DE1669513A1 - Synthetic polycarbonamide thread and process for its manufacture - Google Patents

Description

^J P 16 69 513. 9-43
New documents

E. "I. Du POHT DE NEMOLHS AND COMPANY 10th and Market Streets, Wilmington, Delaware 19898, V. St. A.

Synthetic polycarbonamide thread and process for its manufacture

This invention relates to a new synthetic polycarbonamide thread and a method for its preparation · In particular the invention relates to a synthetic polyofaonamide thread, a unique combination of high strength, whiteness, high dye absorption and durability against degradation by heat and light.

Shaped objects, such as fibers, yarns, threads, staple fibers, Films, pellets and the like made from a polyamide are well known. Such substances are in known in the art as nylon. The manufacture of polymers, the aioh for the manufacture of such shaped objects can be used according to the guidelines in U8A ~ Pat® 2 071 250, 2 071 253 and 2 130 948 t * aohrlet »·

- ^l -. 109812/172 fv υ «documents in accordance with Art. 7 § 5Ab ₉ .2 _N r ι inu 3 *

BATH ORIGINAL

, v, 4, 9,

HD-1351

In order to achieve various improvements for and epeal purposes, numerous modifications of the method have been proposed. For example wire; in the US patent publication 2 510 777 (Gray) reports that the Hylon undergoes severe discoloration during the dye fixation! This, however, the discoloration process is inhibited »if the Ky, Icduroh Kinaohluoa is a uerivatee of the bvpophosphorigeß Slhire aiofcifieiert * According to the teaching of the US Patent Achirift _f 2 7CS 221 u> * araatojff) \ cawn the combination increases resistance against acidative aft & muuir duooh are: (1) / Siß * jfeieiste Kapferverbindunr, (2) a halogen bite and (3) a derivative of the phoephorigenic acid _a gene of the original patent specification 3 078 248 (Ben) the staining strength of polyamides can be provided by increasing the amine ends » oils corresponding Sunahne to "pinntropfen C'apinniHj: drips") may »» ^ will prevented aßadat: polyamide be atimmte Phoaphinate and fhoaphinaäuren trains networked

Eo would be expected "that" on "if one were to rename these technologies, a very weaker value of the Iylongn? N received on Orund from ./eoheelviffekt" wiaohen den vereohled "! ** n.Best! But sharing results in a single product and &% n mhl stereo process. ^:

The aim of this office is the sheepdog

109812/1720

RD-1351

Polyoarbonavldfadens old high strength «which both against the Exposure to heat As auoh light is stabilized and enhanced Able to absorb acidic dyes.

Another aim is to provide a process for the production of a stabilized "acid-dyeable Polyocarbonaaidfadens" which can be run continuously without rapid clogging of the spinnerets or the polishing filter medium

These objects are achieved by the present invention, which an acid-stainable, heat-stabilized polyacrylate thread and provides a process for its production

The subject of the invention is now a synthetic Polyearbonasddfaden, known by a content "based on the customary Polyaeren"
(a) at least about 0.01 Gw ₀ -Ji, a "Phosphonsts of Porael

0
RP-OX,

0
X »

where R signifies alkyl * aryl or ^{arylalkyl radicals and I 1} and X signify hydrogen

109812/172 0

BAD ORlGlNAl.

RD-1351 *

(b) 0.001 to 0.0? Wt .- ^ of a copper compound, preferably of copper acetate, and

(e) up to 5 wt .- ^ of a halide, preferably of potassium iodide,

and a process for the production of this thread, which is characterized in that the polyearbonamide is made by Schraelzpoly- ^ merization in the presence of, based on the weight of the polymer,

(a) at least about 0.01% by weight of a phosphonate of the formula

0
RP-OX,

0
X '

where H denotes alkyl, aryl or arylalkyl radicals and X 'and X denote hydrogen, ammonium, substituted ammonium and / or a metal ion and can be identical to or different from one another,
* (b) 0.001. to 0.03 wt. Ji of a copper compound, preferably from

Copper acetate, and
(e) up to 5 wt .- ^ of a halide, preferably of potassium Io-

did
and that one forms a thread from it.

109817/1720

In a preferred embodiment of the present invention a halide is present during the polymerization.

The phosphonate compound is preferably added to the starting materials for the polymer before the polymerization, but it can also be added during the polymerization. You should _t voranechreitet during the polymerization be in a state of solution. If other additives are used, they are preferably present during the polymerization * so that an even distribution in the polymer is supported without subsequent mixing of the polymer being necessary.

Phenylphosphonic acid is used in the process and product of the invention usable. However, its neutralized salt, which can be obtained by adding hexamethylenediamine to a aqueous solution of phenylphosphonic acids in sufficient quantity, to adjust the pH of the solution to 6.2. The hexamethylenediansnonium phenylphosphonate can be prepared separately and added to the salt solution or the reaction mixture

109812/1720

BATH ORIGINAL

HP-1351

, or it can wordenα prepared in situ Hexaraethylendiammoniuraphenylphoaphonat precipitated from aqueous solution when its concentration exceeds 15 Gew.jt the solution "Its melting point is 230 ⁰ C, and it thermally decomposes rapidly at about 300%

It has been observed that the addition of any amount of a phosphonate auxiliary improves the absorption capacity for acidic dyes to a certain extent. Preferably, however, at least 0.01 £, based on the weight of the iolymeren added, and in general, it is desirable to add at least about 0.5 Sometimes _c 1 °, it is advantageous to administer amounts of up to the Lösliohkeitagrenae special Phoophonats in a special To use polyamide »

The addition of a soluble copper compound and a halide, ζ. Bo potassium iodide, as described in US-iatentechrift 2,705,227 is, however, not essential Optionally, about 0.001 to 0.03 wt. £ a copper compound and are added up to 5 wt _o # of potassium iodide to the polymer.

The following examples are intended to further illustrate the invention, however in no "limit trip"

10 9 81 ? / 17 2 0

^ß AD ORIGINAL

RD-1351

example 1

This example illustrates the method according to the invention and the improved dyeability of the mixture according to the invention in comparison with a similar mixture in which a dyeing aid is excluded ο

A polymerization technique similar to that of Example 1 of U.S. Patent 2,163,636 is followed. A 94.5 liter stainless steel autoclave equipped with a kit of a screw-shaped belt stirrer was purged of air and charged with aqueous solutions of the following ingredients;

Table I. Component dry weight Hexane ethylenedin ammonium adipate 23.65 Potassium iodide 0.041 Copper (II) acetate monohydrate 0.0041 Acetic acid 0.027 Hexacethylene dianunoniuaphenylphosphonate 0.123 Total water (approx) 29.1

The contents of the autoclave were ^{heated to about 210 °} C. and 17.6 kg / cm ² pressure. At this stage, water vapor began to flow out, and the contents of the autoclave were now forced to move

109812/1720

BATH ORIGINAL

RD-1351

began"

After a cycle in which the pressure was maintained, the temperature was dee autoclave to about 290 ⁰ O increases, while the pressure on Atmoaphärendruck was lowered * The acetic acid was used as Wk Aminendßruppenverechluss, to regulate the length of the polymer chain β After completion of the The polymerisation reaction had a relative viscosity of 38 <i The polymer is extruded in the form of a tape onto a casting drum »After being sucked, it is cut into pieces that are suitable for remelting on the host of a spinning plant ^ The poly (hexamethy lenadipamide) flakes are first geomolten in a steam atmosphere according to the teaching of Uü patent 2 571 975 (v / altz) and then spun at a speed of 375 m per minute into a yarn (A) and about five times into a 840 Din- 140-thread yarn veratreokt.

When omitting Hexamethylendiammoniumphenylphosphonat, one erhä'.it a polymer blend which delivers the yarn (B) ", if one of copper (Il) -acotat-rionohydrat and potassium iodide and Hexaraethylendiamtnoniumphenylphosphonat omit, one obtains a Polymerenmiaohung _t which the yarn (C) provides “The yarn (D) does not contain hexamethylene d iamuioniumphenylphoephonat.

The drawn yarns (A), (B), (C) ^ Q ^ jf ^ J ^ f ^^ ' ! Anß

BAD ORiGJNAL

RD-1351

washed in carbon tetrachloride to remove the finish and then air dried. These yarns are made with regard to compared the dye absorption by a 5 g strand of yarn 1 child was hung for a long time in a stirred, boiling solution (pH 6.5) containing 0.01 wt.% CL Acid Red 57.

Table II yarn

* 'Calculated from "Analytical Chemistry", Volume 19, p. 448, July 1947, j "Determination of. The Molecular Height of Nylon" by VaItB et al.

The values shown in Table II indicate that the Zueatz of hexamethylene diamine lumphenylphoephonate iu 66 polymers the Dye absorption capacity measured by this test method increased from 66 polymer to 1.5 times. The table furthermore shows that the Zuer.t «of copper acetate and

Potassium iodide in the specified concentrations has no effect

which is capable of dye absorption.

109812/1720 bad original

Amine end groups t /
(Equivalents / 10 ° g) Percent absor "
bated dye 49.0 55 43.3 36 53.4 36 49 53

JtD

HD-1351

B β i 8 P ie 1 2

Quarters produced according to Example 1 were tested in the tlas Model XVO Weather-o-meter according to the τοη of the Society of Automotive Engineers (ü.AE - J4C par 4,5 and 7 »5) described Öspeci-P cations ο The Indians Järgebnlese reproduced in Table III show that yarns A and B withstand degradation by heat and light much better than required aA ₀ Uc J4C (at least 60% of the strength must be retained) «

Table III

Yarns ψ retention of strength A 76

B 85

C 40

Case 3

This example illustrates the method of the invention and the improved processing that came with hexamethylene diammonium phenylphoaphonate is achieved.

The polymerization is based on the teaching of US patent specification

2,361,717 carried out to in «Inen continuous polymerization system Provide polymer. Oeaohnolsenes will rolymerei

- 10 - 109812/1720

BATH ORIGINAL

RD-1351

conveyed to a spinning plant, and yarn samples are spared from the polymer solution. A yarn equivalent to yarn A of Example 1 was spun, and an increase in the spinning pumping pressure of only 4.9 kg / hour. applies. This sample lost only 21% of the copper added to the system in the form of copper acetate in the polymer! The replacement of the hexamethylenediammonium phenylphosphonate in the polymer mixture with 0.5%, based on the weight of the polymer, of hexamethylenedlammoniurophenylphosphinate led to an increase in the spin pack pressure of 15.9 kg / hour when the polymer was spun into yarn. Up to 70 % of the added copper was lost in the polymerization spinning system. A high copper loss due to a reduction of copper ions to metallic copper particles is detrimental to the production of an acceptable yarn. Sr causes clogging of the spin pack and significantly reduces the service life of the spin pack. A high copper loss veruraaoht also contamination of Polymerisatlonsgefäese and sets their product ionsl level ^J except down. The combination of these three effects! (1) Making a quality product, (2) improving the life of the spin pack, and (3) improving the life of the polymerisation vessel are beneficial features of the present invention.

• 11 -

109812 / 172G BAD OBlGINAt

RD-1351

The invention is broadly applicable to linear polyamides, whose Carbonamidbindungeη an integral part of the Main polymer chain aindo

Typical polyamides of this type are those made from an aliphatic Diamine and an aliphatic diacid are built up and the calibration repeating unit

-X-Z-Y-Z

Contain, in the X and Y divalent, aliphatic, cycloaliphatic pool or gcr.isoht aliphatiach-cycloaliphatisoho groups and Z

the 0 H bond mean "Beaondera useful" Polyamides are the- -C-N-

those where -X- and -Y- (CHg) _n-1 mean »where η is a pooitivo integer from 1 to a hollow number 12 iat« -X- and -Ϊ "can be identical or different to a ₀ poly-hexaraethylene adipamide and polycaproamide (do ho nylon ⁿ 66 ⁿ and "6") are typical. Usable polyamides are also those in which -X- and / or - ¥ - cycloaliphatic or aliphatic-cycloaliphatic aind »t» B ₀ those of hexahydroterephthalic acid, bia- (4-aminocyolohexyl) methane and bia- (4-aminooyolohexyl) - propane-2 derived

Other suitable polyamides are those which repeat the calibration structure

-A-Z-X-Z-

-IS-

109817/1720

BATH ORIGINAL

RD-1351

have, in which -A- means a divalent aromatic heat and -X- and -Z- have the meaning defined above. Polyheirainet'iylenisophthalanid and poly (dimethylhexaraethylene terephthalaroid) are representative of such polymers «

In addition, IoIyamides can be used »welohe aioh repetitive Units like

-AZBZ-
and

-X-Z-B-Z-

have, in which -B- is divalent alkaryl (such as xylylene), provided that only the melt-spinnable polymers and mixed polymers are provided poly- (m-xylylene adipamide) and poly- (p-xylyleneebaoataid) are typisoh «

Another range of suitable polyamides, we loh · other oioh repeating units as aromatic · intra-carbonamide units included are those selected from piperazine, 8 x B. from Piperazine and adipic acid and the like also ethyl-substituted derivatives of piperazine.

The stabilized .polymeren iüsohun ^ s of this invention can also small amounts of ingredients, such as antistatieohtn liittoln,

109812/1720

HD-1351

Coloring auxiliaries and UV light absorbers, contained

Polymers and fish polymers which are modified according to the invention are useful for the firapinnea of continuous threads with round, lobed and irregular cross-sections and with either practically uniform or mixed titers grafted by irradiation aeir and they may have a hollow structure ₀ may yarns These stabilized polymers processed into cables and staple fibers and also made voluminous curled "are textured, etc. ·

The matting agent for the filamentary structures of this invention can be any of the conventional matting agents, . such as titanium dioxide, barium sulfate, aluminum trioxide, and the like. These matting agents are disclosed in dor Uö-fatentechrift 2 205 722.

For the Faohmann there are many other equivalent modifications, which do not deviate from the invention idea, after reading the above description is obvious.

109812/1720

BATH ORIGINAL

Claims (2)

EGG. du Pont de Nemours and Company KD-1351 / P 42 060 claims 1. Synthetic poly carbonamide thread »characterized by a content »based on the weight of the polymer» (a) at least about 0.01 weight percent of a phosphonate of the formula ₀ H-P-OX 0
X ¹ where R is alkyl »aryl or arylalkyl radicals and X * and X denote hydrogen »ammonium» substituted ammonium and / or a metal ion and are identical to or from one another can be different » (b) 0.001 to 0.03 wt% of a copper compound is preferred of copper acetate »and (c) up to 5 parts by weight of a halide, preferably of potassium iodide. 2. thread according to claim 1 »characterized in that the Phoaphonat Hexametbyleadlammonumphenylphosphonate is. 3 · thread according to claim 1 or 2 »characterized» that he Contains at least 0.5 wt% of phosphonate. - 15 - 109817/1720 RD-1351 A 4 · Process for the production of the thread according to claim 1, characterized characterized «that the Polyoarbonaaid by melt poly · ■ Erlsatlon in the presence of, based on the weight of the «poly- (a) at least about 0.01% weight of a Phoephonate of the formula .0 RP-OX » • i where R denotes alkyl, aryl or arylalkyl radicals and X * and X is hydrogen, ammonium, substituted aanonlu and / or mean a metal ion and can be the same or different from one another, (b) O ₉ OOl to O ₉ O? Oeii.- £ a copper compound "vorxuenieise von copper acetate" and (o) up to 5 g of a halide, preferably of potassium iodide,
W and that aan forms a thread from it. 5. The method according to claim 4, characterized in that the phosphonate, the copper compound and the halide torltufern of the polycarbonaaida starts before it polymerizes, - 16 - 109812/1720 bad original