DE2348664A1 - PROCESS FOR MELT SPINNING A FIBER-SHAPED STRUCTURE FROM A SYNTHETIC POLYAMIDE POLYMER, ANTISTATIC POLYAMIDE FIBERS AND ANTISTATIC COMPOSITIONS - Google Patents

Description

German patent application VjJjSÜÜi—- position for input P 23 48 664.8 - Al 43 "of November 26, 1973

Process for melt spinning a fibrous Structure made of a synthetic polyamide polymer, antistatic. Polyamide fibers as well as antistatic Con-oos itions

The present invention relates to a process for melt spinning a fibrous structure made of a synthetic polycmide polymer and antistatic polyamide fibers.

It has been suggested that the utility of synthetic fibers can be increased and their properties, especially their antistatic properties, improved, v: when the polymer contains a high molecular weight polyalkylene ether. In particular, U.S. Patent No. 3,475,898 to Magat and Sharkey discloses the use of poly (ethylene propylene) ether glycols for this purpose. In U.S. Patent 3,657.386 disclosed that certain propylene oxide-ethylene oxide copolymers _t on Athylendiaminbasis in the preparation of an antistatic Polyamidfaser- are particularly useful.

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So far there have been polyamide fibers that have an antistatic effect Polyaikyienather with 'high kioiekular weight contain, manufactured, but there were serious ... trials " because of the frequent occurrence of "drips" leg melted Foiyner when it grains out of the spinneret. The term "drips" is to be understood in the usual sense and v; ird verv: ends, un drops out. to denote molten polymer, soft completely prevent the normal extrusion of the polymer and thus the production of threads.

In this case, it is necessary to wipe the surface of the spinneret at short intervals during spinning in order to maintain normal Enable the spinning process. Often the titer (denier, yarn count ") of the spun thread varies depending on the type of yarn Teardrop shape. The frequent interruptions, however, inhibit the industrial operation.

It is therefore an object of the present invention to provide a synthetic polyanide fiber with improved color strength and improved antistatic properties and an improved melt spinning process for their manufacture.

Another object of the invention is to provide an improved melt spinning process for making a antistatic polyamide fiber, in which the formation of drops is avoided or substantially reduced.

According to the present invention, there is an improved one Process for the production of an antistatic polyamide fiber from a synthetic, linear, fibrous end Polyamide polymer that has a small amount of an antistatic

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BATH ORIGINAL

Polyether compound contains which by reacting an amine having at least one primary group with at least • an alkylene oxide having 2 to 4 carbon atoms, preferably a polyether compound of the formula

CH ₃ H (OCH ₂ CH ₂ ) (OCHCH ₂ )

CH ₃ H (OCH ₂ CH ₂ ) _z (OCHCH ₂ )

is obtained. In this formula, a, b, c, d, -w, x, y mean and ζ is an integer each, the sum of a, b, c and d is between 8 and 850 and the sum of w, χ, y and ζ is between 8 and 1000. In this process, the molten polymer is ex ~ trudes. The method according to the invention consists daxin, that he

a) the polyether compound with at least 0.01 mole, preferably 0.1 to 3 moles, per mole of one polyether compound sulfur compound of the formula which is soluble in the polyether compound

O -Metal Il R-S-O η Il 0

and / or a compound of the formula

R-S-OZ

Il

ο -

wherein R is alkyl, cycloalkyl, aryl or aralkyl, η is a integer which corresponds to the valence of the metal, and Z is hydrogen, an ammonium cation or a substituted one Ammonium cation mean, converts and

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, li - :? ■:.? ■ ::.? ■% 0 ^ 1

b) before extrusion in the polyamide polymer about 1 to

based on the weight of the polyamide polymer, the reaction product dispersed from the polyether compound with the sulfur compound.

Under a "synthetic, linear, fiber-forming polyamide polymer" is to be understood as a fully synthetic polymer, which has a predominant number of recurring Has units which have a hydrogen atom on the α-carbon with respect to the nitrogen atom of the amide unit Have chain. Such polymers can be defined quite generally as polyamides, since they contain the carboxamide unit.

= N-C- contained as a link in the polymer chain.

The term "by extruding the molten polymer, through an opening in a quench "is to be understood as referring to the conventional melt spinning process is meant, wherein the molten polymer through an opening in a medium, such as a liquid or a gas in the generally an inert gas - which is pressed to cool it down and into an elongated, essentially solidify continuous structure.

The reaction of the polyether compound with the sulfur compound can be carried out by simply mixing ^{the reactants at temperatures of about 25 °} C. or higher, preferably at a temperature of 75 to 110 ^{° C.}

As noted, the present invention is an improvement over that disclosed in U.S. Patents 3,657,386 and US Pat other previously published patents disclosed processes for the production of antistatic polyamide fibers, the polyether compounds, such as propylene oxide

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Ethylene oxide copolymers based on ethylene diamine, contain, The sulfur compounds which can be used for the present invention . are known, some of them are cheap off-the-shelf connections.

For example, p-toluenesulfonic acid, p-toluenesulfonic acid sodium salt and methanesulphonic acid are readily available and, as can be seen from the examples below, excellent results.

It has been found that the viscosity of the polyether compounds according to the invention is significantly increased by reacting with the sulfur compounds. In addition, this high viscosity is a primary prerequisite for the improved dispersibility of the polyethers in the molten polyamide for the production of antistatic fibers. The increased viscosity of the antistatic additive according to the invention is an essential factor in improving the melt spinning process of the polyamide polymer, since the formation of drips "is thereby essentially eliminated in the molten polymer as it exits the spinneret. The melt viscosity of the improved, inventive anti-static additive is preferably at least 3000 centipoise at 100 ⁰ C.

The present invention is based on the following examples, which are by no means restrictive, explained in more detail.

The ethylene diamine-based propylene oxide-ethylene oxide copolymers used in the preferred process according to the invention are described in US Pat. Nos. 2,979,528 and 3,657,386. These compounds are called "Tetronic" series block copolymers commercially available with molecular weights from 1650 to over 26,000. This series varies in length · the Poly (oxyethylene) and the poly (oxypropylene) chain. One

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Three or four-digit code number gives the molecular composition at. In a four-digit number, the first two digits mean the average molecular weight of the hydrophobic / poly (oxypropyleneJ_7 branches on alkylenediamine. In the case of three-digit numbers, only the first digit has this meaning. The last digit of each code number means the percentage by weight of the hydrophilic poly (oxyäthylenJJ units from 10 to 10%. The "Tetronic" compounds in the examples are described in this way.

Example 1:

About 200 "Tetronic 1504" g are introduced in a 500 ml beaker and heated to 8O ⁰ C. "Tetronic 1504" is a propylene oxide-ethylene oxide block copolymer based on ethylene diamine with a molecular weight of about 12,500 and an ethylene oxide content of 40%. About 6.08 g of p-toluenesulfonic acid monohydrate are added to the "Tetronic 1504" with stirring over the course of 15 minutes. The reaction mixture is kept at about 80 ° C. and stirred for a further 30 minutes. The melt viscosity of the resulting reaction product is 9600 centipoise, measured at 100 ^° C., using a Brookfield viscometer. The original "Tetronic 1504" was at 100 ⁰ C a viscosity of 200 cps.

Example 2:

The procedure described in Example 1 is repeated, except that the p-toluenesulfonic acid is replaced by 6.21 g of p-toluenesulfonic acid sodium salt. The molar ratio of the sodium salt to the polyether is about 2. The melt viscosity of the resulting reaction product is 30,000 centipoise, measured at 100 ^° C. with a Brookfield viscometer. The thermogravimetric analysis of this product shows a weight loss of only 6% within 30 minutes at 285 ° C.

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Example 3: '

The product shown in hexagon according to example 2 is used to in order to obtain an antistatic polyamide fiber containing a polyether compound according to the procedure given below, to manufacture:

A mixture of 1520 g of e-caprolactam and 80 g of aminocaproic acid is introduced into a glass reactor provided with a heat source and a stirrer. The mixture is then purged with nitrogen, stirred for one hour at atmospheric pressure and heated to 255 ° C. to initiate the polymerization reaction. In order to complete the polymerization, heating and stirring are continued for a further 4 hours under atmospheric pressure and under nitrogen. During the last 30 minutes of the polymerization, 60 g of the antistatic agent, which had been prepared according to the process described in Example 2, are added to the polycaproic acid amxd. Stirring is continued to thoroughly mix the antistatic agent with the polymer. Nitrogen is then introduced into the glass reactor, a slight excess pressure being maintained while the polymer is extruded from the glass reactor in the form of a polymer tape (strand). The polymer ribbon or strand is then cooled, pelletized in a Wiley mill, washed, and then dried. The polymer is a white solid having a relative viscosity of about 55 to 60, it is determined at a concentration of 11 g polymer in 100 ml 90% formic acid at 25 ⁰ C (ASTMD-789-62T). The particle size of the antistatic additive distributed in the polymer chips was 3-5 μm .

The polycaproic acid amide pellets containing the antistatic agent are melted at about 285 ° C and then through a spinneret at a pressure of 1500 psig (105 atmospheres) with 16 openings, each of which has a diameter of

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0.014 in., Melt spun to a fiber of Obtain 250 denier. In melt-spinning the antistatic polyamide fiber, there was no problem and it there was also no evidence of the formation of "drips" in the molten fiber as it exited Spinneret. The fiber was collected at a rate of about 1000 feet (304.8 m) per minute and onto the 3 72 times its extruded length drawn or stretched, to make a 70 denier yarn, hereinafter referred to as yarn "A". Following the same procedure a control yarn with no antistatic agent was made and designated yarn "B".

Example 4:

The 70 denier polycaproic acid amide yarn with the antistatic Means and that also produced according to Example 3 Kon- ' Troll yarn has been processed into conventional, simply woven fabrics. The yarns contained a / 2 Z twist. The fabrics were cut into test specimens 3 inches (7.6 cm) wide and 9 inches (22.9 cm) long. The test samples were made according to the "Technical Manual of the American Association of Textile Chemists and Colorists", 1969 edition, Volume 45, Pages 206 and 207, tested method described for their antistatic properties. This test procedure is known as the "Electrostatic Adhesion of Fabrics; Cloth-on-Metal Test" and carries the designation AATCC 115-1969.

The period of time within which each test sample detached itself. Fresh test and rub fabrics were used for each determination, the samples were tested in triplicate in the warp and weft directions with nylon and polyester abrasive fabrics.

The test samples were washed repeatedly to determine the durability of that caused by the antistatic agent

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evaluate antistatic properties. The fabrics were washed in a commercially available washing machine with conventional washing and washing cycles at a temperature of about 70 ° C. with a conventional detergent. The fabrics were then dried in a commercially available dryer at temperatures of about 80 ^° C. for about 30 minutes. Before testing, the fabric samples were ironed smooth with a clean, dry iron with the appropriate setting and then conditioned from the dry side at 20% relative humidity and a temperature of 24 ° C for at least 24 hours (Technical Manual of the AATCC, page 206 , Paragraph 4.3, Note 9.5).

Table I below shows the average times within which each set of swatches completely dissolved by itself after 0 and 25 washes, respectively. The antistatic measurements were made at 20 % relative humidity and at a temperature of 24 ° C as described in the AATCC procedure.

Tabel

Electrostatic adhesion of the Fabrics 25 washes Results of the substance-to-metal test 60 Antistatic
in the fabric middle Average times within
which the swatches of
detach yourself completely from the metal,
in seconds > 300 unwashed after Yarn A 0 Yarn B 0

The textile industry currently considers stick times of 300 seconds or less to be acceptable and indicative of remarkable antistatic properties, therefore the control yarn B was not acceptable, while the addition in this-

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This example gave yarn A good antistatic properties.

Example 5:

The procedure described in Example 2 is followed, but only 3.1 g of p-toluenesulfonic acid sodium salt are reacted with the 200 g of "Tetronic 1504". The resulting antistatic agent has a melt viscosity of 16,000 centipoise at 100 ⁰ C.

Example 6;

The procedure described in Example 3 (yarn "A") is followed, but 90 g of the antistatic given in Example 5 are used Addition. The average particle size of the antistatic additive in the polyamide is about 4 to 6 -u. The polyamide fiber is produced as described in Example 4, the adhesion test on the fabric gives an average Holding time of 78 seconds after 25 I washes.

Example 7:

Proceed as described in Example 3 (yarn "A"), but use 90 g of the antistatic additive from Example 2. The polymer is spun and drawn or stretched, it is formed when the molten polymer emerges the spinneret no "drips". The fabric is woven or knitted and tested as in Example 4, and the adhesion test results an average stick time of 47 seconds after 25 washes.

Example 8:

Proceed as described in example 3 (yarn "A"), but use 90 g of the antistatic agent from example The polymer is spun and drawn or stretched, it

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No drops form when the molten polymer exits the spinneret. The fabric is as in Example 4 woven or knitted and tested, the adhesion test shows an average adhesion time of 43 seconds after 25 washes.

Example 9:

One proceeds as in Example 3 above, but with the exception of the following changes: the Polycapronsäureamxdpellets the antistatic agent-containing melted at about 285 ⁰ C and then at about 15 psig (1.05 atm) pressure through a spinneret having 70 holes, of which each 0.018 inch (0.4 mm) in diameter, melt spun into 4500 denier fiber. The fiber is collected at a rate of 100 feet (304.8 m) per minute and drawn to about four times its extruded length to yield 1125 denier yarn. As described above, a control yarn with no antistatic additive is made. The yarns are textured using a steam jet and then plied into two strips. These yarns are made into a carpet with uniformly high loops with 6.5 stitches and a pile height of 9-10 / 32 inches

processed, shimmered and provided with a latex backing. The static charge on the carpet is tested by measuring the increase in electrostatic voltage on a person walking across a piece of carpet in short, dragging steps. This test is an adapted form of the CRI Stroll test (walking test) for testing smaller carpet samples. The carpet is conditioned at 70 ° F (21 ⁰ C) with a relative humidity of 20%. The resulting voltage is 2.9 KV, while 10 KV was measured on a control carpet.

Example 10:

Proceed as described in Example 1, but set 3.08 g of methanesulfonic acid with the "Tetronic 1504". The

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avowed antistatic agent has a melt viscosity of 6400 centipoise at 100 ⁰ C.

Example 11:

The procedure described in Example 3 (yarn “A”) is followed, but 90 g of the antistatic additive from Example 10 are used. The polymer is spun and drawn without the molten polymer emerging from the spinneret Form drops. The fabric is woven and tested according to Example 4; the adhesion test gives an adhesion time of 63 seconds after 25 washes.

Example 12:

The procedure described in Example 1 is followed, but the 200 g of "Tetronic 1504" are replaced by 200 g of ethylene oxide-propylene oxide block copolymer made from triethylenetetramine with a molecular weight of 34,500 and an ethylene oxide content of 70%. Only 4.37 g of p-toluenesulfonic acid are also used. The melt viscosity of the resultant reaction product is 2800 centipoise as measured at 100 ⁰ C. The melt viscosity of the initial copolymer was 1,720 centipoise at 100 ° C.

Example 13:

The procedure described in Example 3 (yarn “A”) is followed, but 90 g of the antistatic additive from Example 12 are used. The polymer is spun and drawn, it is formed when the molten polymer exits the spinneret no drops. The fabric is woven and tested as in Example 4. The adhesion test gives an adhesion time of 79 seconds after 25 washes.

Example 14:

Proceed as described in Example 3 (yarn "A") with

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with the exception that the polyamide is made from poly (hexamethylene) adipamide salt is polymerized. A fiber is produced and a fabric is knitted from it and as described in Example 4 tested. The average retention time is 60 seconds after 25 washes.

Summary:

In further tests it was found that the molecular weight of the propylene oxide-ethylene oxide copolymer based on ethylene diamine, which is used to produce the antistatic additive according to the invention, preferably more than 1500, in particular between 4000 and about 50,000, and that the ethylene oxide contents about 20 to about 80% of the Molecular weight of this compound. Preferably the antistatic fiber contains between about 2 and about 8 / O of the new anti-static additive.

"Antistatic" fibers are understood to mean those fibers which pass the adhesion and ^{walking tests, 1} as described in US Pat. No. 3,657,386. "Fiber" is to be understood as meaning multi-filament and single-filament yarn and all known forms of synthetic fibers. "Ethylene oxide content" is to be understood as meaning the content of the remainder of the formula - (CH ₂ CH _{2 O) -.}

It is recommended to use the antistatic polyether additive in the to be dispersed substantially evenly in the polyamide.

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Claims (4)

Ι REACHED Patent claims: HU) Process for the production of an antistatic • polyamide fiber from a synthetic, linear, fiber-forming Polyamide polymer containing a small amount of a polyether antistatic compound by reacting one Amine having at least one primary group with at least one alkylene oxide having 2 to 4 carbon atoms and extruding of the molten polymer through an opening in a quenching means, characterized in that for prevention the appearance of drops during extrusion a) the polyether compound having at least 0.01 mole per mole of polyether compound of one in the polyether compound soluble sulfur compound of the formula Il R-S-O -Metal and / or a compound of the formula 0 R-S-OZ ir wherein R is alkyl, cycloalkyl, aryl or aralkyl, η is a integer which corresponds to the valence of the metal, and Z is hydrogen, an ammonium cation or a substituted one Ammonium cation is converted, and b) prior to extrusion in the polyamide polymer about 1 to about 12/0, based on the weight of the polyamide polymer, des Reaction product of the polyether compound are dispersed with the sulfur compound. 2. The method according to claim 1, characterized in that the polyether compound is one of the formula 4098 15/1048 Al 43 - 14 - .! - iiDiSO CAB close-up] H (OCH ₀ CH ₀ ) (OCHCH ₀ )>. > (CH ₀ CHO) (CH ₀ CH ₀ O) H CH, .NCH ₂ CH ₂ N _CH Η (OCH ₂ CH ₂ ) _ζ (OCHCH ₂ ) _d (CH ₂ CHO) _fe (CH ₂ CH ₂ O) _w H used, where a, b, c, d, w, x, y and ζ are integers and the sum of a, b, c and d is between 8 and 850 and the sum of w, x, y and ζ is between 8 and 1000, and that The molecular weight of the polyether compound before reacting with the sulfur compound is more than 1,500. 3. The method according to claim 1, characterized in that the sulfur compound is p-toluenesulfonic acid, p-Toluenesulfonic acid sodium salt or methanesulfonic acid begins. 4. The method according to claim 1, characterized in that 1 mole of the polyether compound with about 0.1 to 3 mol of the sulfur compound is implemented. 5. The method according to claim 1, characterized in that the polyether compound is reacted ^{with the sulfur compound at temperatures between about 75 and HO 0 C.} 6. An antistatic polyamide fiber, which is between about 1 wt -.% To about 12 wt .-%, based on the weight of the polyamide of the reaction product a) a polyether compound with a molecular weight of more than 1500 obtained by reacting an amine with at least a primary group with at least one alkylene oxide having 2 to 4 carbon atoms was obtained, with b) a sulfur compound of the formula R-S-O -Metal Al 43 -15- 409815/1048 BAD'ORIGINAL * and / or a compound of the formula RS-OZ
O wherein R is alkyl, cycloalkyl, aryl or aralkyl, η is a integer corresponding to the valence of the metal and Σ hydrogen, an ammonium cation or a substituted one Is ammonium cation, contains, wherein the molar ratio of the sulfur compound to the polyether compound is at least 0.01. 7. Fiber according to claim 6, characterized in that the polyether compound has the formula CH ₃ 'CH ₃ H (OCH ₀ CH ₀ ) (OCHCH ₀ ). . ^ - (CH ₀ CHO) (CH ₀ CH ₀ O) H CH ₃ ^ * Ά £ Ά # CH ₃ H (OCH ₂ CH ₂ ) _z (OCHCH ₂ ) _d (CH ₂ CHO) _fa has, wherein a. b, c, d, w, x, y and ζ are integers, the sum of a, b, c and d is between 8 and 850 and the sum of w, χ, y and ζ is between 8 and 1000, and the molecular weight of the polyether compound before reacting with the sulfur compound is more than 1500. 8. Fiber according to claim 7, characterized in that the sulfur compound is p-toluenesulfonic acid, p-toluenesulfonic acid sodium salt or methanesulfonic acid. 9. Fiber according to claim 6, characterized in that 1 mole of the polyether compound with about 0.1 to 3 moles the sulfur compound is reacted. 10. A fiber according to claim 6, characterized in that the Polyathervexbindung with the sulfur compound at temperatures of 75-110 ⁰ C is reacted. 4 09815/1048 BAD ORIOiNAL