DE1469106C - Process for improving the dyeability of thread made of polyolefins - Google Patents

Description

The invention relates to the production of improved textile threads, which essentially consist of crystalline polyolefins, obtained by low pressure polymerisation, such as polyethylene, Polypropylene, polybutene or mixtures of these polymers, and are easier to dye,

The subject of patent 1 251 903 is a process for improving the dyeability of threads and films or ribbons of polyolefins by intimately mixing polyolefins or polyolefin blends with one or more polymers with an affinity for dyes that are insoluble in water or during spinning become water-insoluble and which are soluble or emulsifiable in the molten polyolefin, further a Have a molecular weight of at least 1000 and a lower second-order transition temperature than the melting point of the polyolefin, melting the polymer blend and usual molding by extrusion, which is characterized in that polyalkyleneimines, substituted polyalkyleneimines, copolymers of alkyleneimines, by polycondensation polyester resins, polyaminotriazoles, polyamides obtained from dicarboxylic acids with glycols, by polyaddition Polyurethanes obtained from diisocyanates and glycols by polyaddition of diisocyanates polyureas obtained from diamines, polyalkyleneimine-polyamide mixtures or polyalkyleneimine-epoxy resin mixtures used.

Surprisingly, it has now been found in a further development of this process that textile thread can be used with improved dyeability from polyolefins or polyolefin mixtures by conventional shaping from molten masses of dye-affine polymers and polyolefins or polyolefin mixtures can, if one has as dye-affine polymers in the molten masses 0.5 to 25 percent by weight, based on the weight of the polyolefins, a basic nitrogen compound with a resinous character, by reacting dichloroethane with polyfunctional amines, optionally in the presence of solvents or condensation agents and any subsequent alkylation of the reaction product are used.

For this purpose, polymers are particularly suitable with polyfunctional amines, such as Hexamethylene diamine, ethylene diamine, 1,2-propylene diamine or diethylenetriamine.

In their production, alkyl halides such as lauryl chloride, cetyl chloride, Stearyl chloride, octadecyl chloride and the like are particularly suitable. The condensation reaction between the polyfunctional amine and dichloroethane becomes appropriate carried out using one mole of dichloroethane per 0.01 to 2.5 moles of the polyfunctional amine. If amounts smaller than 1.02 moles of polyfunctional amine are used, undesired results result Crosslinking phenomena in the condensation product, which becomes infusible as a result and is then no longer suitable for the purpose according to the invention. The alkyl halides can be in a Amount "of 0.01 to 2 moles can be used. A mixture preferably used is a mixture of polypropylene with 4% of a product obtained by reacting 1 mol of dichloroethane with 1.25 mol of hexatriethylenediamine and 0.5 mole of lauryl chloride is obtained.

Particularly suitable amine compounds are obtained by condensation of diethylenetriamine with dichloroethane with molar ratios of amine: dichloroethane between 1: 2.5 and 1: 0.5 or by condensation obtained from ethylenediamine with dichloroethane in a molar ratio of 1: 0.5 or below.

The above-mentioned polyfunctional amine compounds contain various amounts of nitrogen as. primary, secondary or tertiary nitrogen, depending on whether NH ₂ , NH or N groups are bonded to the carbon atoms of the chains.

Polyamines with nitrogen kept between 25 and 32 ° / ₀ (determined either according to Kjeldahl or by potenliometric titration) have proven to be particularly advantageous. These polyamines can be pasty liquids or rubber-like products, the solubility of which in water decreases progressively to products which only swell with the formation of jelly-like masses. "

The polyamines can also be obtained by condensation of dichloroethane with triethylenetetramine or tetraethylene pentamine or higher homologues of these series can be obtained. The reaction or condensation between the amine compound and dichloroethane can either be in the presence or in the absence of solvents or condensation agents are carried out.

The nitrogen-containing product is mixed with the polyolefin or the polyolefin mixture by working through these compounds at room temperature in Werner mixers, ball mixers or similar apparatus. The melt can be deformed in the usual way by extrusion.

The polyolefin can also be homogeneously impregnated with a solution of the nitrogenous product, whereupon the solvent is removed.

The spinning of the mixtures is preferably carried out in the presence of small amounts of a "solid dispersant", which facilitates the homogeneous dispersion of the nitrogen-containing product in the polymer mass. The preferred dispersant is cetyl alcohol, stearyl alcohol, stearic acid, terephthalic acid, benzoin, furoin, vinyl stearate, a mono-, di- or tristearic acid ester of glycerol, monoethanolamine stearate, stearamine, N-diethanollauramide, aliphatic C ₆ - to C ₃₀ -amines Ethylene oxide with alcohols, amines and phenols, polystearamide, polyacrylic acid, polystyrene or styrene copolymer or terpene polymer are suitable.

By pressing out mixtures according to the invention, mono- or polyfiles can be produced, those for the production of continuous or staple yarns or for the production of bulky Yarn or staple can be used. The monofilaments or polyfiles produced according to the invention can be treated be subjected, by which the basic nitrogen compound becomes water-insoluble. For such Treatments are particularly suitable formaldehyde, diisocyanates such as phenyl diisocyanate and toluene diisocyanate, Diepoxy compounds (ethylene glycol diglycidyl ether, Diepoxybutane, etc.) and crosslinking agents such as divinylbenzene; these treatments can be felt before or after stretching.

The spun threads are entangled with Ratios between 1: 2 and 1:10 at temperatures between 80 and 150 C, with the stretching

3 4

directions by hot air, steam or a suitable head temperature 220 ° C

Liquid to be heated. Spinneret temperature 210 ° C

In addition, it was found favorable that the threads have a maximum pressure of 25 kg / cm *

in an aqueous formaldehyde bath or preferably _A ". ,,,. ,. ,. """,,.

with formaldehyde vapor at 110 to 120 ° C about 5 winding speed 320 m / mm.

10 minutes to treat the modifier

to fix in the threads. If you bring the threads with the 'The threads leaving the spinneret will be with you

Decomposition gases produced by heating Paraform- a 10% aqueous solution of ethylene glycol-

aldehyde can be obtained at about 150 ° C, moistened in glycidyl ether; then they are under

stirring, the nitrogen-containing modifying steam is mixed with an extension ratio of 1: 6.4

medium in the fiber even more stable and in larger stretches and finally crimped and cut.

Fixed amount. The threads then have the following serimetric

The threads obtained according to the invention can have the following properties: acidic metallized disperse dyes or vat dyes to be colored. 15 tensile strength 3.7 g / den

The invention is illustrated in the following examples. Elongation 29%

purifies.

B e i s ρ i e 1 1 ^ ie are metallized with the following acidic

Dyed disperse and vat dyes, whereby

1160 g of hexamethylenediamine are colored in a 20 with very good intensity and fastness.

6-1 glass flask with stirring at room temperature in opposite washing, rubbing and light can be obtained: 1800 ml of water dissolved. Then the solution will come up

9O ⁰ C heated; at the same time, 897 g of dichloroethane color index no.

and 725 g of aqueous 50% sodium hydroxide solution were added. _{rT Dirplftfrelh} -. -, _400na

After the addition has ended, the reaction will be 3 hours 25 ^ ¹ ' ^uireKX g ^{eiD iJ} - ^{w uuu}

continued at 90 ⁰ C, the flask then to 20 ^C - ^L Acid Red 115 27 200

cooled to 25 ⁰ C, with an upper solid layer CI. Acid blue 45 63 010

from a lower aqueous layer (containing C.I. Acid Black 1 20 470

Sodium chloride) separates. The aqueous layer becomes q I Acid Red 216 1182

removed. 30 r ¹ τ pt ■ 11- «in i4.nir»

^{2000 ml ^ 1- öeiz} § ^{elD iU i4 υιυ} are added to the solid mass obtained

Water added and the whole thing for 1 hour under Ruh- ^C - ^L Dispersgelb 20 1 667

Ren heated to 70 to 80 ° C. Then the mass becomes CI. Dispsrsrot 18 1 695

decanted again and the aqueous layer removed. C.I. Vat yellow 2 67 300

The water remaining in the condensate is below 35 ^ I Vat-Rot I 73 360

distilled off under reduced pressure. That in an Aus' _{v R]} . "^ a om

yield 92-94 ° / ₀ product obtained ^{inter alia} · "" ⁴ is suitable ^{oy ÖUJ}

already mixed with polypropylene for use CI. Acid green 25 61 570

in the manufacture of fibers. CI. Pickled Yellow 42 S 132

1300 g of the polyamine condensate (3.5%) are dissolved in 40 C.I. Disperse blue 2 1 713

1300 ml of methanol dissolved and 36 kg of polypropylene ([η], determined in tetrahydronaphthalene at 135 ° C

= 1.25, ash content = 0.06%> residue according to Hep- B e i s ρ i e 1 2

tan extraction = 95.5%) added. In a mixer

which is connected to a vacuum pump, the 45 will become four different condensation products

Alcohol removed by drying at 60 ° C. The Pro- according to the procedure described in Example 1

The product is produced by pressing in a screw device. The molar ratios used are in

granulated at 160 ° C. of the following table 1, the spinning conditions in days

The granulate is specified at belle 2 under the following conditions.

spun: 50 The threads obtained give very intense colors with good fastness to washing, rubbing and

Spinneret type 60 / 0.816 light, if they are used with the color

With a screw temperature of 230 ° C.

Table 1
Preparation of the color modifier

Dichloroethane

polyfunctional amines
(Hexamethylenediamine)

Alkylating agents

990 g (1 mole)

1540 g (1.33 moles)

Lauryl chloride

510 g (0.25 mole)

990 g (1 mole)

1355 g
(1.15 moles)

Lauryl chloride
1180 g
(0.58 moles)

990 g (1 mole)

1355 g (1.15 mol)

Stearyl chloride 864 g (0.3 mol)

990 g (1 mole)

1241g (1.07 moles)

Table 2

Manufacture of fibers from blends containing polypropylene and 4% modifier

Polypropylene [η]

Ash content,%

Residue after heptane extraction,%

Spinneret

Screw temperature ^{, c C}

Head temperature, ° C

Spinneret temperature ^{, 0 C}

highest pressure (kg / cm ² )

Winding speed (m / min.)

Sizing agents

Draw ratio (in the presence of steam)

Tensile strength of the threads (g / den.)

Strain, %

In a conventional resin mixing an intimate mixture of 95 g of polypropylene (intrinsic viscosity [η] measured in tetrahydronaphthalene at 135 ⁰ C = 0.96, heptane extraction residue after 88% and ash content 0.02 ° / _0), and 5 g of a polyamine prepared . The polyamine product is obtained as follows: 103 g (1 mol) of diethylenetriamine, 160 ml of water and 99 g (1 mol) of symmetrical dichloroethane are placed in a glass flask equipped with a stirrer and reflux condenser. The mixture is refluxed for 10 hours. As the condensation progresses, the hydrochloric acid released is neutralized with 15% sodium hydroxide solution. 470 g of 15% strength sodium hydroxide solution are added during the 10 hour reaction time. The water is then distilled off and the common salt is filtered off. The residue consists of a thick oily product with a nitrogen content of 29.8%, which can be separated off by distilling off the unchanged diethylenetriamine in vacuo.

While the polyamine is being mixed with the polypropylene, the rollers of the mixer rotate with it different speeds and are heated to 130 ° C. The product is through several times run the mixer with the scraper lowered and the rollers held close together will.

The processing time is 8 minutes. There is obtained a product in the form of friable pulp which is introduced directly into the heated to 225 ⁰ C spinning apparatus. The threads are drawn in a hot room at a ratio of 1: 5 and then placed in a flask heated to 110 ° C and connected via a gas inlet tube to another flask which contains paraformaldehyde and is heated to 150 ° C. At this temperature the paraformaldehyde is decomposed with the formation of gaseous aldehyde. This treatment is continued for 10 minutes, then the threads are removed and kept in a ventilated drying cabinet at 75 ° C for 1 hour. The threads obtained in this way are dyed with the following colors:

1.3 1.3 1.3 1: 6.2 By S 1: 5.9 1.3 0.067 0.067 0.067 3.51 3.7 0.067 95.5 95.5 95.5 25th 22nd 95.5 60 / 0.8 x 16 60 / 0.8 x 16 60 / 0.8 x 16 game 4 60 / 0.8 · 1 230 230 230 230 220 220 220 220 210 210 210 210 29 37 25th 34 270 225 310 250 ethylene glycol diglycidyl ether (10% aq : ige solution 1: 6 1: 6 3.12 3.1 33 35

Acid Yellow 11
Acid red 115

(CI-No. 18 820)
(CI-No. 27 200)

Intensive color tones are obtained which are soapy water.

Following the procedure described in Example 3, 96.5 parts of polypropylene ([η] = 1.1, residue after heptane extraction = 92%, ash content = 0.02 ° / ₀ ) are added at 150 ° C. in a roller mixer with 3.5 parts mixed a polyamine obtained as follows:

103 g (1 mol) of diethylenetriamine, 160 ml of water and 148.5 g (1.5 mol) of symmetrical dichloroethane are used placed in a glass flask equipped with a stirrer and reflux condenser and the whole mass for 14 hours boiled under reflux, the hydrochloric acid released being continuously neutralized with sodium hydroxide solution. To the 670 g of a 15% strength sodium hydroxide solution are used for neutralization. Water is distilled off and Separated sodium chloride. In order to facilitate the separation of the sodium chloride, after the distillation of about 500 ml of water and, after filtering, 100 g of diethylenetriamine as a solvent added. The water is completely removed, the salt is filtered off and the diethylenetriamine is distilled off in vacuo. The residue is a pasty product with a nitrogen content of 27% · It only partially dissolves forming a gel in water.

The preparation of the mixture of polyamine and polypropylene is then carried out as described in Example 3. The mixture is spun at 260 ⁰ C, the filaments are treated for 10 minutes by gaseous formaldehyde, washed in a water bath at 40 ⁰ C and dried in a drying cabinet at 75 ° C. The threads obtained are odorless; they are colored with the following dyes:

Acid blue 45 (CI No. 63 010)
Acid red 115 (CI No. 27 200)
Diachromator orange H

Dyeings with good soapfastness are obtained.

Example 5

Following the manner described in Example 4 will be

90 parts of polypropylene ([η] = 1.2, residue after heptane extraction = 94%, ash content = 0.02%) mixed at 150 ° C with 10 parts of a polyamine product obtained as follows:

51.5 g of diethylenetriamine (0.5 mol), 100 ml of water and 99 g of symmetrical dichloroethane are in a flask equipped with a stirrer and reflux condenser

brought. The mixture is refluxed for 15 hours, the hydrochloric acid released is neutralized as in the previous examples with 406 g of 15% sodium hydroxide solution.

After the water has been distilled off and the sodium chloride has been separated off, as described in Example 4, a Obtained a product with a rubbery appearance that is difficult and only partially soluble in water and one Has a nitrogen content of 25.1%.

After mixing as in the previous examples, the mixture is spun at 260 ° C. and drawn. After treatment with formaldehyde, the threads are washed and dried, as in the example 4 and colored with the following dyes:

Wool red B
Acid black 1
Acid green 25

(CL No. 20 470)
(CI-No. 61 570)

Threads with intense hues and good soapfastness are obtained.

Example 6

A mixture is made of 94 parts of polypropylene (M - 1.25, residue after heptane extraction = 94%, Ash content = 0.067%) and 6 parts of an amide product produced by condensation of the in Example 4 described polyamine with the same weight of salicylic acid up to the removal of a certain Water amount of 1 mole per mole of acid with xylene as the carrier solvent was obtained.

The amide product is a clear, light yellow mass that is easy to grind and soluble in methanol. The resin-modifier mixture is made by moistening the polypropylene powder with an alcoholic Solution of the modifier and subsequent evaporation of the solvent prepared.

The mixture obtained in this way is introduced directly into the spinning apparatus, which is heated to 225.degree.

The filaments are initially at a ratio of 1: 4.5 then subjected stretched at 15O ⁰ C and the stabilization treatment for the Amidmodifikatiqnsmittel using formaldehyde or Äthylenglykoldiglycidyläther; they then have good thermal stability and very good absorption capacity for acidic dyes. Threads with intensely glossy shades and good color fastness are obtained.

B e i s ρ i e 1 7

A mixture is made from 94 parts of polypropylene (Iv) ⁼ l> 30, residue after heptane extraction = 97%, ash content = 0.06%) and 6 parts of an amide product obtained by condensation of the polyamine described in Example 3 with the same weight of stearic acid was obtained until a certain amount of water of 1 mole per mole of acid was removed with xylene as the carrier solvent. The modifier compound is a waxy mass soluble in methanol. It is distributed in the resin with the aid of an alcoholic solution, whereupon the solvent is evaporated off.

The mixture is spun in a chamber extruder heated to 225 ° C. Thereafter, the filaments are in air at 15O ⁰ C at a stretch ratio of 1: 5 stretched and crosslinked as described in Example 6 with an aldehyde or a Diepoxydlösung.

The ability of the threads to absorb acidic dyes is remarkable, and they become intense obtained glossy shades with good authenticity.

Example 8

A fiber is made from a mixture of 94 parts of the polypropylene described in Example 6 and Dividing an amide product made by reacting a polyamide (made by condensation of diethylenetriamine with dichloroethane according to Examples 3 and 7) with lauric acid, as in the previous, previous example given, was obtained.

The fibers have after drawing and after treatment with the stabilization baths for the Modifying agents, as described in Example 6, have a good absorption capacity for acidic dyes. It threads with solid intense and bright shades are obtained.

Claims (2)

Patent claims: 1. Further development of the process for improving the dyeability of threads made of polyolefins by blending polyolefins or polyolefin blends with one or more Dye-affine polymers, melting of the polymer mixture and customary shaping according to the patent 1251903, characterized in that that as dye-affine polymers in the molten masses 0.5 to 25 percent by weight, based on the weight of the polyolefins, basic compounds with resinous character usedj ' by reacting dichloroethane with polyfunctional amines, optionally in Presence of solvents or condensation agents and, if appropriate, subsequent alkylation have been produced, and the threads optionally before or after drawing with formaldehyde, isocyanates, diepoxy compounds or crosslinking agents for the purpose Treated water insolubilization of the nitrogen-containing compound in the mixture. 2. The method according to claim 1, characterized in that one uses dye-affine polymers, that by condensation of 0.01 to 2.5 moles of a polyfunctional amine per mole of dichloroethane have been manufactured. 009 548/397