DE1745254A1 - Polyamide threads, fibers, films and fibrids - Google Patents

Description

■ B.I, DU PONT DE HEMOtJRS AND COMPANY? 10th and Market Streets, Wilmington, Delaware 19 898. V.St.A.

Polyamide threads, fibers, films and fibrids

The present invention relates to fully aromatic polyamide threads, fibers, films, fibrids and laminates which are characterized in that they have an orientation angle of up to 35 ¹ and a modulus of elasticity of more than 200 g / denier. The aromatic polyamide consists of
80 to 100 MoI ^ of repeating units of the formula

The remaining 0 to 20 mole $ can be repeating units the general formula

N - Z -

New »Un'G.ic:;:

OO 9 0 5 2/202 2

..2 Mr. 1 Sau 3 des AndaruflpsM * · % 4, ί> ! ^Γ -

Q-928-R

8ein _f in the Z is an m-phenylene radical or a substituted m- or p-phenylene radical which has one or more (identical or different) substituents, the halogen atoms, lower alkyl, lower alkoxy, iaopropenyl, methylthio, ethylthio , Cyano, nitro, acetyl, carbomethoxy, carboethoxy, acetamido, dimethylamino, diethylamino, ethylsulfonyl, dimethylearbaiaoyl, diethylcarbamoyl, methylsulfonyl, dimethylsulfamoylri or 1-fluorosulfamoyl or a remainder of the general formula

means which can be substituted by one or more halogen atoms, lower alkyl or lower alkoxy radicals »at in which the terminal bonds are in the 3 »4 or 5 position, and in which X, denotes a single bond or

the meaning CH ₃ Has, -σ-,
ι -σ-,
Il -OH ₂ -, CH, O J 0 or -0-0-

Il

Il

H 0

f H

-H-C-,

H 0

J H

-N-S-

It

or they can be made up of equal parts of up to 10 each of repeating units of the general formula

and the general formula

009852/2022

Q-928-R %

OO
η μ

Y-Rι-γ »

besteben, in which Q and Q ^{1 are} hydrogen atoms, methyl or phenyl radicals, R is a divalent organic radical or a single bond and R 'is a divalent organic radical, while Y and Y ^{1 mean}

Il 11

-C- or -ει «

have, and the polyamide if it is essentially a homopolyaraid is.t, an inherent one determined in sulfuric acid at 30 ° C Viscosity of at least 0.7, a ratio of the X-ray diffraction maxima to 0.86 and has the property of not leaving any sediment if 0.1 g of the polyamide with 10 ml. a 6.9% strength by weight solution of lithium chloride in tetramethylurea Mechanically stirred for 24 hours and left to stand at room temperature for 24 hours, and the polyamide if it is a mixed polyamide, one at 30 ° C in sulfuric acid has a certain inherent viscosity of at least 0.5 »

The for the production of the threads, fibers, Foils, fibrids or laminates can leave the polymers used can be made as follows.

The substantially homopolymeric poly (p-benzamide) can by solution polymerization of p-aminobenzoyl halide salts the general formula

II

009852/20 22

Q-928-R ,,

can be produced at a low temperature. In the above formula, X ₁ denotes an arylsulfonate, alkylsulfonate, acidic sulfate or halogen radical, preferably a bromine or chlorine ion, and X _{2 is} a halogen radical, preferably bromine or chlorine.

The preferred monomer is p-aminobenzoyl chloride hydrochloride. Other monomers suitable for this purpose are p-Amlnobenzoylbromid-hydrobroraid, p-aainobenzoyl chloride hydrobromide, p-aminobenzoyl chloride methanesulfonate, p-aminobenzoyl chloride benzene sulfonate, p-aminobenzoyl chloride toluenesulfonate, p-aminobenzoyl bromide ethanesulfonate and p-aminobenzoyl chloride sulfate. The preferred p-aminobenzoyl chloride hydrochloride can be in high yield from an ethereal solution of p-thionylaminobenzoylchloril according to the general method of Graf and Langer, Journal for practical chemistry, Volume 148 (1937), Page 161, divide under anhydrous conditions. That Drying and storage of this monomer in an anhydrous state are preferably carried out at room temperature, because the connection at. tends to polymerize at higher temperatures.

Those mixed polyamides that except for recurring units the formula

still up to 20 MoI ^ recurring units of the general formula

009852/2022

Q-.92.8-fi

contain, in which Z has the above meanings, can be obtained by copolymerizing a salt of the general formula II with a minor proportion of at least one hydrohalide salt of the general formula

XH ₃ Nt-ZCX ₂
obtained, wherein X ₁ , X ₂ and Z have the above meanings.

Monomers of the general formula III which are preferred for the preparation of the mixed polyamides are, for example, m-aminobenzoyl chloride hydrochloride, m-aminobenzoyl bromide hydrobromide, 2-methyl-3-aminobenzoyl chloride hydrochloride, p-aminophenyl-p- (chlorocarbonyl) -phynylsulfone -hydrochloride, p-aminophenyl-p- (chlorocarbonyl-phenyl ether hydrochloride, p-amino-p- (chlorocarbonyl) -biphenyl hydrochloride, m-amino-p- (chlorocarbonyl) -berizophenone hydrochloride, p- (chlorocarbonyl) - phenyl p (amino) benzoate hydrochloride,
3-fluoro-4-aminobenzoylchloride-hydrochloride,

2, o-dichloro - ^ - aminobenzoyl chloride hydrochloride, 3-bromo-4 ~ aminobenzoyl chloride hydrochloride, 2,6-dibromo ~ 4-aminobenzoyl chloride hydrochloride, 3-J ■ od-4-aminobenzo; 5rlchloride hydrochloride, 2- Fluorine-4-aminobenzoylohlorid-hydΓochlOΓid _f 2,3-dimethyl-4-amiaobenzoylchloride hydrochloride, 2, ö-Biraethyl ^ -amiaobenzoylchlorid-hydrochloride, 3-Äthyl-4-aminobeni5oylchlorid-hydrochloride, 2-ritro-4-aminoben ^ oylchlorid -hydroohlorid, 3-Ä * thoxy-4-arainofceazoylchlorid-hydroohlorid _f S-lthoxy-S-nitro - ^ - aminobenzoylchlorid-hydrochlorid, 2-pΓopoxy-4-aminob8nzoylohlorid-hydΓOohlor ^ ä,

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2-Iaobutoxy-4-aminoben2oylchlorid-bydroctalorid, * 2-8ek-butoxy-4-aminobenzoyl chloride hydrochloride, 3 ~ I ^ opoxy-4-arainobenzoylcblorid-bydrocblorid, 3-isopropoxyM-arainobenzoylcblorid-hydrochloride, 3-butoxy ~ 4-aminobenzoyleblorld-bydrocblorid, 2-MetbyltbioM-aminobenzoylcblorid-bydrocblorid, 2-Ätbylthio-4-aminobenzoylcblorid-bydrooblorid, 2,5-dimethyl-4-aminobenzoylchloride-hydrochloride, 3 »5 ~ Diinetbyl-4-aminobenzoylchloride-bydrocblorid, 2-ethylsulfonyl-4-aminobenzoyl chloride hydrochloride,

2-Dimθthylaulfamoyl-4-aminobβnzoylchloΓid-hydΓochloΓid, 2,3 »5» e-Tetramethyl ^ -aminobenzoylcblorid-hydrochloride _t

4-methyl-3-aminobenzoylcbloΓid-hydΓocbloΓid, 4-ethyl-3-alninobβnzoylcblOΓid-hydrocblorid, 4-IβopΓopyl-3-aminobβnzoylcbloΓid «byärocblorid, 4-I8opropβnyl-3-aininobenzoylohlorid-bydrocbloΓid, 4-tert-butyl-3-aminobenzoylchloride-bydrocblorid, 2,6-dimethyl-3-aminobenaoylcblorid-b.hydrochloride, 2-chloro-3-aminobenzoylcb, loride hydrochloride, 4-ChloΓ-3-aminobβnBoylohlorid-hydrocblorid, 5-bromo-3-aminobenzoylchloride-bydrocb.lorid, 2-iodine-3-aminobβnι! Oylcb.loΓid-bydrochloΓid, 2,5-Dlotalor-3 ~ aminobenzoyletalorid-hydrochloride, 4,6-SiobJL or-3 ~ aminobenzoyl chloride ~ bydrocbloride, 5-liitro-3-aminobtllaoylchloΓid-hydΓocbloΓid _f 4-Bimetbylaaino-> 3- ^> aminobenzoylcblorid-bydrocblorid _t 2-Butoxy-3-aminQbenzoylchlorid-hydrochloride, 2-18opropoxy-3-aminoben ^ oylobXorid-> hydrooblorid _f 4-PΓopoxy-3-aminobnzoylcblorid-bydroohloΓid, 2-acetyl-3-aminobenzoylchloride hydrochloride, 4-Httbyltblo ~ 3 ~ amiaobenaoyloblorid * bydrooblorid, 4-Ethylthio-3-arainobeTizoylcblorid-hydrochlori (3.

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Mixed polyamides of high molecular weight, which su at least 80 M0I96 from repeating units of the formula

and in equal parts up to 10 mol # of recurring Units of the general formula

- AA and the general formula

BB

consist, where R, R * Q, Q ^! , Y and Y * have the above meanings can be prepared by copolymerization of a salt of the general formula II with smaller, stoichiometrically isobically equivalent amounts of the corresponding intermediates for the units AA and BB. Suitable intermediate products for the AA units are aromatic diamines and tetraamines, such as p-phenylenediamine, m-phenylenediamine, benssidine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ketone, 4 4 '~ diaminodiphenyl sulfide, 4,4'- Diamiiaodiphenylulfon, 4,4'-Diaminodiphenylather, 4,4'-Diaminodiphenyl-1,2-Uthane, 4,4'-Diarainodipheny1-2,2-Propane, 4-Methyl-m-Phenylenediamine, 2,6-Diehlor-p -phenylenediamine, 3,3'-dichlorobenzidine, 4- (4-aminobenzamidο) -aniline, 3 »3 ⁽ -Biaainobenzidin, 1,2,4,5-tetraeminobenzene and 3t3'-I> ihydroxybenzidin, dibydraside, like oxalyl- ,

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Q-928-E

Isophthalpyl, terephthaloyl, bibenzoyl, adipic acid, carbonyl, 2,5-pyridinedicarboxylic acid dihydrazide, and hydrazines, such as hydrazine, methylhydrazine, phenylhyärazine, !!, N'-diaminopiperazine, N, N'-diaTnino-trans- 2,5-dimethylpiperazine, NjN'-diamino-4 »4'-dipiperidylhydrazino Suitable intermediates for the BB units are! ^ Carboxylic acid halides and disulfonic acid chlorides, such as adipic acid chloride, sebacic acid chloride, cyclohexane-1,4-dicarboxylic acid chloride, 1,4-pherylenediacetyl chloride, Cyelobutane-1,3-dicarboxylic acid chloride, terephthalic acid chloride, terephthalic acid bromide, isophthalic acid chloride, 2,5-diolorterephthalic acid chloride, 5-chloroisophthalic acid chloride, 5-tert. » Buty / isophthalic acid chloride, bibenzoyl chloride, diphenic acid chloride, sulfonyldibenzoyl chloride, kaphthalene-2,6-dicarboxylic acid chloride, naphthalene-1-dicarboxylic acid chloride, pyridine-2,6-dicarboxylic acid chloride, benzene disulphonic acid chloride, p-benzenedisulphonyl chloride, naphthalene-1,5-disulphonic acid chloride, naphthalene disulphonic acid chloride -4,4'-disulfonic acid chloride, Qxy-bis- (4-benzoisulfonic acid chloride), methylene-bis (4-benzenesulfonic acid chloride), N, N'-carbonyldiaulfallyl chloride, 4,5-diehlobenzene- »1,3-disulfonic acid chloride, hexane 1,6-disulphonic acid chloride, 4 »chlorocarbonylbenzenesulphonic acid chloride, bisanhydrides, such as pyromellitic dianhydride, cyolobutanetetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, methylene-bis (4-phthalic anhydride, such as hexamethylene-1,4-di-anhydride), and isocyanates ~ diisoeyanate, phenylene-1,3-diisocyanate, 4-methylphenylene-1,3-diisocyanate, biphenylene-4,4-diisocyanate, bis- (4-isocyanatophenyl) -methane _t bis- (4-isocyanatophenyl) ~ 8ulfone, 3 »3'-dimethylbiphenylene- _! 4 _f 4 ⁱ -diisocyanate, 3,3 ⁱ -dichlorobiphenylene-4t4'-diisocyanate, cyclohexylene-1,4-diisocyanate, 1,2-bis- (4-isocyanatophenyl) -ethane, 4-isocyanatobenzoyl chloride and 4-isooyanatobenzenesulfonic acid chloride.

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In the case of solution polymerization at low temperatures, ie below 60 ° C. and preferably from 0 to 20 ° C., the solvent used is preferably tetramethylbarnstoff, hexamethylphosphosamide, Ν, Ν-dimethylacetamide or N-methylpyrrolidone. Other suitable solvents for polymerization are N-Methylplperidon, N, N * Mmethyläthylenharnetoff, NtNtHSK'-Tetramethylmalonsäureamid, N-methyl caprolactam, N-Aoeifylpyrrolidin, Ν, Ν-diethylacetamide, N-Äthy! Pyrrolidone, N, N-DimethyIpropionsäureamid, N _f N «I) imethylbutyramide and N, H-dimethylisobutyramide.

Your choice of solvent for the preparation of the mixed polyamides may depend in part on the particular one being considered Combination of AA units and BB units depend on. if the homopolymeric poly- (p-benzamide) and the polymer from the respondents »for the AA units and the BB ^ units can be prepared separately in the solvent in question, then this solvent is generally also suitable for copolymerization.

The polymerization reactions described above can be carried out by mixing the monomer or monomers in dissolves the solvent and vigorously stirs the externally cooled solution until it becomes very viscous. Bas polyamide can then isolated by adding water. But you can also choose the monomer or monomers initially in a low- » Slurry a generous amount of an inert organic liquid before adding the solvent. After a modification of this The first-mentioned method can be used to mix the solvent in the frozen state with the monomer or monomers. Ban one reads thaw the solvent and stir the resulting Mud until a gel-like mass has formed. To that

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0098 52/20 22

Q-928-R

Limiting the molecular weight of the polyamide can mean these A chain terminator can be added to reactions. Polymerization is used to achieve the highest molecular weights carried out under strictly anhydrous conditions. The reaction vessel and the auxiliary equipment as well as the solvents and respondents are carefully examined prior to use dried, and the reaction vessel is continuously flushed with a stream of dry inert gas, such as nitrogen, during the polymerization.

Such a polymerization can be carried out by first adding a certain amount of an anhydrous to the gas-flushed polymerization device with stirring organic liquid, such as tetrahydrofuran, bioxane, benzene or acetonitrile, to a certain amount of the desired Adds monomers. This liquid also contains the calculated amount of a chain terminator such as benzoyl chloride, if used. Bas so obtained Mixture is then stirred at increased speed and quickly with a large volume of the anhydrous solvent, such as tetramethylurea, Η, Η-bimethylaeetamide, Hexamethylphosphoramide or SMSethylpyrrolidone, added. Bie externally cooled solution is constantly stirred until its Viscosity has increased significantly. The solution can then be left to stand overnight or longer at room temperature permit. If the polyamide is to be isolated in bulk, will the polymerization mixture is mixed with water in a mixer and then converted into a fine powder. The powdery polyamide is after washing with water and with alcohol dried overnight in a vacuum oven at 80 to 90 ° C and then stored or brought into solution for further processing.

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As. mentioned above, the polymerization can be carried out in the presence of chain terminators. By having the chain terminator controlling the molecular weight of the. support the resulting polyamide, they facilitate the subsequent dissolution of the polyamide and increase the resistance of the polyamide spinning liquid for use in the coupled polymerization and spinning process. Suitable chain terminators are monofunctional compounds that react with the terminal acid chloride groups of the polyamides, such as ammonia, monoamines (e.g. methylamine, dimethylamine, ethylamine, butylamine, dibutylarain, cyclohexylamine _s aniline, etc.), compounds that contain a single amide-forming group, such as Ν, Η-Diethylethylenediamine, compounds containing hydroxyl groups, such as methyl alcohol, ethyl alcohol, Ieopropy! Alcohol, phenol, water, etc., and monofunctional compounds that react with the terminal amino groups of the polyamides, such as other acid chlorides (e.g. acetyl chloride), acid anhydrides (e.g. acetic anhydride, phthalic anhydride etc.) and isocyanates (e.g. phenyl isocyanate, m-toluyl isocyanate, ethyl isoeyanate, etc.). Suitable bifunctional chain terminators are, for example, the above-described intermediates used to form the AA units and the BB units. These can also serve as chain terminators in the preparation of the mixed polyamides if the reactants forming the AA units and the BB units are used in small excess, or a small amount of a suitable bifunctional compound can be added to the reaction mixture during preparation of the homopolyamide of the formula I or in the preparation of the above-described mixed polyamides from A units and B units. Suitable bifunctional chain terminators are, for example, terephthalic acid chloride, isophthalic acid chloride, sebacic acid chloride, biphenyl-4,4 ^c -disulfone-

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0 0 9852/2022

Q-928-R

te

acid chloride, pyromellitic dianhydride, p-phenylene diisocyanate, Benzidindiisoeyanat, Bi9 «(4 ~ iaoöyanatophenyl) - methane, p-phenylenediamine ,, m-pherylenediamine, benzidine, bis- (4 °> amino " phenyl) ether, NyN'-diaminopiperazine, adipic acid dihydrazide, Terephthalic acid dihydrazide and xsophthalic acid hydrazide. As well as the monofunctional as well as the bifunctional chain terminators are particularly effective and evenly distributed, if you have them at the beginning of the polymerization or before the addition

^ of any acid neutralizing agent (e.g. lithium

™ hydroxyd) added.

The spinning liquids of these polyamides can be extruded, cast or, if necessary, converted into fibrids. The most resistant spinning liquids, which are suitable for spinning the homopolyamide given above into threads or for casting into films, contain 4 to 30% by weight of 6, preferably 10 to 15% by weight of polyamide, 3 to 22% by weight of 96% Litfaium aurid and consist <aum reads of Tetrahyron! Urea. For each recurring polyamide unit, at least 0.5 mol of LiO1 should be present. The presence of LiCl is not necessary, however, if the spinning liquid is used within a not too long time after its preparation. Thus, in order ZX ensure that the spinning liquid is in a suitable condition for the dry or wet spinning, the polyamide is prepared either in tetramethylurea, or in a mixture of Tebramethylharnstoff and Lithiumehlorid, optionally followed by the acid that has formed as a by-product, completely or partially neutralized and the product is spun directly (coupled process). You do not need to neutralize the acid formed as a by-product if it does not have a corrosive effect on the spinning system. Another method is used

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first the polyamide is made and isolated and then how described below, with tramethyl urea and lithium » ehlorid combined.

A more special method of making a spinning fluid is the following:

A mixture of the homopolyamide, setramethylurea (TMU) and lithium chloride in the proportions given above is placed in a vessel equipped with a stirrer. With this one. The homopolyamide can be crrsetJBt with a mixed polyamide ₈ if the solubility (determined according to the sedimentation test) allows this. If the mixed polyamide is insoluble in this medium, other solvents are used. The mixture is heated to 130 to 150 ° C for at least 1 hour while stirring. While the mixture is at this temperature with stirring, it generally turns into an extremely viscous, gelatinous mass which is completely unsuitable for spinning. This material is then cooled to 0 ° S or below in a bath of solid sole dioxide or other coolant for about 1 hour. This alternating heating and cooling may have to be repeated four or more times in order to obtain a spinnable solution.

The amount of heating and cooling required to obtain a spinning liquid with the fluidity required for smooth spinning by this method varies with the inherent viscosity, the degree of crystallinity and the size of the polyamide as well as the type of agitation. In the preparation of these solutions must be carefully gaaohtet that no local overheating of the solution takes place and see no "dry ¹¹ points or

009852/20 2 2

SAD

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Form gel spots. Such. Parts of the polyamide go namely not easily back in solution.

When the solution polymerization at low temperature in Tetramethylurea with p-iminobenzoyl chloride hydrochloride is carried out as a monomer »achieves what is formed Polyamide usually has a useful molecular weight after allowing about 15 minutes to 1 hour or long to polymerize.

M ger has allowed it to progress, and the mixture obtained in this way is suitable as a spinning solution for spinning or for casting. gel formation can begin within a reaction time of 0.5 to 2 hours, which depends at least in part on the degree of polymerization achieved. By adding the chain terminators described above, the stability of such spinning solutions can be extended by many days. If the polymerization is long in tetramethylurea than about 0.5 hours continues, 'can mn a directly spinnable solution obtained by fjine to the Löaung in tetramethylurea before polymerization certain amount of lithium chloride is added, or by au which a half hour old Reaktionsgemisoh a certain henge (up to 2 equivalents of lithium each

} Moles of monomer used if an acid chloride hydrochloride is used) of an inorganic salt or salt former, such as lithium hydroxide, lithium acetate, lithium hydroxide, Lithium carbonate or lithium oxide, useful. Furthermore, one can Subsequently heat the contents of the Haaktionsgafässes to the To facilitate the formation or persistence of a spinnable solution. The above-mentioned alkaline substances react with the hydrogen chloride which forms during the polymerization with the formation of lithium chloride. Preferred catfish used one does not use bases such as lithium hydroxide or lithium oxide larger amounts than are needed to neutralize the chlorine water

-U-

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BATH ORIGINAL

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Substance or other acids, oils during the implementation form, are required. The solutions described above in tetramethyl urea are particularly suitable for spinning Spinnerets made of platinum sold and solution containers, filters, lines and the like made, for example, of corrosion-resistant stainless steel. Also with polytetrafluoroethylene tibereogenic metals, equipment clad with glass as well as acid, Heat »and solvent resistant plastic parts can be used.

Molded products and their manufacture

The spinning solutions described above (prepared in stages or by the coupled process) can easily be converted into Transfer pollen, threads, fibrids and coatings. Your wet extrusion according to the usual »methods are obtained from these Polyamides tough, clear, flexible films. Tie spinning solutions can also be used as a liquid coating agent, which can be applied to a wide variety of webs, paper, wires, wire nets, Fibers, fabrics, foams, solid or microporous objects, etc. can be applied as a carrier. These carriers can made of glass, ceramic materials, bricks, concrete, metal (e.g. copper, steel, aluminum, brass) or polymer materials (e.g. wood and other cellulose materials, wool, polyamides, Polyesters, polyacrylic acid ^ tril, polyolefins, polyvinyl » halogen, hardened epoxy resins, hardened aldehyde-urea resins, etc.).

The production of the polyamide threads can be carried out according to known methods Wet or dry spinning processes are carried out. Hat spinning is a spinning solution of the polyamide in tetramethylurea (or another suitable solvent) whose temperature

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door can be in the range from room temperature to about 150 ° C, spun in a precipitation bath, e.g. a water bath kept at 65 to 90 ° C. Other suitable precipitants are ethylene glycol, Glycerine, mixtures of tetramethylhine and water, Mixtures of alcohol and water and aqueous salt solutions. These are preferably to 40 to 45 ° G or higher temperatures held. The formation of good fibers (i.e. those with improved tensile strength properties) is promoted by keeping the threads taut in the precipitation bath. This can E.g. by placing the threads in the felling bath around guiding organs running around.

Dry spinning can be carried out by removing the threads from a polyamide ~ tetramethylurea ~ LiCl- »spinning solution which is preferably kept at 5Θ to 150 ° 0, in a heated Column squeezes, whereby the tetramethylurea evaporates. Other solvents are required for some mixed polyamides.

After production, the threads are passed over a finish application roller and wound onto spool cores at high speeds. Then they can easily be unwound again. It helps to develop the most advantageous thread and yarn properties if the bobbins are treated in water or mixtures of water with water-miscible inert organic liquids (e.g. fetramethylurea, dimethylaeetsmid, acetone, ethyl alcohol, glycerine) in order to remove the remaining solvent and SVIz to wash out. Residual solvent and salt can also be washed out by continuously passing the yarn through aqueous baths, spraying the bobbins with water during the manufacture of the yarn, or by washing the yarn not being wound on

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Coils, but rather on strands. The yarn will be fine stronger by washing with small amounts of water.

The fibers according to the invention have a high strength and a very high modulus of elasticity, namely over 200 g / denier and often over 300 g / denier, as is required for many purposes for reinforced plastics. They are crystalline and have an orientation angle of less than about 35 °. As can be seen from the examples below, threads made from homopolymeric joly- (p-benzainide) and from certain malpolyamides "if si" have been produced and treated as described above in general have these unusual and surprising tensile properties without being drawn to have become. The freshly spun threads usually have a slight hollow roughness. The use of spinning-stretching factors (as defined below) of approximately 1 in sock spinning or occasionally also in horse spinning leads to spun fibers with an orientation angle of more than 35 ° and a module below 200 in these polyamides. In this case, the Fastür Heated for 2 to 5 seconds under nitrogen in a tensioned state to 400 ° C to give the orientation angle! to decrease and to increase the modulus.

They heat treatment of the spun threads under tension only a low level of diversification leads to a noticeable increase in strength and modulus. Heating is generally carried out above 330.degree. They have tensile strength properties these PHden can also be improved by that the undrawn threads are subjected to heat treatment in relaxed state tintervirfb. Suitable for these treatments Luftöftn, hot pens, üexsse Schiita ·, hot plates and liquid Heisbädiiv

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0 0 9852/2022 BAD ORIGINAL

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Some of the polyamide fibers develop advantageous properties, such as high modulus, high tensile strength, etc., only after stretching. In these cases stretching can be used be carried out according to methods known per se. The above-mentioned heat treatments make the fibers special suitable for reinforced laminates, in which the proportion of fibers can be up to 75 wt .- #, while the rest consists of an embedding compound made of plastic.

The chemical and thermal resistance of the according to the invention Processes made from poly (p-benzamide) filaments and yarns are excellent. The fibers keep theirs Tensile strength properties still after 1/2 hour heating in boiling 1 # aqueous hydrochloric acid or 1 # aqueous Caustic soda. The properties of the fibers remain practically unchanged if they are immersed in the for 1 hour at 60 ° C commercially available dry cleaning agents such as perchlorethylene or trichlorethylene. Keep for extended periods of time during or after heating in air at 300 ° G the fibers in excellent condition hate their strength properties at. If the fibers are removed from the open flame, they will go out by themselves.

The polyamide threads according to the invention show only a lot slow growth, even at higher temperatures.

Crystalline and highly oriented fibrids from these Polyamides can be obtained from the spinning solutions described above by precipitation under the action of shear according to the USA patent Manufacture 2 999 768. These fibrids can be pressed into paper

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ÖAD ORIGINAL 009852/2022

The polyamides can be used depending on the bet purpose before or after fiber production additives such as Dyes, fillers, ultraviolet stabilizers, Oxydati onsver retarders, etc., are added.

Mes Sunke n _ ,, and inspection method s

Orientation Angle The orientation angle of the fiber is determined by the general method described by Krimm and Tobolaky in "Textile Research Journal", Volume 21, 1951, pages 805-822-. Using .OuEot radiation, a laser foil with a thickness of 0.05 cm, a wide-angle X-ray diffraction diagram (iranamissicusiiagramm) of the fisary is recorded at a distance from sample to film of 5 cm and an exposure time of about 45 minutes . Measuring the arc length in "degrees" at the half-maximum intensity of the first equatorial diffraction spot, which is 2 Q = 20.3 °, and Ba bstracbtet This large as the Orientierungewinkel the sample. Intensity line a substantially Gaussian * 'see * curve and the determination is made at half maximum intensity, the physical meaning of the orientation angle given by this determination is that approximately 77 $> of the crystallites are oriented around the fiber axis within this angle.

The ratio of the diffraction maxima is a measure of the relative Intensity of the two main equatorial diffraction maxima. A suitable method for determining this ratio is to use a reflection method for registering the intensity line of the Hontgen diffraction diagram with a x-ray diffractometer Gefcyauch. 0.5 g of that of water and tetramethylurea freed polyamides are under a pressure of 219.7 kg / cm pressed in a sample age. Under use

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CuKoC radiation produces a line of intensity from 2 β = 6 ° to 2 Q u 40 ° at a scanning speed of 1 ° / Uin. (2 Q) and a curve sheet speed of 2.54 cm / min, and a time constant of 2. Here, 2 Q means the angle between the undiffracted ray and the diffracted ray. The full scale deflection of the recorder is set in such a way that the maximum intensity space is at least $ 50> the linear scale. In order to calculate the ratio of the diffraction maxima, a baseline is determined on the diffraction diagram by drawing a straight line between the curve points for 2 0 = 8 ° and 2 Q = 38 °. From the maxima in the area of IQ β 20.3 ° and 2 Q »23j4 °, perpendicular lines are drawn to the base line, and the height of the maxima is determined in curve sheet units above the base line. Then the ratio of the diffraction maxima is calculated according to the following equation:

Ratio of the diffraction maxima »A.

Herein, A AEIE height of the situated at approximately 2 Q = 20.3 ° peak to the base line in graph B units and the height of the ungsfähr located at 2 Q "23.4 ° to the peak in curve Grundlinia blade units.

A typical curve of this type is shown in the attached figure shown. A smooth curve line has been drawn here to compensate for the instrument noise, and the measurements will be taken made on this "

Sedioentation test: 0.10 g dry polyamide powder that, like is described in the examples below, isolated and comminuted to grain sizes below 3.84 mm, are in entered a dry test tube. For this purpose 10.0 ml

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«Η

a 6.9% strength by weight solution of lithium chloride in setraoethylurea added. Paa test tube comes with a stopper sealed and set in motion by putting it through for 24 hours at 21 ° C at a speed of 110 rpm the center-going diametrical axis is rotated. Then let the Raagensglas stand upright for another 24 hours. Mach this tent has no polyamide residue on the bottom of the glass discontinued.

Spin-stretch factor (S.E.F.):

ο _ -, speed of the yarn when winding (m / min.) la.κ.jr. The speed of the spinning solution through the spinneret

(m / min.)

Herein means

5l?; SSi _e ! ^ttr - ^oh ■ ■ {number apinnause; sausage area of a spinneret hole (ητ)

Inherent viscosity: The inherent viscosity (ΎΙ inh) is defined by the following equation

Owner

; 0

Here, ( ⁴ V) rei) denotes the relative viscosity and (G) a concentration of 0.5 g of polyamide in 100 ml of solution. The relative viscosity (^ rel) is determined by dividing the flow rate in the dilute solution of the polyamide by the flow rate of the pure solvent using a capillary cosimeter. The diluted solutions used for the determination of {yi rel) have the concentration given above (0)?

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Q-928-R

the Durohflusazeiten are determined at 30 ° C using concentrated sulfuric acid as solvent

The fiber properties »namely tensile strength (T), elongation at break (E) and Young's modulus (Hi) are given as T / E / Mi in the usual units. The titer is given in the. The decoction treatment of the fibers prior to the physical test consists in soaking the fibers for 30 minutes in a 0.1 # boiled aqueous sodium auryl sulfate solution, then rinsed, Dried 1 hour at 40 ° C and 16 hours at 21 ° C and a relative humidity of 65 # conditioned. The tensile strength properties are tested on yarn samples from 2.54 cm between the jaws of an Instron tester under such a load determined that a stretching rate of 10 # / Hln. at 21 ° C and 65 # relative Humidity is achieved.

Example I.

Production of the polyamide A 2 liter polymerisation kettle equipped with a stirrer, nitrogen inlet pipe and calcium chloride drying tube is heated with the Bunsen burner flame and flushed with nitrogen at the same time. The kettle is then closed and placed in a drying cabinet, ie a chamber kept under anhydrous conditions. 520 ml of hexaraethylphosphoramide, distilled over potassium hydride through a spinning band column under reduced pressure and stored over calcium chloride hydride, are filtered in an Erlenmeyer flask in the drying cabinet, which is then closed and cooled in iia. 75 ml of distilled tetrahydrofuran stored over sodium (water content less than $ 0.0001) are placed in the drying cabinet

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flask filtered, which is then sealed and chilled in ice will. 124.0 g (0.646 moles) of p 1-aminobenzoyl chloride hydrochloride are weighed out in the! drying cabinet and put into the polymer! - · transfer boiler. The kettle is removed from the drying cabinet removed, back to the Rühnaotor and the nitrogen line connected and chilled in an ice bath. Immediately before the start of the polymerization, the tetrahydrofuran 1.20 ml of distilled benzoyl chloride exposed.

The benzoyl chlorite solution in tetrahydrofuran is poured into p-aminobenzoyl chloride hydrochloride with moderate stirring, and the mixture is stirred for 1 minute. The stirring speed is then increased and the hexamethylphosphoramide is added rapidly. The solution is then stirred in an egg bath for 1 hour while cooling. With this treatment, the solution gradually turns into a gel. The cooling bath is removed and the polyamidines are left to stand at room temperature overnight. The solid gel is then stirred together with water in a mixer with a capacity of 3r785 1 at high speed, during which it turns into a fine, white powder. The polyamide is washed three times with water and once with alcohol by stirring in a mixer and filtering on a glass frit groove with a medium pore size. The polyamide is then dried in a vacuum oven at 80 to 90 ° C. overnight. The yield of poly (p-benzamide) is 92.3 % {\ inh * -T, 35). The polyamide has a ratio of the X-ray diffraction maxima of 0.78. The sedimentation test does not leave any solid residue at the bottom of the Rsagena glass.

Preparation of the spinning solution: A 700 ml capacity, with a bottle provided with a compressed air driven stirrer with 20 g of the polyamide obtained and 180 g of a 6.5 wt .-? 6-

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igen solution of lithium chloride in tetramethylurea charged. The mixture is heated to 150 ° C. in an oil bath while stirring. An externally viscous gelatinous mass is obtained. This mixture is cooled in solid carbon dioxide for 1 hour. The mixture is then heated to 150 ° C for 4 hours while stirring « Where one is a liquid, somewhat gelatinous, cloudy solution receives. The latter is cooled in solid carbon dioxide for 1 hour. The mixture is then heated to 130 ° C. for 4 hours with stirring heated, whereby an easily spinnable, cloudy dispersion solution arises, which is then cooled again for 1 hour in solid carbon dioxide. This smooth, cloudy dispersion solution flows slowly at room temperature and reflects when Stir light.

Production of fibers by dry spinning: The diapersion solution produced in this way is heated to 130 ° C. and at a rate of 0.9 ml / min, under a pressure of 4.921 kg / cm ² through a spinneret heated to 140 to 144 ° C. with 4 Holes each 0.01 cm in diameter and a capillary length of 0.02 em spun into a dry column, the walls of which are kept at 202 to 210 ° C. At the same time, the column is flushed at a rate of 0.142 xsr / Kln » with cocurrent dry nitrogen which enters the column at a temperature of 265 to 270 ° C. The emerging threads of 2 denier and oval cross-section are passed over a small guide roller, which carries a finishing solution, and wound onto a spool at a speed of 183 m / min. This corresponds to a spinning / stretching factor of 6.58. The threads do not stick together and are easy to unwind. By treating with individual batches of fresh water at 25 ° G for the purpose of removing the remaining LöoungEimitt «! and salt become the opaque

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original threads shiny white. The inherent viscosity of the polyamide in the filaments is 1.32. Pie auegelaugten with Wasaer, air-dried (21 ° C, 65 1 "relative humidity) yarns aind crystalline and have an orientation angle of 21 °. A 32-thread yarn made from these threads shows the following T / E / toi / aen value 6.02 / 2.17 / 431 / 58.5 in the uncooked state. After boiling, the threads show the following T / E / tei / den values: 4.75 / 1.38 / 429 / 1.72.

Heat treatment of the fibers The threads or the yarn are guided in a one-step operation in a tensioned state over a heating plate with a diameter of 7.62 cm, kept at 438 ° C., so that their length j increases by 0 to 1 $> . The dwell time over the heating plate is 5 seconds. The threads obtained in this way are crystalline and have an orientation angle of 13 °. After boiling, the threads show the following T / E / Mi / den values: 7.66 / 1.2 / 599 / 1.87.

Other "threads made according to the above process will be Heat treatments both in a relaxed and in a tense state subject. It is found here that the tensile strength properties of the threads are improved.

In Table 1 below, the improvements in the tensile strength properties of similar but not exactly the same catfish as described above, leached in water, air-dried, undrawn poly (p-benjsamld) fibers are compiled Fibers receive the specified heat treatments in both the relaxed and the tensioned state for periods of 1 hour each. Furthermore, comparative figures are given for a control sample * All values are based on boiled "threads and be determined after the threads on Raumbedingsngon (21 ⁰ Of 65 $ RH) have returned,

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BATH ORIGINAL

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This example explains the production of poly (p-benzamide) fibers according to the invention by a coupled method, in which the manufacture of the polyamide and the spinning to be carried out threads immediately one after the other. It should be noted that the fiber properties are due to the fact » treatment can be significantly improved.

In a dried with the flame ,, filled with dry nitrogen, equipped with stirrer,! Ürockenrohr and nitrogen inlet tube equipped and located in an ice water bath 250 mi-ßundkolben. 11.5 g of p-aminobenssoylechloride are mixed together with 61 ml of cold fetramethylurea. In this case, solution occurs immediately. The mixture is stirred at 0 ° C. for 2 hours and at 26 ° C. for 16 hours. The polyamide separates out as a swollen precipitate. Then 2.87 g of lithium hydroxide are added as an anhydrous powder and stirred in. It develops a considerable 'heat of neutralization, and shortly thereafter to form an almost clear _s swine "liquid solution of the polyamide containing lithium chloride and now to 120 ° C has the requisite for dry spinning consistency in 100th {The inherent viscosity of an isolated polyamide sample is 1.12 «The sample shows a ratio of the X-ray diffraction maxiiiia of 0 * 73 and also passes the sedimentation test»

This solution is subjected to the dry spinning process under the following conditions: spinneret attachment temperature 120 ° 0 {pressure on the solution 7 »031 kg / cm ² ; Spinneret with 3 holes of 0.01 approx diameter each j Spinneret temperature 135 to 140 ° Ci Column wall temperature 195 to 205 ° 0} Winding-up

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speed 183 m / min. The Spinn ~ stretching factor is 6.13. The yarn is leached out on bobbins several times, starting with fresh water at room temperature * until it is practically free of tetramethylurea and lithium chloride.

The T / E / Mi / den ^ value of the washed and boiled pasers are 7.16 / 2.16 / 486 / 2.80. The fibers are crystalline and have an orientation angle of 16 °.

After passing the washed, dry paser over a hot plate of 438 ° C is the T / E / Mi / den values of one decocted sample of threads 10.7 / 1.7 / 695 / 2.82. The threads are highly crystalline and have an orientation angle of 12 °.

At sjplel 3

This example illustrates the preparation of poly (p-bensatnide) fibrids according to the invention as well as the production of a Fiber sheet from the pibriia. Fibrids are in the United States patent 2 999 788.

20 ml of a 10 ^ igan spinning solution of poly (p-benzamide) (ratio of the X-ray diffraction maxiraa 0.80; yi inh «1.51) in a 6.5% solution of lithium chloride in tetraethylurea prepared according to Example 1 are according to the method nasty. Example 1 is produced by alternately heating the mixture of polyamide and solvent to 130 to HO ⁰ C and cooling in feotem carbon dioxide. This spinning solution is slowly poured into 300 ml of water at 30 ° C. at room temperature in a mixer with a capacity of 0.946 l, the shear blades rotating at full speed. The fine, fibrous particles are collected on a fritted glass funnel and washed, and after drying

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BATH ORIGINAL

a firm, coherent sheet. The sheet will see two aluminum foils pressed in a press with printing plates heated to 200 ° C. for 2 minutes under a pressure of 703 »V kg / cm ^2. A smooth, firm sheet is obtained. The fibrous particles (pibrids) show a high degree of crystallinity and a high degree of orientation in the X-ray analysis. The fibrid orientation angle determined by electron diffraction is 18 °.

For β ρ ie 1 4

This example explains the production of a film from a mixed poly (1,4-benzamide / 3-methyl- »1,4-benzamide) (molar ratio 90sIO).

One equipped with a stirrer, drying tube and nitrogen inlet tube, 250 ml dry round bottom flask comes with, 0.618 g (0.003 mol) 4 "amino-3-methylbenzoyl chloride hydrochloride charged, whereupon 5 * 185 g (0.027 mole) of 4r aminobenzoyl chloride hydrochloride can be added. With the addition of 3.5 ml of cold Tetrahydrofuran, the mixture is cooled with stirring in an egg bath. Then 25 ml of cold hexamethylphosphoramide in admitted to a shot. The mixture is stirred for a further hour at 0 ° G and then left to stand at 25 ° 0 for 16 hours. The polyamide precipitates out of the reaction mixture. The crowd is stirred vigorously in water in a mixer and then thoroughly washed with water and ethanol. The yield of fine powdery white polyamide is 97 # and the inherent one Viscosity 1.06.

Aue a batch of 0.5 parts of the above mixed polyamides, 0.32 parts of lithium chloride and 4.18 parts of tetramethylurate a film is produced «by mixing the mixture with the help of a

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3ο

Squeegee is spread out on a glass plate with a gap width of 0.234 mm. The coated plate is immersed in water, removed and the film obtained in this way is washed thoroughly with water and then pressed for 6 minutes between paper towels at TOO ⁰ 0 under a pressure of 43 * 9 kg / cm. The film is self-supporting, translucent and tough.

Example 5

A polymerization tank with a capacity of 2 l is charged with 153 »6 g (0.8 mol) p-aminobenzoylechloride hydrochloride with stirring and charged under nitrogen. A 2 $ solution of lithium chloride in distilled tetramethylurea is heated to 60 ° C heated, whereupon any water present is driven off in a vacuum will. 800 g of this solution quickly becomes the monomer powder in the polymerization kettle with stirring at 30 ° added. After 3/4 hours, 4 ml of diethylamine are added to interrupt the polymerization. After 5 minutes it will be a further 4 ml and, after a further 30 minutes, a further 4 ml of diethylamine were added. 18 minutes later mm sets 70 g (0.946 mol) lithium carbonate. The viscous mixture will then heated in an oil bath to 115 to 120 ° C, with 150 ml of tetramethylurate diluted and stirred in vacuo to remove the water formed during the neutralization and the excess solvent to distill off. The polyamide concentration of the solution thus obtained is 9 #.

One approach of this mixture is made with a mixture on 95 ropes Dimethylformamide and 5 parts of lithium chloride and diluted coagulated in water. The precipitated polyamide is washed three times in distilled water and then in acetone. Then it is dried in vacuo at 60 ° C. Ss has an in-

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inherent viacosity of 0.97 and a ratio of the X-ray diffraction maxima of 0.80 and leaves no polyamide residue on the bottom of the test tube during the sedimentation test.

Manufacture of fibers by wet spinning: The solution is pre-filtered through a stainless steel sieve with a mesh size of 74 μ in order to remove excess lithium carbon powder. Then 300 g of the solution are introduced into a spinning cell and filtered through a sand and sieve filter before the solution reaches the spinneret. The spinneret has 100 holes, each 0.076 mm in diameter, the holes are arranged in "three" circles with a total acidity of 1.27 cm. The spinneret ejects the solution into a 65 ° σ hot bath of distilled water, which is constantly circulated and filtered. Furthermore, the bath is constantly diluted with fresh knowledge to prevent excessive accumulation of salt and solvents in the bath. The sample was passed through a bath 135 cm long over a spool of 9.53 cm in diameter and wound onto a second spool of 9 cm. The spinning draft is controlled by varying the winding speed on the first bobbin. The lowest pulverization speed that is possible without accumulating yarn in the bath is 16.6 cm / Sefc. The calculated ejection speed of the unextracted polyamide solution is 25 _t 61 cm / sec. This means an extraction sofirutnp :. ^v ung; _:. lengthways from $ 36.5 before d £ to spooling. The smooth winding speed is 22.86 cm / sec., While the high winding speed, with continuous spinning still possible, is 26.88 cm / sec. amounts to. The values correspond to spin draw unus values of 1.4 and 1.65, based on the normalized value of 16.16 cm / sec. bfi a spin draw of 1.0. In relation to the discharge rate. this value is * 0.8> 3 or 1.05.

■ "'. - -'" '-. - 0098 & 2/2022

Q-928-R

The spun yarn is leached in water for 2 hours and then left to dry on the bobbins. The spun yarn has an orientation angle determined by X-ray analysis of 27 °. The T / E / Mi / den values for the spun yarn are after boiling 5.9 / 4.8 / 354 / 3.1.

The yarn is then heat treated by moving it at a speed 15.24 cm / sec. is pulled over a 30 cm long, grooved heating shoe, which is a contact time of 2 seconds. This heating zone is / is under nitrogen.

The wet-spun sample has after the various heat treatments when cooked the following properties:

Thread-

T / E / Mi titer, orientation, g / den /% / g / den 2 € »23.4 °

400 ° C 7.0 / 1.7 / 596 2.9 16 °

450 ° C 8.9 / 1.4 / 773 2.9 15 °

500 ° C 8.4 / 1.0 / 990 2.9 14 °

550 ° C 6.9 / 0.8 / 937 2.8 12 °

Example 6

This example explains the influence of the heat treatment on the strength and the modulus of the fibers according to the invention as well as the production of a laminate from the fibers.

A polymerization kettle with a capacity of 2 l is dried with the flame and allowed to cool under nitrogen. The cauldron is with an aluminum stirrer of the type of a snow club,

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a nitrogen inlet tube and an outlet. 150 g of p-aminobenzoyl chloride hydrochloride are charged into the polymerization kettle while a slow stream of dry nitrogen is passed through. To this end, 770 ml of tetramethylurea precooled to -10 ° 0 are quickly added with vigorous stirring. (This solution has previously been dried by distillation over calcium hydride to a water content of less than 0.015% by weight). Considerable heat is initially developed, which is absorbed by immersing the kettle in an egg bath for the first 15 minutes after the reaction has started. After stirring the kettle contents for 2 hours at 21 ° C, 38.0 g of powdery anhydrous lithium hydroxide are added and the mixture is heated to 120 ° 0 with continued stirring. After stirring for 30 minutes at 120 ° C, the highly viscous, rubber-like mixture is transformed into a more flowable spinning solution. By distilling off 50 ml of solvent under a vacuum of 20 cm Hg, most of the water formed by the reaction with the lithium hydroxide is driven off * The spinning solution now has a polyamide content of 10.2 % Z.

5 g of spinning solution are added to 200 ml of water in a Waring mixer. After stirring for 5 minutes, the aqueous liquid is decanted from the polyamide precipitate. After adding a further 200 ml of water, the mixture is stirred for a further 5 minutes. Then the treatment is repeated with 200 ml of ethanol instead of the water. The polyamide is filtered off and dried for 15 hours at 70 to 80 ° C in a vacuum oven fitted with a nitrogen inlet at 20 to 40 cm Hg. The polyamide has an inherent viscosity of 1.3ö and an X-ray diffraction ratio of 0.76 and, in the sedimentation test, does not leave any polyamide residue at the bottom of the reagent glass after 43 hours.

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Spinning: This spinning solution is spun as follows using the dry spinning process: From the spinning vessel in which the solution is kept at 115 ° C., the solution is passed through a piston under a pressure of 4.780 kg / cm via a spinneret approach kept at 125 ° 0 Spinneret pressed out at 160 ° C. The spinneret is a protrusion spinneret that consists of 9 effective holes, each 0.01 cm in diameter. In the approach, the solution runs through a filter, which consists of a sieve with a mesh size of 0.297 mm, three sieves with a mesh size of 74ju, a cotton cloth (81 _t 5 g / m ² ) with a plain weave with 148 weft threads each 25.4 mm and 160 warp threads each 25 , 4 mm and a felt pad with a basis weight of 95 g / m 2 and a density of 0.125 g / cm *, at atmospheric pressure. The spinning solution is ejected through the spinneret at a speed of 2.92 ml / min, into a spinning cell with walls heated to 200 ° 0, which is filled with nitrogen at a temperature of 235 ° C and a speed of 0.142 nr / min. * ^a direct current flows through it. The fibers emerging from the cell are passed through water and wound up at a speed of 123.5 m / min (spinning-stretching factor 3.2). The fiber is wound up at this speed for 1 hour. The spinning cake is then immersed in a large excess of distilled water at 21 ° C. for 15 hours in order to extract the salt and the solvent. The wet spider cake is stored in a polyethylene bag. The spun and extracted yarn has T / E / Mi / dea values of 8.22 / 3.1 / 509 / 3.06 after drying.

The extracted and dried yarn was carried out at one speed of 3.66 m / min, under nitrogen through a hot one Stainless steel pipe with a clear width of 7.26 mm and a length of 81.3 cm passed through it without changing its length

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BATH ORIGINAL

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IS

changes significantly. The nitrogen is passed through the tube from the yarn inlet end at such a speed that the atmosphere in the tube is renewed once per day. The pipe is heated from the outside in a 0.3 w long furnace, for the control of which a thermocouple is brazed to the middle part of the outer surface of the pipe, which is connected to a "Pyrovane" control unit (Minneapolis-Honeywell). The nominal heat treatment temperature given in Table III is the temperature indicated by a thermocouple which is brazed in the center of the tube on the inside thereof. A profile of the temperature in the tube for a "nominal temperature" of 536 ⁰ C as it is obtained by varying the position of the measuring Thermcelementes, .is given in Table 11 below.

T abe 1 1 e II

Temperature profile in the heat treatment tube 135 Distance from the entry end. cm temperature, ° C. 179 O 336 15.24 452 25.4 515 30.48 532 35.56 537 38.1 536 40.64 527 43.18 474 45.72 368 50.8 270 55.88 213 60.96 184 71.12 handle different temperatures 81.28 ι Table III. The properties of the *> ei ten yarns result from

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Production of a laminate; Yarn from the above spinning Process is heat treated by moving it at one speed from 3 to 53 m / min, through a hot pipe at a nominal temperature of 536 ° C is passed. The yarn is in shape of a thin spider cake about 3.81 cm. Width to one Coiled with a 10.5 cm diameter spool. The speed of the back and forth movement when winding is 1 stroke each 11 turns; the yarn threads in the spinning cake are almost parallel. A sample of the yarn shows the T / B / Mi value of 2.967 / 16.17 / 1.7 / 1096. '

A laminate is produced from the above fibers as follows: A mixture of 10 g of epoxy resin ("Epon 815"), 9 g hardening agent (mixture of bicyelo- (2,2,1) -heptene-2,3- "dicarboxylic acid anhydrides") and 0.1 g of benzyldimethylamine is poured into a mold that has a 15.2 cm cavity long, 1.27 cm wide and 2.29 cm deep. Form is kept with its contents in a vacuum chamber for 1 hour for the purpose of degassing. Then the mold is out of the vacuum chamber removed. The fibers are cut from the spool and in 15.2 cm long ribbons that are parallel to the fibers are stacked in a stack along the longitudinal axis of the tapes. The fibers weigh 4.84 g. The fibers are on the surface of the resin mixture and pressed in under gentle pressure, being careful that the parallel orientation of the fibers is preserved. The form and its contents are then returned to the vacuum chamber for 30 minutes used to remove unwanted gases. The mold is then taken out of the vacuum chamber, and a flanged punch (1-4.6 cm χ 1.27 approx χ 1.54 em) is pushed into the mold cavity and slowly down on the resin-fiber Gemiac'i pressed so that air bubbles and over «

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009862/20 22

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resin through the gaps between the ends of the punch and the ends of the cavity can escape without destroying the fiber arrangement. The punch flange rests on washers, which have such a thickness that between the inner surface of the mold bottom and the punch Gap of 0.254 cm remains. The form and its contents are then placed in a Pasadena press, its press plates are heated to 150 ° C. The press is closed and a total pressure of 1.36 t is exerted on it brought. The mold is left in the press for 2.75 hours, then taken out and allowed to cool to room temperature.

The ends of the fabric sample are cut and off Hand sanded with sand. The dimensions of the sample are 13.5 cm 1.27 cm 0.24 cm, its weight is 5 »68 g and their density 1.35 g / cm. For the determination of the elastic modulus of elasticity Select a four-inch section in the center of the laminate. The sample is considered more supported at both ends Rod attached in an Irbtron tester and in the Middle burdened. The loading organ becomes at a speed of 0.508 mm / min, deflected from its home position, until a load of 9 »07 kg has been brought into effect

op

is. The flexural modulus of elasticity is 10.13 χ 10 g / cm. in the In comparison, commercially available aluminum has a flexural modulus of 70.3 to 140.6 χ 1θ "g / cm at a density of 2.56 g / cm '. Laminates made of "E" glass have a theoretical one Limit of flexural modulus of elasticity of 56.2 χ 10 'g / cm at a density of 2.22 g / em'.

Example 7

Mixed polyamides are generally described below Process produced: All for the polymers -

009852/2022

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The glass utensils used are 2 to 24 hours dried at 150 ° C. The reactions are carried out in a polymerization kettle carried out, which is equipped with a compressed air stirrer, a nitrogen inlet tube and a drying tube. The monomers are weighed out in a drying cabinet, and the polymerization kettle is placed in the drying cabinet charged and assembled and then to the stirrer motor and the nitrogen line connected in a fume cupboard. Solvents are measured out in the drying cabinet and then in a feather-closed graduated cylinder or Erlenmeyer flask chilled in a mixture of salt and ice.

The monomers are cooled with stirring in an ice bath, and that cold solvent is added immediately. The mixture will Stirred under cooling until it becomes impossible to stir Mass thickened. If not within an hour occurs, cfas cooling bath is removed and the mixture another Stirred for hour at room temperature. Usually you leave that The reaction mixture stand overnight at room temperature. That Polyamide is worked up in water, five times in a mixer Washed with water and once with ethanol and then in a vacuum oven:. * Dried overnight under nitrogen at 80 to 100 ° C.

The individual polyamide production tests are shown in Table IV summarized.

009852/2022

BAD ORJGiNAL

Tab ell e

IV

Attempt no.

1 2 3

Monomers *, g

28.5 A 1.5 B

54 A 6 B

17.28 A 2.84 C

Solvent *, ml polyamide *

DMAc, 150
DMAc, 300
DMAc, 100

t IO f * L inta to (S ₂ SO ₄ )

1.18 0.78

1.00

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Polyamide X is a mixed polyamide with units

I.

the formula

and the formula N in a molar ratio of 95: 5.

Polyamide Y is a mixed polyamide with units

the formula ί, IT and the formula - £ --N

in a molar ratio of 90:10.

Polyamide Z iat a mixed polyamide with units

/ H of the formula f N

and the formula -. [. Ν in a molar ratio of 90 $ 10.

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Making fibers dunoh dry spinning: one with one A polymerisation vessel equipped with a Sohlitz disk stirrer driven by compressed air is filled with 90 g of a solution of 5 wt. 56 lithium chloride in 95 wt .- »# Dime thy lace tamid be · sends. To this end, 10 g of the polyamide prepared according to Experiment No. 1 are added. The suspension is stirred in Heated oil bath to 90 ° C. Forms in 5 minutes at 90 ° C a clear gel. The heating is interrupted and the Hasse stirred for a further hour while cooling in an ice bath. A viscous solution suitable for spinning is obtained.

This solution is pressed out according to the dry spinning process through a nozzle with 5 holes, each 0.05 cm in diameter, at a speed of 2.05 ml / min, at a winding speed of 137 n / min. The spin-stretching factor is 2.7. The yarn is put into water and then one overnight leached another hour in fresh water. The washed yarn is dried on the bobbin in a slow stream of air at 50 ° C for 2 hours. Then the yarn is over one Hot plate stretched at different temperatures and a stretching ratio of 1.05, with the following significant Increase in the modulus of elasticity is achieved t

Tabel

Maintenance a / d en E. Wed liter, Orientation bedineuneen 3.2 JL g / den the angle, ^σ no 5.2 4.2 192 2.5 33 380 ° C 7.4 1.0 348 2.3 12th 425 ° 0 11.2 2.1 379 2.2 11th 480 ° 0 1.8 . 680 2.3 13th

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11 g of the mixed polyamides prepared according to experiment no. 3 are dissolved in 99 g of a solution of 5 wt .- # lithium chloride in 95 wt .- # dimethylacetamide while stirring with a Schiits-βeibenrührer and heating in an oil bath at 80 ° C for 20 minutes. A viscous solution is obtained. The viscosity of this solution is reduced by cooling to tree temperature and then stirring for 30 minutes. This solution is pressed out according to the dry spinning process at a speed of 2.05 ml / min, through a spinneret with 5 holes, each 0.01 cm in diameter. The yarn obtained is washed continuously in water and wound up at a speed of 183 m / min (spin-stretch factor »3 * 6). The yarn is extracted with water overnight, leached for a further two hours in fresh water and then dried in warm air for 4 hours. The yarn is then drawn under the conditions specified in the table below and the following properties are achieved:

Table 1 e

VI

Sample treatment

2
3

in freshly spun condition

heated to 385-390 ° C

at 426 ° C to 1.1 times stretched

knitted 1.1 times at 480 ° C

örieiätie-

TE Mi titer, rungswln g / den # g / den kel _t °

2.5 8.7 111 2.1

5.2 2.0 320

7 * 9 2.5 385

11.1 2.6 470 1.7

47

1.7 14 1.6 23

14th

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A mixture of 8 g of that prepared according to Experiment No. 2 of Table IV Mixed polyamides, but with an inherent viscosity of 1.27, and 3 »0 g of the same mixed polyamide, but with an inherent viscosity of 0.97 »is obtained in 99 g of an Lb'-aung of 5 wt .- # lithium chloride in 95 wt .- # dimethylacetamide by stirring for 30 minutes with a slotted disc stirrer and heating in an oil bath to 80 to 90 ° C and then followed by stirring Cooling down to room temperature dissolved. The solution is extremely viscous and becomes the same with another 12 g Diluted solvent. A very good result is obtained after 30 minutes at room temperature with occasional cooling in ice water viscous, clear spinning solution with only a few gel-like lumps contains. The final concentration is 9 wt .- ^, and the Spinning solution is after the dry spinning process at a speed of 2.34 ral / min. through a spinneret with 5 holes, each 0.01 cm in diameter, pressed out. The yarn is wound up at a speed of 111 m / min. The Spinn-Reek factor is 1.91.

The yarn is made with distilled water and then overnight Extracted with fresh water for 2 hours. It is then dried on the bobbin in warm air for 2 hours. The yarn will stretched under the conditions indicated in Table VII below and with the achievement of the indicated properties.

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sample

Stretched at oc

T, g / den

Mi, g / the titer _t the orientation angle,

T 1 a b e 1 1 e VJCI 2

in fresh 426 ° O to 480 ° C on spun 1.24 times 1.1 times Conditions

9.5 165 2.9

47

8.6 2.2 518 2.2

12th

11.2 2.6 577
2.5

14th

This results in a significant improvement in properties through the heat treatment of the fiber. In the freshly spun state, the yarn of sample 1 had a modulus of 165 and an orientation angle of 47 °. The heat treatments specified for samples 2 and 3 increase the module and reduce the orientation angle to 12 ° and 14 °, respectively.

B e L a ν ie 1

The example illustrates the manufacture of fibers from a Misahpoly- (1,4 »benzamide / 3-m'3thyl-1,4-benzamide) (molar ratio

Hfretstellung of the mixed polyamide j A with stirrer, nitrogen inlet tube and calcium chloride trooke tube 1 l PolymeriaatiOnskesael is flushed out with dry nitrogen and heated with the FLamcie, in a drying cabinet the device with 3.1 g (0.018 mol) of 3-methyl-4-aminobenzoyl eblorid-hydrochloride and 65.68 g (0.342 mol) 4-aminobenzoyl " oalorld hydrochloride beiicbiokt. The device is made of the

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Removed drying cabinet and chilling in ice, whereupon stirring is started. 54 ml of cooled tetrahydrofuran and 700 ml of cooled hexaraethylphosphoramide are then added in succession. This is immediately resolved. The reaction mixture is cooled under pipes in the ice rink. ! Precipitation begins after 50 minutes. The mixture is stirred for an additional 10 minutes with cooling. After stirring the kettle contents for a further 0.75 hours at room temperature, the contents are completely solidified. The white reaction mass is left to stand overnight at room temperature, then transferred to a mixer and stirred with Wanser. The white powder that forms is filtered off, washed three times with water in a mixer (it is filtered off after each washing process), washed once with alcohol in the mixer, filtered off and dried overnight in a vacuum oven at 90 ° C. This gives 45.02 g of mixed polyamides f £ inh * 1,7i _e

Production of the Lb'aungr A 500 ml polymerization kettle equipped with a shear disk stirrer, condenser and Tyocken tube is filled with 20 g of de? above mixed polyamide and 180 g of a 6.54 wt .- # solution of lithium chloride in tetramethylurea charged. 33 kettle and its contents are cooled in solid carbon dioxide for 2 hours and then left to stand overnight at room temperature. The contents of the kettle are then heated to 125 ° C. for 3 hours, cooled in solid carbon dioxide for 2 hours without stirring: and then heated to 125 ° C. for 2 hours and to 120 ° C. for 16 hours with stirring. Then it sets a further 20 g of the solution of Lithiumohlorid in tetramethylurea to, whereby the polyamide ion concentrate at 9 f> is reduced. The contents of the vessel are then cooled in solid carbon dioxide for 2 hours, heated to 125 ° C. for 4 hours with stirring, again in solid carbon dioxide for 2 hours. Chilled carbon dioxide, then 16 hours at room temperature

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Left to stand on the door, heated to 125 ° C. for 4 hours with stirring, cooled in solid carbon dioxide for 2 hours, more Left to stand for 16 hours at room temperature, to 138 ° C heats and ultimately processed by dry spinning.

Production of fibers by dry spinning: The solution produced in this way is ^{pressed into a dry column under a pressure of 5.625 to 7.031 kg / cm 2} through a spinneret heated to 140 to 142 ° C. and having 7 holes, each 0.01 cm in diameter, the walls of which are in Temperature range of 190 to 200 ° C can be maintained. At the same time, the column is flushed out with 0.127 nitrogen in cocurrent, which enters the column at a temperature of 235 ° C. A finishing solution is applied to the threads emerging from the column, whereupon the threads are wound up at a speed of 167 m / min. The bobbin is leached for 62 hours with two batches of distilled water at 25 ° C * The water-leached and air-dried at 2.1 ° C and 65 # relative humidity are crystalline and have an orientation angle of 21 ° and the following tensile strength values: T / E / Mi / den «4.58 / 1.3 / 425 / 2.36.

Heat treatment of the fibers: The threads or yarn produced in this way are guided in a tensioned state under nitrogen in a one-step operation over a hot plate with a diameter of 7.62 cm, which is kept at 440 ° C. The dwell time over the heating plate is 4 seconds. The thus treated yarns are highly crystalline, have an orientation angle of 12 ^C and show the following tensile strength: T / E / Jii / d "m" 9.07 / 1.3 / 744 / 1.91.

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Example 9

This example explains the production of fibers from a mixed polyamide with a random distribution of the monomer components from p-aminobenzoyl chloride hydrochloride, p-phenylenediamine and Terephthalic acid chloride.

Production of the mixed polyamide: A stirrer with a disc stirrer, A 1! Polymerization kettle equipped with nitrogen inlet tube and calcium chloride drying tube is flushed out with nitrogen and heated with the flame. In a drying cabinet this device is charged with 62.22 g (0.324 mol) of p-aminobenzoylechloride hydrochloride. Then the device turns off removed from the drying cabinet and chilled in ice, whereupon vigorous stirring is started. 352 ml of im Poured tetramethylurea into an ice bath, whereupon the contents of the kettle immediately dissolve. You bet on this immediately a mixture of 3.89 g (0.036 mol) of p-phenylenediamine and 7.31 g (0.036 mol) of terephthalic acid chloride, which was previously placed in the mortar ground together and stored in a sealed conical flask. The boiler content is under for 15 minutes Cooling and then stirred for a further 2.25 hours after removal of the cooling bath. Then the kettle contents are put into a mixer poured and stirred with water at high speed for 5 minutes to precipitate the mixed polyamide. The product will filtered off, washed by stirring with water in a mixer (three separate washes of 5 minutes each, between which the product is filtered off), whereupon the Product is washed once by stirring with alcohol in a blender for 3 minutes. The mixed polyamide is isolated and dried at 90 ° 0 in a vacuum oven for 16 hours. The yield is 47 g; 71 inh «1.40.

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Preparation of the solution: One with a shear blade stirrer, Kubier and Sroekenrohr equipped 500 mi-Polymerlsationekesael is with 30 g of the above mixed polyamide and 270 g of a 6.54 wt .- ^ solution of lithium chloride in tetramethylurate loaded. The kettle and its contents are first cooled in solid carbon dioxide for 2 hours, then heated to 125 ° for 2 hours with stirring, for 2 hours without stirring solid carbon dioxide cooled »stirred for 15 hours at 125 ° C, Cooled in solid carbon dioxide for 2 hours without stirring and then initially for 5 hours at 130.degree. C. and then for 15 hours at 120.degree stirred »whereupon so much tetramethy! urea is evaporated» that a 13 # spinning solution of the mixed polyamide is created.

Production of fibers by dry spinning: The spinning solution produced in this way is heated to 110 ° 0 and under a pressure of 5.625 to 5> 66O kg / cm ² through a spinneret heated to 119 to 125 ° C with 6 holes of 0.01 each om diameter pressed into a dry ice, the walls of which are kept in the temperature range from 198 to 207 ° 0. The column is at 0.135 m '/ min. flushed with dry nitrogen in cocurrent, entering the column at a temperature of 235 ° C. A finishing solution is applied to the threads emerging from the column, whereupon the threads are wound up at a speed of 183 m / min. This corresponds to a spin-stretch factor of 4.1. The coil is leached in two batches of distilled water at 25 ° C. The water-leached and air- dried at 21 ° 0 and 65 1> relative humidity are crystalline, have an orientation angle of 25 ° and show the following tensile strength values: T / B / Mi / den * '8.66 / 3, 1/426 / 3.37.

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Heat treatment of the pasers: The threads produced in this way are under nitrogen in a tensioned state in a single operation over a heating plate kept at 440 ° C a diameter of 7.62 cm. The dwell time over the heating plate is 4 seconds. The threads treated in this way have a high degree of crystallinity and an orientation angle of 11 ° and show the following tensile strength values: T / B / Mi / den «11.2 / 1.7 / 725 / 2.98.

Example 10

This example explains the production of a tough film from a different mixed polyamide.

First a 10 # mixed polyamide solution is prepared, by 0.5 g of in a manner similar to that of Example 9 from p-aminobenzoyl chloride ~ hydrochloride, p-phenylenediamine and Terephthalic acid chloride in a molar ratio of 90:10:10 produced copolyamides with randomly distributed monomer units (^ inh β 1.03) with 4.5 g of a 6.54 wt .- # solution of Mixing lithium chloride in tetramethylurea. After cooling the mixture for 1 hour with solid carbon dioxide and heating for 2 hours with stirring at 140 ° C, solution is complete occurred. This solution is spread out according to Example 11 of this OS on a polytetrafluoroethylene plate, in water dipped, washed and undrilled to prevent shrinkage; a solid, coherent, self-supporting, transparent film is obtained.

Example 11

This example illustrates the preparation of a tough poly (p-benzaride) film according to the invention.

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First a 5 # polyamide solution is prepared by adding 0.25 g of poly (p-benzarid) C ^ inh »1; mean ratio of the X-ray diffraction maxima> 0.77 1 divided according to the general procedure of Example 1) and bringing together 4.75 g of a 6.54 wt.% solution of lithium chloride in tetramethylurea. The mixture of these two substances is alternately cooled twice for 1 hour each time with solid carbon dioxide and heated to 140 ° C. for 2 hours each time, whereupon a clear, almost colorless solution is obtained. This solution is spread out on a polytetrafluoroethylene plate with a gap width of 0.127 mm using a doctor blade. The coated plate is dipped one after the other in two batches of distilled water. The solidified polish and the plate are removed from the bath, covered with a paper towel and dried in a press at 150 ° for 5 minutes, preventing shrinkage, under a pressure of 22 kg / cm. colorless, transparent polie.

Another sample of poly (p-benziamide) (γ, inh »1.53 J ratio of the X-ray diffraction maxima a» 0.74, prepared according to the general method of Example T) is in a concentration of 10 wt .- 56 in the above-described solution of lithium chloride dissolved in Tetrataethylharastoff and cast according to the method of the preceding paragraph to a polie. The tough, flexible polie ha ·; a tensile strength of 2.28 × 10 g / cm, an elongation at break of 1.1 # and a modulus of elasticity of 2.71 × 10 ⁸ g / cm ² .

The following examples illustrate the production of pas- sers from mixed polyamides, the au »p-aminobenzoyl chloride hydrochloride and comonomers for the repeating units AA and BB are made.

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Example 12

One with a glass stirrer with polytetrafluoroethylene flights, a nitrogen inlet tube and a drying tube equipped 1! -Polymerisat! onskeeeel by brushing Freed from moisture with a flame and placed in a drying cabinet. The vessel is charged with 51.84 g of 4-aminobenzoyl chloride hydrochloride and, after pouring into the pan, cooled in an ice-water bath. While the solid is being stirred, 293.6 ml of tetramethyl urea are added. After 15 minutes Long stirring is added to 1.62 g of p-phenylenediamine and, after a further 5 hours, 2.91 g of pyromellitic dianhydride. When stirred, the mixture turns into a light yellow, viscous one Solution. After 2 hours of reaction, this viscous solution is poured into water, which is in a large mixer, with stirring. Repeated filtering and washing in the mixer gives a fine-grained product which after drying, weighs 36.7 g and has an inherent viscosity of 0.54 in concentrated sulfuric acid.

A dope is made by putting the polyamide in a solution of lithium chloride in tetramethylurea 125 ° C is brought into solution. The weight ratio polyamide: tetramethylurea LiCl in this solution is 12: 82.3: 5.7.

After the dry spinning process imter the following conditions fibers are produced t

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■ ft "

Temperature in the anaatz, ^Q C spinner head temperature, ° C bridge, kg / βτη

Spinning speed ml / min. Spinneret

Column temperature, 0

Nitrogen flow rate, m '/ min.

Winding speed, m / Hin. finish

125 to 226 130 0.127 5 * 6 128 4.8 and detergents 10 holes of each 0.01 cm average knife, 141 ° C 235 water

The paser is extra hiert for 2 days with various water sutures and then dried in the air. The boiled fiber has the following properties2 T 2.46 g / denj E β 1.1 ia \ Mi «240 g / den; Titer «2.70 den. The dry fibers are passed on the scent over a heating plate heated to 440 ° C (in contact with the same) and then have the following properties: £ 3.1 g / den; E * $ 1.0; Mi »322 g / denj titer« 2.86 den.

Example 1 ?

The Polymerisatlonsgefäß described in the previous example is with 375 ml of pure Sioxan, 8.85 g of 5-Ohlorieo « phthalic acid chloride and 64.80 g of p-aminobenzoylochloride hydrochloride are charged Ice cooled and quickly mixed with a solution of 4.05 g of m-phenylenediamine in 375 g of tyridine. The suspension turns orange and the color fades in 2 hours suiesliob. The polyamide precipitate is filtered off and three times in one Mixer washed by stirring with water and filtering off.

009852

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PT

ethanol is used for the final wash, after which the polyamide is dried. The yield is 50.5 g * the inherent viscosity 0.64.

The polyamide is dissolved in a solution of lithium chloride in dimethylaoetamide at 120 ° C. to form a clear, viscous spinning solution which contains 18% by weight of polyamide and 5.33% by weight of lithium chloride.

Fibers are made from this solution by dry spinning under the following conditions:

Temperature in the approach, ⁰ O 120 Spinner head ^{temperature, 0} C 120

Pressure, kg / cm ² 21 to 42 spinning speed, ml / hin, 2.3

Spinneret 5 holes

Each 0.127 mm in diameter, 124 to 128 ° C

Column ^{temperature, 0} C 214-203 Flow velocity

of nitrogen, m3 / min. 0.142

Winding speed, m / Hin. 93 «3 Finishing water and detergent "

The wet fiber is extracted with water until it is free of salt and then air dried. The T / E / Mi values of these Fibers are 1.0 / 8.0 / 51 after boiling off. After stretching 2.2 times at 360 ° 0, the T / E / Mi values are 3 * 2 / 2.0 / 234. The orientation angle of the fiber is 16 °.

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Example 14

Manufacture of the polyamide: One with stirrer, nitrogen inlet tube 250 ml round bottom flask equipped with calcium chloride drying tube is heated with a flame Bunsen burner flushed with nitrogen. The dry flask is placed in a drying cabinet with its accessories and charged with 11.52 g of p-aminobenzoylehloride hydrochloride. The flask is then connected to a stirrer motor and a source of nitrogen, and slowly bubbling is started of nitrogen with stirring while the flask is in the ice bath is cooled. Then 58.7 ml are quickly added in one shot cold tetramethylurea added. The monomer immediately goes into solution and polymerization begins. One stirs more 2 hours with cooling in an ice bath and then 2 hours without K'Uilung. The resulting polyamide forms a viscous, somewhat cloudy dope. One out of solution after 4 hours Polyamide sample isolated by precipitation with water has a inherent viscosity of 1.38. "

Production of a film: A sample of the polyamide solution is made Poured into a film by applying the solution with the aid of a doctor blade with a gap width of 0.127 mm on a flat polytetrafluoroethylene plate is spread. The plate with the coating is immersed in water, and the by coagulation of the The resulting film is washed with several water mixtures. The film is dried by placing it between polytetrafluoroethylene sheets and a paper towel at 125 ° C for 5 minutes is pressed under a pressure of 21.9 kg / cm. the Foil is glossy, practically colorless and flexible.

Manufacture of fibers: a sample of the following example, but from a second reaction mixture, produced

* ■ 55 -

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th polyamide solution is placed in a 15 ml beveled, syringe-like cell made of stainless steel with a mechanically driven piston. In the cell of a filter packing made of a stainless steel sieve with 74 μ Hash length, a thin layer of fine glass wool and three successive sieves of 297 by means of a ring nut with the interposition / i, 74 μ and 297 μ mesh size of a spinneret of a platinum alloy with 20 Drilled holes of 0.076 mm in diameter each. The spinning solution is squeezed out of the spinneret at low speed into a water bath kept at 50 ° C, and the fibers are wound up at a speed of 18.6 m / min after they have passed through a 0.91 m long bath. The fibers have the following properties (Table VIII).

Table VIII

Titer, TE Mi

Treatment of the g / den jo g / den

Washed and air dried

Heated to 440 ° C. for 4 seconds under nitrogen

Heated to 530 ° C for 2 seconds under nitrogen

The polyamide of the frisoh developed Paser has an inherent Viscosity of 1.12 and a ratio of the X-ray diffraction maxima of 0.78.

Example 15

Polymerization: All glass rods are prepared before use 15 hours at 160 ° C and dried in a drying cabinet

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5 , 67 3, 6th 4, 1 221 4th , 86 5, 8th 1, 0 619 5 , 05 6, 7th 1, 2 577

Q-928-R

Allowed to cool to room temperature. In the {drying cabinet a with nitrogen inlet tube, stirrer and one through one A 500 ml, three neck, round bottom flask equipped with a Trooken tube protected outlet is charged with 10 g (0.052 Hol) of p-aminobenzoyl chloride hydrochloride. Then the device is removed from the Dry cabinet removed and connected to an electric stirrer motor and source of dry nitrogen. In the fluted reaction vessel, 120 g are cooled to -10 ° 0 Entered tetramethylurea, whereupon one begins to stir. When the p-aminobenzoylehlorid-bydroehlorid has completely dissolved, the solution is allowed to reach room temperature and then heated to 50 ° C in a hot water bath. After 30 to 60 minutes at this temperature, a viscous pouring solution has formed added to a mixer to water and washed the precipitated polyamide with water and ethanol and under nitrogen im Vacuum oven dried at 80 ° C. The inherent viscosity of the Polyamide is 1.4 or more.

Pouring a film: The viscous solution is immediately applied using a Rikel with a gap width of 0.381 mm poured onto glass plates. The solutions spread out on the glass plates are treated by two different methods, both of which result in clear, foldable films with a high modulus of elasticity. The first method uses the Solution coated * Glass plate placed directly in a draft oven at 130 to 1> 0 ° 0. After 65 hours the Slide from the cooled glass plate by immersing it in water replaced. It is then dabbed with blotting paper and allowed to air dry. According to the second method, the freshly coated glass plate is immediately placed in water at 25 ° C.

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5 *

dives. After 3 minutes in water, the gelled film will detach itself from the plate. This swollen film will clipped to a plate coated with a polytetrafluoroethylene film and dried in a draft oven at 130 to 160 ° C. After 65 hours of drying, a clear » tough, flexible foil.

Properties of the foils: The foils produced by the above processes have practically the same physical properties Characteristic values, e.g. a film has a density of 1.39 g / cm ', a tensile strength of 2.1 10 g / cm, an elongation at break of 1.5 # and a modulus of elasticity of 1.76 χ 10 g / cm. You determine the orientation using the ultrared band at 1020 cm "* according to the method of Schmidt (Journal of Polymer Science, A1, page 1271 / J9 &% 7) shows that the polyamide chains in the film have an unusually high degree of unipolar orientation. The film described in Example 11 also has a high degree of uniplanar orientation of the polyamide chains. This uniplanar orientation, in which the diffraction planes are aligned parallel to the plane of the film, is further confirmed by the arc diffraction spectra.

Example 16

This example illustrates how to make threads from a Mixed poly (p-benzamide / m-benzamide).

The polymerization takes place under the conditions described in Example 7. 17.28 g (0.09%) of p-aminobenzoyl chloride hydrochloride and 3.1 g (0.01 mol) of 4- (3 ° -aminobenzamido) -benaoylohloride hydrochloride are mixed together and cooled in an ice bath. 100 ml of dry, ice-cold material are added to the mixture

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Ν, Ν-Dimethylaeetamid added * whereupon the mixture with a Snow-sole-like stirrer is stirred rapidly. The temporarily formed solution solidifies into one in 20 minutes white mass that can no longer be stirred. After allowing the reaction mixture to stand overnight, it will poured in water. The precipitated polyamide is isolated and washed in a mixer five times with water and once with 2B alcohol. After drying the product in a vacuum oven at 80 ° C 12.3 g of mixed poly-Cp-benzamide / m-benzamide are obtained) (91: 9 molar ratio) inherent viscosity 0.82.

A 9 # spinning solution of the above mixed polyamide is prepared by adding a mixture of 9 * 0 g of the mixed polyamide and 91 g of a mixture of 95 wt. S ^ N, N-dimethyl acetamide and 5 wt .- ^ Lithium chloride is heated on the steam bath for 10 minutes with vigorous stirring. The mixture is left to stand overnight « a clear solution which is viscous at room temperature forms. This solution is squeezed into a warm water bath using a small, syringe-like device. The fibers obtained in this way are extracted with water, dried and heat treated under nitrogen. Table IX shows the tensile strength properties of the so produced and treated fiber. "

Tab e 1 Ie

Attempt no.

2
3

Heating the fibers

No; in a freshly spared condition

480 ° C 525 ° C

Fiber properties T E Mi

i t / den # g / den

3.9

17.7

1.0
1.2

56

428 466

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Go

Example 17

This example explains the production of threads from a mixed poly (1,4-benzamide / 3,5-dimethyl-1,4-benzamide).

A polymerization kettle is filled with 17.28 g (0.09 mol) of p-aminobenzoylechloride hydrochloride and 2.20 g (0.01 mol) 3,5-Dimethyl-4-amiiaobenzoylchloride-liydrochlorid charged. to 10 ml of ice-cooled material are added to the monomer mixture while stirring Tetrahydrofuran and then 100 ml of hexamethylphoaphoramide were added. The content of the polymerization vessel becomes 1 hour stirred at 0 ° C and 1 hour at room temperature. Then you let 'stand overnight at room temperature without stirring, the Content freezes. The polyamide is precipitated by pouring the contents of the reaction vessel into water. The poly » amide is then isolated, washed five times with water and once with 2B alcohol in a mixer and at 80 ° C in a vacuum oven dried. 11.5 g of mixed poly (1,4-benzamide / -3,5-dimethyl-1,4-benzamide) are obtained; inherent viscosity 1.63.

A mixture of 9.6 g of the above mixed polyamide is placed in a kettle and 87 g of a solution of 7% by weight of lithium chloride in 93% by weight of tetramethylurea with stirring in an oil bath Heated to 135 ° C. A stiff gel forms in 20 minutes. The oil bath we! replaced by a bath of solid carbon dioxide, in which the reaction vessel with its contents is 0.5 hours is cooled. Then the polymerization kettle and its contents are again immersed in a hot oil bath at 135 ° C and 4 hours. This creates a mobile liquid that contains undissolved, gel-like particles. then the contents of the 3 reaction vessel are restored as described above, refrigerated and stand at room temperature overnight

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calmly. Then the mass is reheated, frozen out, heated again, frozen again and reheated, everything as described above, whereupon a spinnable solution is obtained.

This solution is dispensed at a rate of 1.75 ml / min. spun through a spinneret with 5 holes, each 0.01 cm in diameter, into a drying column, the walls of which are kept at 200 ° C, and which with 0.119 nr / min. dry nitrogen in Co-current is purged, with the nitrogen in the column enters at 265 ° 0. The yarn obtained in this way is wound up at a speed of 125.5 m / min, with a finish is applied from water and a detergent. The thread spool is in distilled water over the weekend and then leached again for 24 hours in fresh water. The yarn is dried in warm air and then heat treated by it passed by hand over a hot plate under nitrogen will. The various fiber samples have the properties given in Table X.

T a b e 1 1 e

Ver
search
No. Heating
on of the fibers egg T
'the 3 E. Wed Orientie
rungswin
kel 1 No j in
crazy freshly
State 7th , 4 1 , 0 388 28 ° 2 450 ° C. 10 , 6 1 ,8th 595 13 ° 3 480 ° C. 9 ,8th 1 ,8th 600 12 ° 4th 530 ° C. 9 , 7 , 5 688 12 °

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Example 18

This example explains the production of threads from a mixed poly- ^ iminocarbonyl-p-phenyleneVioxyearbonyl-p-phenylene iminocarbonyl-p-phenylene ^ J.

A polymerization kettle equipped with a stirrer, drying tube and nitrogen inlet tube is connected to a stirrer operated by compressed air. The boiler is in The drying cabinet is charged with 17.28 g (0.09 mol) of p-arainobenzoyl chloride hydrochloride and 3.12 g (0.01 mol) of p-aminobenzoic acid p- (chlorocarbonyl-phenyl ester ahydrochloride.) The reactants are mixed with one another by stirring and chilled in an ice bath. Then 100 ml of dry, ice-cold Ν, Ν-dimethylacetamide are added in one shot with rapid stirring. In 30 minutes, the reaction mixture solidifies to one cloudy mass that can no longer be stirred. The reaction mixture is left to stand at room temperature overnight and is set then add water to interrupt the reaction. The contents of the reaction vessel are stirred with water in a mixer, whereupon the polyamide precipitates. The polyamide is filtered off, washed five times with water and once with 2B alcohol in a mixer and dried overnight at 80 ° C. in a vacuum. 12.7 g of mixed poly- / riniinoearbonyl-p-phenylene) / (oxycarbonyl-p-phenyleneiminocartonyl-p-phenylene) 7 (molar ratio 91: 9), the recurring units of the formulas

0 -NH-C - ^ \ - and

having.

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009852/2022

BAD ORIQfNAL

Q-928-R

A 5 # spinning solution is produced by first 1.5g of the above mixed polyamide to form 28.5 g of a mixture 94% by weight of tetramethylurea and 6% by weight of lithium chloride added and this mixture is stirred at 100 ° 0 for 36 hours. The something cloudy, gel-like mass is then produced in a small, motor-driven hate spinning device by a Spinneret with a single hole 0.127 mm in diameter in Squeezed out water. The laser obtained in this way is wound up, extracted with water and dried. Small strands from these Fibers are heated to 480 ° 0 or 525 ° C under nitrogen. The properties of the fibers treated in this way result from Table XI.

table XI

Heating of the pasers

_ on

No? in fresh eraponnanem State

4? J0 ° 0
■? 25 ° (J..

TE g / den

j, 7 11.9

4.8 6.9

1.0 1.3

Wed
g / den

100

592
636

Orientation angle

55 °

20 °

not determined.

Commercial value: The fibers according to the invention are particularly suitable for reinforced plastic laminates because they have a high modulus of elasticity, a low density, high volume stability, high strength, high heat resistance and high _{flexural rigidity for a given plastic material (} ; weight. Special applications are spiral-shaped wrapped pressure vessels, skis, bows, fish 3 rows la and golf club handles.

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009852/2022

BATH ORIGINAL

Q-928-R

Due to their high modulus of elasticity, their high strength, Fatigue resistance and shock resistance, the fibers are also suitable for rubber goods, such as!

The fibers are also suitable for sewing threads and for manufacture of protective clothing, ironing board covers, filter fabrics, technical hoses, felts for drying devices and for everyone other uses in which fibers of high heat resistance are required.

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009852/2022

Claims (1)

1. Polyamide threads »fibers, films and fibrids, characterized in that they have an orientation angle of up to 35 ° and have a modulus of elasticity of more than 200 g / den and that the polyamide is made of (a) 80 to 100 mol # of repeating units of the formula (b) 0 to 20 mol # of repeating units of the general formula -z- in Z an m-Phenylenreat or a substituted m- or p-Phenylenrest, one or more Has (identical or different) substituents, the Halogen atoms, lower alkyl, lower alkoxy, isopropenyl, methylthio, ethylthio, cyano, nitro, aoetyl, Carbomethoxy, carboethoxy, acetamido, dimethylamino, Diethylamino, ethylsulfonyl, dimethylearbamoyl, Diethylearbamoyl-, methyls ^ alfonyl-, dimethylsulfamoyl, Are diethylsulfamoyl or fluoreulfonyl radicals, or a remainder of the general formula - 65 - New UnttflG ^ Q! ι {. '■ · · -ο> / w5. 2 ux. 1 sow a atw 009852/202 2 BAD OPJQINAl Q-928-R Ct means which can be substituted by one or more halogen atoms, lower alkyl or lower alkoxy radicals, in which the terminal bonds are in position 3, 4 or 5, and in which X »means a single bond or the meaning CH ₅ , O
κ HO H O ti It ^C »WW It or -0-C- has, or equal to files of up to 10 mol # each of recurring units of the general formula H-R-N and the general formula Y-R'- consists, χorin Q and Q ¹ hydrogen atoms, methyl or phenyl radical, R a divalent organic radical or a single bond and R 'a divalent organic radical, while Y and Y ^{1 mean} N H -C- or -S- to have, 009852/2022 Q-928-R and the polyamide when it is essentially a homopolyamide is, an inherent one determined in sulfuric acid at 30 ° C Vlecosity of at least 0.7, a ratio of the X-ray diffraction maxima up to 0.86 and the property of leaving no sediment when 0.1 g of the polyamide with 10 ml of a 6.9% strength by weight solution of lithium chloride mechanically stirred in tetramethylurea for 24 hours. and Let stand at room temperature for 24 hours, and the polyamide, if it is a mixed polyamide, one at 30 ° C has an inherent viscosity determined in sulfuric acid of at least 0.5. 2, process for the production of polyamide threads, fibers, Fibrids and films according to claim 1, characterized in that a polyamide or copolyamide according to claim 1 is used 1 with tetramethylurea, preferably in the presence of. Lithium chloride, mixed with heating and jades, foils or fibrids produced from the mixture obtained and optionally the threads or foils heated or warm stretched and / or optionally the threads obtained Staple fibers processed. 3. Spinning mass, characterized in that it is a polyamide or copolyamide according to claim 1 in tetraraethy! Urea, preferably in the presence of lithium chloride. - 67 - 00985 2/202 2 BAD ORlGiNAL