while cooling with an egg / kaseer bath. Within a few minutes (ie 2 minutes) the mass shows stirring propensity and after about 3 hours 2.22 g (0.030 mol) of MgGOa are added to give a stirring mass which is depolarized under crossed light.

A sample of all isolated polymer has a logarithmic scale see viscosity grade of 0.36 *

B e i s ρ i e, 1 7g

The present example illustrates the production of poly (3j3 ⁱ ~ dichloro «4,4 ⁸ -ßiphenyli3terephthalamiä) aui5,3» 3 ~ HichlGebenzidin and terephthaloylochloride, as well as threads from them.

In a 500 ml resin container, which is equipped with a disk stirrer, a nitrogen eirem and a xrook tube Outlet is provided, 250 ml of hexamethyl

-22.9 -

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phosphoramide, 250 ml N-MethyXpyrrolidon ~ 2 and 25 ₁ 3 g 3 "3 ^f " -Dichl0rbenzidin given. When a solution is formed, the container is cooled with a bed of solid carbon dioxide and 20.3 g of serephthaloyl oil are added with stirring. Initially, a clear solution forms, which soon turns into a slurry that remains tubular. The cooling bath is removed after 15 minutes. After 1 hour, 14-8 g lithium carbonate powder is added. It turns white for about 1 hour, after which the mixture Can not be stirred with this equipment. The closed container with its contents is left to stand at room temperature for about 16 hours. The polymer is isolated by precipitation in water *, washed thoroughly with water and dried in a vacuum oven. The yield is 38.92 g and the inherent viscosity of the polymer is 1.69 «

Masses » , and

10 g of the above polymer are dissolved at about 45 ⁰ g in 100 g konseiatrlerter (95 to 98 $ strength by weight) sulfuric acid ice, clear, viscous mass form shown below. At 26 ^° C. the mass becomes stiff and opaque. The mass is extruded from a heated skin through a spinneret with 20 holes, each 0.075 in diameter, into a water bath kept at 45.degree. The threads are soaked at 22 m / min. The thread is soaked on perforated bobbins in separate batches of distilled water for a total of 24 hours and then dried on the loft following 2ugelgonschaft 'Jß / E / Mi / den: 1.8 / 32.3 / 68.8 / 8.3 »the speed of sound is 2 / α km / sec _and after 1.75 times expansion, pull slowly with the Hand over a 300 ⁰ C hot rod (1.27 cm Ba;. 'Ühziingsober £ lache) the threads have the following properties T / E / Mi / dan: 2.07 / 0.6 / 326 / 6.3,

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OA s "12 ° and medium-sized crystalline did!" If that Sara be in 2ustand as extruded in the manner just described, except that the bar, a temperature of 40O eist ⁰ G v /, ^ is extended, the following Thread properties observed: T / E / Mi / den = 3.35 / 0.9 / 372 / 5.9, OA β 12 ° and high crystallinity.

The present example illustrates the production of TOXi thread kit high modulus from ordered poly-chlorophenylene terephthalamide).

Manufacture of H _s sr ^l ~ 3is «» (4-nitro ™ 2 ~ chlorophenjri) -. Terephthalamide

A solution of 52.56 g (0.3 mol) of 4-nitro-2-chloroaniline (recrystallized in water) in 250 ml distilled hexame «- thylphoephGramid. The solution is cooled with an ice bath and 30.45 g (0.15 mol) of terephthaloyl chloride are added in small portions over the course of 11/2 hours. When the addition is complete, the ice bath is removed. Over 4 hours a precipitate forms and the resulting suspension is stirred for 20 hours. After this period, 1 liter of water is added to precipitate the product. The pale yellow powder is filtered off and mixed with hot water in a mixer. After drying at 80 ⁰ O in a vacuum oven 68.2 6 (95 # of theory) product is obtained, P a 339 ⁰ C (determined by thermal differential analysis).

The IR spectrum shows carbonyl absorption at 5.87 / U, NO «-

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Manufacture of N, N '~ bis (4- ^ ino «2-chlorophenyl) ~ terephthalamide

40 g of the above dinitro compound can be reduced in 320 ml of H> I "Di methylacetaxaid using RaneyrNickel ^ Kat & lysa tor at 100 ⁰ C and 63.2 kg / ora hydrogen iia over 3 hours. Which is ergebende.Lösung erhitist ⁰ C to IQO, filtered free of suspended catalyst and treated at 90 to 95 ° to sum SJrübuzigspunkt with water. Upon cooling, a fine precipitate separates out, "This is collected, gewaachen twice with water and dried in a vacuum oven at 100 ⁰ C. Me yield of Dituuin is 26.4 g, F "261 ⁰ C. The infrared spectrum increases carbonyl absorption at 6.05 / u _F amine absorption and is in agreement with the expected structure.

Analysis "20 16 4 2 ¹ 2 ^Ϊ C. 84 3 H - N , 49 57, 92 3 , 88 13th , 37 calculated: 58 , 83 13th found ί

Production of threads with a high modulus from an ordered «« Poly (chloro-p-phenylene terephthalamide)

In a 500 ml resin kettle equipped with an air driven stirrer basket type, a StickstoffeinläS and a drying tube, are 6.23 g (0.015 mole) H, H ^l-bis ~ (4-amino-2-chlorpheEyl) terephthalamide, 1.25 g lithium chloride and 120 ml Ν, Ν-Diinethylacetaraid given. The solution is cooled with a wet ice bath for 15 minutes, to which 2.74 g (0.0135 mol) of terephthaloyl chloride are added. The resulting mixture is stirred rapidly . After 5 minutes, 1.11 g of sodium carbonate are added.

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setat. The healing appears mixed for a further 5 minutes as a somewhat viscous solution «an additional 0.25 g Teraphthalene chloride is added in small amounts and allowed to react until the reaction mixture appears as a soft gel. The solution is stirred overnight and after standing for several days a solution forms that viewing light between crossed polarizers dapolarislert. Your part of the solution will be in water precipitated and the resulting feet © polymer It is washed several times with water and acetone and then dried in a vacuum oven. The polymer has a Logarithmic viscosity range of 3 »25.

The mass produced above is centrifuged to remove air bubbles and then extruded through a spinneret with 60 holes, each 0.05 μm in diameter, into a water bath at 10 ° 3. The threads are wound at a speed of 15 »2 m / min and in distilled. Waasar washed overhead. After the yarn has been dried in air at room temperature, the following thread properties are observed: S / E / Mi / deB β 10.6 / 6 _β 6/343 / 1.49 , orientation angle 32 °. A speed of sound of 5 »91 kffi / sec., Measured at 0.1 g / don tension, is observed.

Yarn is heat-treated by passing it through a tube (device A) heated to 4370 ^{0 at a rate of 7/6 m / min, the yarn being drawn 1.06 times} while it is passed through that pipe. The threads then have the following properties of T / E / M / den. = 13.3 / 1.9 / 763 / 1.36, Orientierm> gswiMikel «· ■ 13 °.

Be is Ό Ie I 81

- * irrr ι T-tiir-'iirün -Jirri ι ι ~ τ AMKIMHHMaailM · '

This example verazieohaulloht the production of "High modulus filaments made from poly-C2,6-diohlor-p-phenylene» rephthalamiä),

* 233 «· BAD ORIQWAL

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In a ILtr, resin container with a luftgstriebenen Rtihrar basket type, a nitrogen inlet and a 3 roc4: enrohr is provided to be 17.70 g (IO O ₃ mole) of 2,6-Dlehlor-p-phenylendiasain and 410 ml N , M-Biinethylacetamld given. The solution is cooled with an ice bath compositions for 15 minutes, after which 20.30 g (O ^ .10 mole) of powdered terephthaloyl chloride ssugegefosn ₉ wäb "" rend the solution is stirred rapidly, "The ice bath is siacli 20 minutes and by a Replaced water bath kept at room temperature. The viscosity of the solution increases gradually. After standing for 3 days, the reaction mixture forms a clear, very viscous solution. A sample of the polymer is precipitated from the reaction mixture by combining a rope with water. The solid polymer is more Maia with wat =?, And washed once with acetone, after which it Ixa gatrooknet a vacuum oven Wi ^ t ¹³ Ij _n J ₁ ^β 3 "77 <" 7 »3 g (0.10 Hol) lithium carbonate are? added with stirring to the clear reaction mixture. A stirrable gel is formed. The polymer is precipitated by combining the reaction mixture with water. OaB :? olymorisate is repeatedly washed with water and then with acetone dried in a vacuum fan, \ _inh a 3.84.

A SpinrtQBsae is prepared by mixing 23.9 g of the polyamide prepared above and 75 ml konaentrierte (100.2 ^ ig: e)? .N a sulfuric acid unMmiteltsii Karabehälter% are ereinigt geaHihrt USID the mixture with a stirrer of- shear Soheibentyi) until a uniform, pale pink mass is formed, the RÜliropalesaenz aeigt. This Masae depolarizes linearly polarized light when observing awißoheii ^ eicreuaten polarizers. The mass is centrifuged and then using an a

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oil gear! ; βη piston through a spinneret with 20 holes

rdt jöweiL · 0.076 mm in diameter. esitrudiert is a held at 4 ⁰ C WaseöiMsd. The threads are not wound up with the windshield tob 1.98 m / Miru \ wA iibgr washed in running distilled water. After Sroclc-: ': - 92 ?. in Lu;? ·; At room temperature the pods have the following properties: '- ihaft'. 3? / E / i € i / dea = 8.73 / 5.6 _{/ 241/3 e} 16, Orientieximgsv / isiko '. = 31 °, peeling resistance = s 5 _$ 51 loa / sec "

Ei ^ prob-5 G-srnes vrird wänaebehandelt 'by being guided with an insertion ihrragsgeschwlndigkeit V03A 7 _S 7 m / min through a 454- to ⁰ O ^ IRMT tes Eoiir (device .4). ,, wherein the fern is stretched to 1.05 times the length of the pipe. The threads have the following traction properties ι Τ / ϊ / Mi / den »14» δ / 3.5 / 490 / 2.65 _y angle of orientation = 15 °, the threads have high crystal! » nity mad lie sound resistance is 7 ₅ 27

vorlie send example illustrates the preparation mden nit high modulus avs poly (p-phenylene-2 _t 5 ° * Di.-chlortereplthalamld).

One Lb'sHWg of 17 _e 28 g (0.162 mol) of p-fbenylenediaioin in 120 ml of He: diethylphoaplioreaiid and 240 ml of .I-methylpyrrolidone-2 is produced under mechanical stirring in a 1 liter resin container 43 ₂ 52 g (0.162 mol) 2 _f 5 ^ dicholoterephthaloyl chloride are added, cooling with a water bath.The contents of the container quickly become extremely viscous and the polymer falls in about 1 minute A spatula yielding a wet powder which is allowed to stand over NaeM. After agitation of the powder

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. *. ,, -.-- AOU -: Afe 009836/2187

Q-1031-B

! ISIT water in a blender and isolating the sick resulting product, washing and drying in a Yakuumofan at 7O ⁰ C. 49.5 g of poly - "(p-phenylene" -2.5 "* ₁ diuhlorterephmit a ¹ L _n J ^β · 1 »59 received.

A Spimuuasse ird prepared v / by 3 * 5 g of the polyamide prepared above with 46.5 grams of concentrated (99 s 5 $ strength) are combined sulfuric acid _f wherein a Plügelrühr is used r & MX® mixing. This mass is O erxtrudisrt through a spinneret having 60 holes, each with ₅ 05 mm diameter into a water bath maintained at 8 ⁰ C ". The resulting threads are wound up at a speed of 7j6 m / min and washed on the bobbin overnight in cold running water -eMsn EigenBchaf-i: en: ΐ / E / Mi / den β 2.40 / 24.4 / 85.3 / 1 _P 6 _O Bie Ma; a have gerix.ge crystallinity and traces of orientation ■. is heat-treated ₉ by applying a

6 m / min "heated by a avf 305 ⁰ O iiohr (device Λ) where the yarn during the Durchleitena through the pipe to the multiple Is3- = '* is extended is directed constantly & eit * 7 *,. The yarn will be strangled like this, passed at the same speed through the same bore (which is heated to 502 ⁰ O). 'T / B / Mi / den "7.36 / 2 ^ 1/386 / 0.95, the" is 24 ° iisf the filaments have / low crystallinity

B e i sp J. β 1 83

In the present example, Hen Prosentsat looks at one of the following: Angled crystallines which are half as large as the orientation: eunga angle of the Eadea axis _t at £ * p @ jsieulen Poljnnerieatpr Jben from some of the foregoing

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009836/2187

BAD OBtGlNAt

1 Q-1031-R 1

Examples in the state as extruded. The intactness curve of this diffraction pattern of the thread is not necessarily a Gaussian-like curve for each of these samples *

The Orientierungßwinkel of each of the following samples in the state as extruded is bestirnt using the above besohriebeaen method 1 and the Prosentsats of crystallites "is precisely the case in the above described manner · Hex determined optionally present difference in the specified orientation angle value in comparison with the foregoing in ». According to Method 2 1st zurücksufuhren examples specified values on the larger degree of accuracy of the method 1 · The values for the Orientie "approximate angle and Krlstallitprozentsata are shown in the following Table XVII" How seigt the table in each Pail, are more than about 50 fc "of Crystallites aligned in half of the angle of orientation.

Table XVII

assssassiisssssssasss

example Orientation angle 29 ° ■% Qh aligned - 30 ° Crietallites 2 33 ° 65 % 6th 24 ° 70 % 14th 24 ° 68? 6 16 25 ° 64 1 ° 18th 28 ° $ 65 20th 20 ° 66 # 23B 24 ° $ 71> 40 24 ° $ 56> 46 25 ° 66 ^ 76 68 # 81 76 #

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SAD OHiGINAL

009836/2187

Claims (1)

Claims (I) Polymerj.sat, which consists essentially of 'at least one type of carbocyclic, aromatic homo- or Kieeh = polyaiaic. with chain-extending bonds of each aromatic nucleus, which are coaxial or parallel imii in opposite directions, and (II) at least consists of a liquid medium that is under (A) Amides and ureas from the following group Ν, ϊ-Dimethylacetamid * N, N-Bimethylpropionamid, N, F-Dimethylbutyramid, N, N-Dimethylisobutyrajnid, Ν, ϊί-Dimethylmethoxyaoetamid, HpH-Diethylacistamiä, N-Kethylpyrrolidon-2, N-Kethylpyrrolidon-2, N-Methylplperidon-2, N-methyl, N-lthylpyrrolidon-2, N-acetyl "· pyi / rolidin, N-Aoetylpiperidln, H, N ^r -Dimethyläthylen" urea, N ^ '- Dimethylpropylenharnstof.fe Hexaaiethylphosphoramid and NtNtN'fN ' (B) concentrated sulfuric acid, (C) hydrofluoric acid and (D) chlorine, fluorine or methanesulfonic acids is selected, the polymer in one concentration is above the critical concentration point 2. & Mae e according to claim 1 "characterized in that the liquid medium is let an amide, a urea or a mixture thereof, and a calcium and under Lithiumohlorld SAD ORIGINAL QQ2833 / 2H7 133 Contains ohlorid selected sals. 3 «. Mass according to claim I ₅ thereby. known _? that the liquid medium can contain concentrated sulfuric acid with a concentration above about 98 (rew _e - ^ _r the free SO ,, is _β 4 «. Composition according to Claim l _s, characterized in that the concentration of the polymer is at least approximately
5 ßew. »^ The hatred is» 5- mass according to claim 1 "characterized in that the polymer in the liquid medium essentially
forms rod-like aggregates * 6. Fa & an baw. Paser made of polymer "that essentially consists of at least one 9? Yp of carbocyclic®, aromatic HöHio- or mixed polyamide with chain-shifting lines" = fertilize every aromatic nucleus that is coaxial or pa-. parallel and oppositely directed, "consists of the orientation of the thread fosv /" the paser through a
OrientieruBgswinlcel is characterized under about 45 ° and the Padszi, respectively. the pass he one ». Start module of min- " at least about 300 g / den. 7. Fadsm BSW _o fiber according to claim 6, gekennseichnet by a strength τοη at least about 5 g / den. 8. Pedsn or fiber according to claim 7 »characterized in that the Orientierimg by a speed of sound of at least about 4.0 km / sec. characterized
is. ' 9 “Paöan baw. Fiber according to claim 8, characterized in that that the Orientierucgöv / inkel less than about 009836/2187 SAD Q-1031-H 55 ° and the speed of sound at least about 6.0 km / Se & o ". 10, "thread" or "fiber according to claim .9" ₄ characterized in that the Sehallgeschwindigkelt is at least about 7 «0 km / Selu, 11. - load bsw «Easer according to claim 9» thereby gekena « Seichsset that the orientation! mgswinkel v / saiger than about 25 °. 12. Fsden bssw «fiber aacih claim 9, characterized in that that the Anfaagsmociul at least about 400 g / den amounts to. 15. Is the bsv / _e fiber in the "state" as extruded from polymer which consists essentially of at least one type of carbocyclic! aromatic Hoiac- or Hißchpolyamid with Kettexverläiigernden Binsiiaigsn of each aromatic nucleus, the coaxial or parallel and oppositely directed bind, ordered, if "the orientation of the thread or" the laser is characterized by an orientation angle of about 45 ° and the thread baw. the fiber has a strength wedge of at least about 5 g / den " 14. I'aden bjsw. Fiber η i claim 13, characterized by eißi- Dehaimg of at least etv / a 5 S ^ c 15. I'aden bsw c fiber according to claim 14 V characterized .by "a" - n Aiifsngemcdul voi at least * about -200-g / den " 16 .. l'aden'bawc fiber "characterized overall" to "Anspruoh 15p * kennKeifjhriefe that the orientation • dizzy by a S'challge-. Eit lon ,? of at least about 4.0 / sec charakterisiert- 'Urü - 140 ~ 09836/2117 _BAD Q-1051-H Mi 1939694 17. Heat-treated pad or heat-treated fiber from polymer, which essentially consists of at least one lyp of earbocyolehem asomatic homo- or mixed polyamide with lengthening bonds of each aromatic Core, which are coaxial or parallel and oppositely directed, consists of the thread or the fiber an orientation angle of about 45 ° »a speed of sound of at least about 4.0 km / sec Initial modulus of at least about 300 g / den rad a strength of at least about 5 g / den. 18. thread or fiber according to claim 17, characterized by an orientation angle of less than 25 °, a speed of sound of at least about 7.0 km / Selc. and one Initial modulus of at least about 400 g / den. 19 · fibers or fibers made of polymer, which consists essentially of at least one type of carbocyclic © aromatic homopolyamide or mixed polyamide with random distribution with chain-extending bonds of each aromatic Kar.i, which are coaxial or parallel and opposite, where the orientation of the thread or the fiber is characterized by an orientation angle of less than about 45 ° and the thread up to and including the fiber has an initial modulus of at least about 200 g / den. 20 Fad to or fiber naolr claim 19, characterized _s ά% & the orientation duroh a Schallgeaohwin ~ digkelt mindeetens of about 4.0 Kia / sec. is characterized and def the strength is approximately 5 g / den - - 241 - - SAP 009836/2117 ill Lee rse i te