DD236747B1 - METHOD FOR THE PERMANENT OBJECTIVE STRUCTURAL EQUIPMENT OF POLYMERS FOR TEXTILE FIBERS - Google Patents

Description

Field of application of the invention

The invention relates to a process for the permanent antistatic treatment of polymers for textiles and silks, in particular of polyamides

Characteristic of the known technical solutions

Textile materials, especially synthetic fibers, are widely used in particular for the production of clothing and home textiles. Synthetic fibers have advantages over natural fibers, in B in strength and abrasion resistance. A significant disadvantage, however, is the tendency to electrostatically charge End consumers of such final products in B in the form of anemanderklebens of garments, disturbing electrical discharges when wearing textiles or when walking on synthetic carpets unpleasantly noticeable But not only the utility value of the textiles is impaired Due to the high static charge diverse production problems occur in the Production of fibers, fabrics and final products

The disadvantages presented demonstrate the need to produce polymeric fibers with high non-electrostatic properties without affecting the positive desired properties. Many attempts have been made to overcome these disadvantages

Thus, processes are known, by the incorporation of hydrophilic substances in the polymer phase, such as Β Β polyethylene glycols of different molecular weights (DE-OS 2315990, DE-OS 251 940, DE-OS 1 494720, DE-AS 1 286683), ethoxylated long-chain alcohols ( DE-OS 2110412, DE-OS 2109030, DE-OS 2214119), ethoxylated acid amides (DE-AS 131 890), ethoxylated polypropylene glycols (DE-OS 1,694,459 and DE-OS 2,251,280), terminally alkylated polyethylene glycols (DE-AS 1 273124) to achieve anti-electrostatic properties

Disadvantages of these methods are the insufficient permanent antistatic properties of the polymeric fibers made therefrom

The modification of the polyethylene glycols by hydrophilic salt-like groups (DE-OS 2243425) or the use of inorganic salts or ionogenic organic compounds could not eliminate the disadvantages listed

Of course, the listed chemical compounds can also be applied via the path of the aftertreatment or surface treatment. However, the permanence of the antistatic equipment is thereby further worsened

It is known that by adding ethylene oxide onto high molecular weight primary amines containing a long-chain hydrocarbon radical, surfactants can be prepared which are highly versatile. Thus, they are used in cosmetics, as textile treatment agents, as anticorrosion agents and as antistats for finishing textile fibers and polymeric materials used

The production of said polyaddition products from amines and EO is known from DRP 667744, CH-PS 346225 from the relevant literature (Schonfeld, N, interface-active ethylene oxide adducts). It is usually carried out in the presence of alkaline catalysts such as metallic Na or alkali metal hydroxides at elevated temperatures (170 ⁰ C) under pressure

The oxethylates of long chain amines are widely used as modifiers for the anti-electrostatic finishing of polymers. The use of these low level of alkoxylation agents in combination with other static electricity accumulation charge promoters on polymers such as polyolefins, styrene polymers, PVC and textile materials (polyacrylonitrile, polyester) is taught in US Pat DE AS 1 083225, DE-AS 1 089725, DE-AS 1 248932, DE-AS 1 262593, DE OS 1544712, DE-AS 1694525, DE-AS 1949421, DE-OS 2033642 also describes the use of fatty amine-alkylene oxide Adducts of higher degree of alkoxylation than antistatic agents for thermoplastics and man-made fibers are known from the following patents NL-PS 291 116, US-PS 3519561, US-PS 3592879, DE-OS 2306066, DD-WP 139606 The known alkylamine polyglycol ethers are not suitable for the permanent antistatic Modification of polyamide by way of dosing prior to polymer production at temperature in excess of 260 ^° C. and residence times in the reaction vessel of a large 20 hours are carried out, since an unacceptably high drop in the degrees of whiteness of the modified polyamides occurs in the same way too high a catalyst concentration and too long a reaction time in the preparation of Alkylaminpolygiykolether have a negative effect on Whiteness of the polyamides modified with these compounds

When using carpet texturides in velor products that are modified with additives of alkylamino polyglycol ethers usually prepared, the antistatic effect and its permanence does not meet the international requirements

Object of the invention

The object of the invention is to improve the properties of polymers and the fibers and silks made therefrom so as to have sufficient permanence with respect to antistatic effect, high whiteness and higher, more stable processing properties than products synthesized by known methods it continues to achieve this antistatic finish through modifiers that are not combinations of several substances

Explanation of the essence of the invention

- The technical problem of the invention

The invention is based on the object of providing a process for the permanent antistatic treatment of polymers for fibers and silks, in particular polyamides, by using an alkylamine polyglycol ether of the formula

-GH ₂ -O) ε Η

E-N- ~

(CII ₂ - GH ₂ - 0) b H

where R is an alkyl group having 15 to 22 carbon atoms and a + b is 80 to 150 ethylene oxide units. The modifier is said to be added prior to the polymer preparation and to meet the high demands placed on the substance by the polymer manufacturing conditions

Features of the invention

The technical object is achieved according to the invention by using an alkylamine polyglycol ether containing up to 12% polyethylene glycol. The alkylamine polyglycol ethers having the reduced polyethylene glycol content are prepared by adding the ethylene oxide to the long-chain alkylamines at temperatures <145 ^° C., at catalyst concentrations of 1, 5 to 3% Alkahhydroxyd and high reaction rate The modifier according to the invention is added in concentrations up to a maximum of 5% based on the polymer

These polyglycol ethers of long-chain fatty amines are characterized by a low content of by-products and a high thermostabihtate which, in contrast to the known methods of antistatic modification of polymers and synthetic fibers or silks, allows the antistatic modifier to be economically obtained prior to polymer production It was found as a decisive advantage of the inventive method that the use of an alkylamine polyglycol ether with a reduced proportion of polyethylene glycol as antistatic agent for polyamide fine silk and polyamide carpet synthetic silk leads to a very good antistatic effect with sufficient permanence. The melting behavior on the spider extruder is improved seriously and it becomes more stable processing properties achieved in the subsequent stretching process The threads have a high degree of whiteness Further advantages of the inventive method are that the antistatic modifier or in a one-step reaction can be prepared in a simple manner from long-chain alkylamines and ethylene oxide and need not be combined with other modifier components. Accordingly, additional inhomogeneities in the modifier distribution and resulting processing and quality problems do not occur

The metering of the antistatic agent into the VK tube prior to polymer production brings significant technological and economic advantages over other antistatic modification techniques, such as modifying the modifier into the extruder or the known surface treatment methods, and also results in a higher permanence of antistatic effect over the prior art Process for the treatment of surfaces

embodiments

The solution according to the invention is illustrated by the following examples

example 1

A continuous reaction tube was fed 15 kg / h reaction mixture of the following composition

Caprolactam 95.39%

Water 2.00%

Matting agent 0.35%

Acetic acid 0.06%

Antistatic modifier 2.20%

As antistatic modifier was a polyglycol ether of the formula

(GH ₂ -CH ₂ -O) aH

R-N

^^^ - (CH ₂ -CH ₂ -O) 1) H

used, wherein R is an alkyl radical of C number 16 to 18 and the sum of a + b is 100 and which was prepared under the following reaction conditions by ethoxylation of the monoalkylamine: reaction temperature: 135 ⁰ C.

Catalyst concentration: 2.0 wt .-% The average throughput time in the reaction tube was 20 hours, the reaction temperature is about 265 ⁰ C. After extraction and drying were carried out on the obtained granules have a relative solution viscosity of 2.53 and the residual extract with 0.9 % certainly. The granules were spun on an extruder to fine silk with a linear density of 4.4 tex. The warp knit fabrics were tested for their permanent antistatic properties and whiteness of the silk. At the same time, the by-product constituents as well as the color appearance and the thermostability of the antistatic modifier prepared according to the above synthesis conditions were determined. The results are included in Table 1.

Example 2

As Example 1, but with the difference that was used as an antistatic modifier, a polyglycol ether of a monoalkylamine of the same formula, but prepared under the following reaction conditions: reaction temperature 175 ° C.

Catalyst concentration 2.0 mass% The results are shown in Table

Example 3

As Example 1, but with the difference that was used as an antistatic modifier, a polyglycol ether of a monoalkylamine of the same formula prepared under the following reaction conditions: reaction temperature 142 ⁰ C.

Catalyst concentration 1.0% by mass The results are shown in Table

Example 4

As Example 1, but with the difference that was used as the antistatic modifier, a polyglycol ether of a monoalkylamine of the same formula prepared under the following reaction conditions: reaction temperature 150 ⁰ C.

Catalyst concentration 5% by mass The results are shown in Table

Example 5

The following reaction mixture was added to a continuously operating reaction tube:

Caprolactam 98.2%

Water 0.5%

Matting agent 0.1%

Antistatic 1.2%

Acetic acid 0.03%

The antistatic agent was chosen according to Example 1. The average residence time in the reaction tube was 26 h at a reaction temperature of about 265 ^° C.

The rel. Solution viscosity of the polyamide after extraction and drying was 2.82 for a residual extract of 1.1%. The spun-dyed granules were processed through a spider extruder and a stretch-texturing machine to make carpet purse silk with a fineness of 260tex. The velor carpets made from this material after twisting and saturation were tested for their permanent antistatic properties according to TGL 16-650576.

The resistance was measured according to TGL 16-650272. The washes or secondary cleaning were carried out under the following conditions:

Washing temperature 3O ⁰ C

Wash time 30 min

Detergent 1 gWofapon / l water

Rinse 2 χ at 30 ° C and 1 cold

Fleet ratio 1:50 The results are shown in the table

Example 6

As example 5, but with a modifier according to example 3. The results are given in table 2.

The processing properties achieved according to Examples 5 and 6 are shown in Table 3 while maintaining the numbers of

Embodiments set forth.

Example 7

The following reaction mixture was added to a continuously operating reaction tube:

caprolactam 98.2% water 0.5% matting agent 0.1% antistatic 1.2% acetic acid 0.03%

As antistatic modifier, a polyglycol ether was selected according to Example 1, which, however, was prepared by ethoxylation of the monoalkylamine under the following reaction conditions:

Reaction temperature: 130 ^° C.

Catalyst concentration: 2.5%

The mean residence time in the reaction tube was 26 h at a reaction temperature of about 265 ⁰ C.

The relative solution viscosity of the polyamide after extraction and drying was 2.80 for a residual extract of 1.05%. The spin-dyed granules were processed analogously to Example 5. The produced velor carpets were as in Example 5

described tested. The results of all tests are shown in Tables 1-3.

Table 1

Ex. - Ex. Antistatic modifier PEG content Iodine color number (%) 2 30-40 10-20 10-20 Thermostability Weight loss (%) up to 200 ° C to 225 ° C 53.5 59.5 68.5 56 Oxide. Oxide, start max. ⁽⁰ C) CC) synthetic silk whiteness surface resistance n.Ou. LOW BOUNDS 0 100 8.0-10 ¹² 2.0 · 10 ¹³ 3.9 · 10 ¹³ 9.1-10 ¹³ 4.5-10 ¹³ 9.5-10 ¹³ 2.0-10 ¹³ 8.9-10 ¹³ 1 2 3 4 11.9 • 30.6 31 40.6 30 37.5 46 36 151 182 140 170 143 178 145 175 83-84 68 70 66 Table 2 Thread resistance unwashed ρ N (Ω / cm) Velor carpet body potential (kV) untreated after 3 wet cleanings Execution example

1.8-10 ¹² 1.6-10 ¹³ 1.4-10 ¹²

2,3-1O ¹³ 8,4-10 ¹³ 1,9-10 ¹²

2.2 4.7 2.3

Table 3 Processing properties

Example Thermooxidation Polyamide Extruder Abschmelzleistung

T _Beg T _max at comparable speed

CC) 'CC' '(kg / h)

Yarn breaks / IOOkm stretch texturing

Yarn breaks / kg of turmoil

UI 158 180 260 0.3 0.03 6 133 168 225 0.4 0.06 7 156 181 260 0.25 0.02

Claims (1)

Process for the permanent antistatic treatment of polymers, in particular of polyamides for fibers and silks, with alkylaminopolyglycol ethers of the formula _ (pp) _n H B-N r 2 2a ^ - - (GH ₂ -CH ₂ -O) _b H wherein R is an alkyl radical having 15 to 22 carbon atoms and a + b represent 80 to 150 Ethlyenoxideinheiten which have a technical grade of polyethylene glycol and are added before the polymer production, characterized in that Alkylaminpolygiykolether with a reduced content of polyethylene glycol to max. 12% by weight.