DE1469105B - - Google Patents

Description

It has been proposed to use condensation resins made from epichlorohydrin and various others organic compounds with functional groups, e.g. B. diphenols to produce. It has now been found that condensation products of epichlorohydrin with certain amines are particularly interesting because they are mixed with crystalline polyolefins such as polyethylene or polypropylene, or polyacrylonitrile as fiber-forming polymers improve the dyeability of these polymers.

Although it is already known, threads made of a mixture of polypropylene and one made of epichlorohydrin and aniline obtained epoxy resin. This condensation product of epichlorohydrin and an aromatic amine, however, is in contrast to the solid epoxy resins used according to the invention a viscous liquid, and thus the mixture with the polypropylene is more difficult to make and to handle as the mixture with the solid epoxy resins. In addition, this can be made from epichlorohydrin and aniline-weighted epoxy resin easily recovered from the fibers by water and organic solvents washed out, which at the same time the affinity of the dye for the thread is lost. The strings, which are made from epichlorohydrin and aniline using this epoxy resin are thus not washable and dry-cleanable.

The invention relates to textile threads or fibers made from a mixture of olefin polymers or acrylonitrile polymers with a basic polymeric nitrogen compound and optionally other conventional additives which are characterized in that the threads contain 1 to 25 percent by weight, based on the polymer weight, of basic polymeric nitrogen compounds with a water solubility of less than 0.1 ° / ₀ included, namely at

a) a condensation product of epichlorohydrin and a primary aliphatic monoamine with 3 to 30 carbon atoms or secondary aliphatic monoamine with 4 to 60 carbon atoms, which is subsequently implemented with a polyamine or an aliphatic imiri has been, or at

b) a condensation product of epichlorohydrin and a primary aliphatic polyamine with 2 to 30 carbon atoms or a secondary aliphatic polyamine with 4 to 60 carbon atoms, which has subsequently been reacted with an alkylating or arylating agent,

and that the threads have optionally been aftertreated with water-insolubilizing agents.

The condensation products used according to the invention have been prepared by reacting epichlorohydrin with amines or their salts, preferably in the presence of a suitable condensing agent, for example an alkali hydroxide or carbonate, or a condensation product of ethylene oxide with an alcohol having 10 to 14 carbon atoms. The preparation of the resin can be carried out in the presence of an inert solvent, for example methyl alcohol. The condensation conditions, the individual components and their proportions are selected so that the water solubility of the condensation product is below 0.1 percent by weight. Hydrochlorides or acetates, for example, can be used as salts of the amines. ^:

The amines used in making the condensation products are either aliphatic primary amines with 3 to 30 carbon atoms or secondary amines with 4 to 60 carbon atoms. Mono- or polyamines can be used

ίο be. Particularly suitable aliphatic monoamines are n-dodecylamine, n-octadecylamine, dioctylamine, Dioctadecylamine. or hexadecylamine. Suitable polyamines include, for example, ethylenediamine, Hexamethylene diamine, tetraethylene pentamine, 1,2-propylene diamine or dipropylene triamine. For the Improvement of the dyeability in relation to certain dyes is the modification of the condensation resin that is used in the mixture from which the fiber is made was used is of importance. At-

zo, for example, if in the preparation of the condensation product an aliphatic monoamine was used, the product obtained with a polyamine Are implemented, for example with ethylene 'diamine, hexamethylene diamine, tetraethylene pentamine, 1,2-propylenediamine or dipropylenetriamine. It has also been found that fibers are obtained that are particularly respond well to acidic wool dyes when a condensation resin is used that is made by Modifying the condensation product of an aliphatic monoamine and epichlorohydrin with an aliphatic imine, for example ethyleneimine, is obtained.

A condensation product of epichlorohydrin and a polyamine is on the other hand with an alkylation or arylation agent, preferably an alkyl or aryl halide, modified. Preferably that The ratio of epichlorohydrin to amine used depends to a certain extent on the particular Amine and also whether the product is subjected to further treatment or not. If the condensation product was obtained from a primary or secondary monoamine, then there is one very suitable molar ratio of epichlorohydrin to amine in the range from 1: 1 to 5: 1. Will be such a thing If the product is modified with a polyamine, there is a preferred molar ratio of polyamine to monoamine in the range from 0.1: 1 to 10: 1. If such a But product is modified with an aliphatic imine, the molar ratio of imine to Amine preferably in the range from 0.1 to 10: 1. A particularly valuable condensation product becomes by condensing a polyamine with epichlorohydrin in a molar ratio of amine to epichlorohydrin from 1.2 to 1.5: 1, further comprising the product obtained with an alkyl or aryl halide is modified so that the ratio of alkyl or aryl groups to epichlorohydrin is in the range from 0.1 to 2: 1. When the ratio of polyamine to epichlorohydrin is below 1.2: 1, shows the condensation product has a tendency to undesirable crosslinking, making it infusible and can no longer be well dispersed in a crystalline polyolefin. A very useful condensation resin is made by reacting one mole of epichloride hydrin with 1.3 moles of hexamethylenediamine and then 0.4 moles of octadecyl chloride. This condensation resin can be added to the crystalline polypropylene in an amount of about 5 percent by weight

whereby a mixture with improved dyeability is obtained.

The condensation products used according to the invention are used to produce textile threads or fibers added to the thread-forming polymers in amounts of 1 to 25 percent by weight and the resulting Blends then spun. If the condensation products become olefin polymers, for example to crystalline polypropylene, the textile fibers or threads are produced by melt spinning. .: - ..;,

The mixing of the condensation products with the olefin polymer or acrylonitrile polymer can be carried out by Mix at room temperature in a Werner mixer, ball mill, or similar device respectively. In the case of using olefin polymers, the mixture of polymers and Condensation product from epichlorohydrin and amine granulated in a screw apparatus, then comminuted again and then melt-spun.

Melt spinning of the mixtures according to the invention is facilitated by adding a small amount, preferably 0.1 to 5 percent by weight, of a solid dispersant to the mixture which contributes to the homogeneous dispersion of the condensation resin in the polymer mass. Very suitable dispersants are, for example, cetyl and stearyl alcohol, stearic acid, terephthalic acid, benzoin, furoin, venyl stearate, mono-, di- and tristearic esters of glycerol, monoethanolamine stearate, stearamide, N-diethanollauramide, C ₆ to C ₃₀ aliphatic amines, condensation products of ethylene Alcohols, amines and phenols, polystearamide, polyacrylic acid, polystyrene and styrene copolymers and terpene polymers. Other additives, such as those generally used in blends for melt spinning fibers, such as optical fillers and stabilizers, can also be added.

Melt spinning can produce mono- or polyfiles are produced, which further to continuous fibers or staple fibers or to bulky yarns or can be processed into staple yarns.

After the fibers are made, they are preferably drawn with a draw ratio from 2: 1 to 10: 1. This stretching can take place at a temperature between 80 and 150 ° C. in an apparatus be carried out, which is heated with hot air, steam or the like.

The fibers are also preferably treated, before or after drawing, with agents which make the resin water-insoluble. A suitable agent of this type is a compound which can condense either with the amine radical or with the epichlorohydrin radical in the condensation product to form a compound with a higher molecular weight. Whether a compound known to react with epichlorohydrin or with an amine can be used to insolubilize the condensation resins of the present invention can easily be determined by a simple experiment in which the fiber is treated with the agent and then the dissolving action of water on the treated fiber is compared to that on an untreated fiber. Such insolubilizing agents are, for example, formaldehyde, an isocyanate or a diepoxy compound or a crosslinking agent such as divinylbenzene.
The fibers from the mixtures according to the invention can be dyed with acidic dyes or with what are known as acetate dyes. The fibers also show a good affinity for basic dyes, metallized dyes, plasto-soluble dyes, and vat dyes.

With other fiber-forming polymers such as olefin polymers and polymers and copolymers of acrylonitrile, slightly different methods can be used. So can with polyacrylonitrile the condensation resin by mixing it with the acrylonitrile polymer and then dispersing it the mixture at ordinary temperature in a suitable spinning solvent (dimethylformamide, y-butyrolactone, ethylene carbonate and other solvents of acrylonitrile polymers) are incorporated into this; it can also be the components are dissolved separately in the spinning solvent, in which the polyacrylonitrile is then dispersed. In both Cases the dispersion is converted into a spinning solution by appropriate heating.

As with crystalline polyolefins, a solid dispersant can also be used here and the fibers obtained can be drawn and with an agent whereby the condensation product is rendered insoluble in water.

Example of the production of the in the erfindungsv according to threads contained basic polymers

Nitrogen compounds ... '. · ■' · ■
30th

1345 g octadecylamine, 925 g of epichlorohydrin and 1000 g of 95 ° / _o hydrochloric ethyl alcohol are charged into a 6-1 three-necked flask provided with a stirrer, thermometer and reflux condenser. ■. ' The mass is heated to approximately 85 ° C and stirred for 8 hours. Then 954 g of hexamethylenediamine are added. · '- ^:

Heating is continued for 4 hours. It is then cooled to 60 ° C. and 400 g of sodium hydroxide are added added in place toe form. Now the

Mixture stirred for 2 hours at 60 ° C and the sodium chloride formed is of the still filtered off warm mixture.

The ethyl alcohol is distilled off under reduced pressure; the solid residue obtained thereby becomes ground and sifted. "■■■.

Solubility of the condensation product

The condensation product shows the following solubility ^{at 25 ° C.} : -. ...... _:

solvent
55 Solved Pro
product g / 100 ml
solvent
Vo Solved Pro
product g / 100 g
solvent
Vo. Hydrocarbons
benzene
60 petroleum ether
Heptane
Vaseline oil
petroleum
Tetrahydronaphthalene
65 alcohols
Methyl alcohol
Ethyl alcohol
Cyclohexanol 1,100
4,500
8,700
0.001
0.080
4,700
0.110
1,300
1,500 1,250
6,700
12.65
0.100
4,850
0.140
1.640
1,570

(Continuation of the table)

Ketones Solved Pro Solved Pro solvent Acetophenone product g / 100 ml
solvent product g / 100 g
solvent Acetone Cyclohexanone 0.530 0.515 Methyl ethyl ketone ... 0.500 0.630 ether 0.300 0.300 Dioxane 0.016 0.020 Ester Ethyl acetate 0.110 0.100 Halogen derivatives chloroform 1,900 2.120 Tetrachlorethylene ... Carbon tetrachloride 4.100 2.750 Trichlorethylene 9,500 5.820 Nitriles 5.070 3,200 Acrylonitrile 3,500 2,420 Acids acetic acid 0.060 0.070 Thioglycolic acid Sulphides 4,500 4,280 Carbon disulfide. '. 3,200 Amides Dimethylformamide .. 0.001 0.001 Nitrogen bases Pyridine 0.100 0.110 Nitrogen derivatives Nitrobenzene 5.180 5.270 Lactones y-butyrolactone 0.005 0.004 Amino alcohols Monoethanolamine ... 0.005 - inorganic compounds water 0.005 0.004. hydrochloric acid sulfuric acid 0.020 0.020 30% ammonia. 0.001 0.001 • 20 ° / ₀ sodium sodium 0.130 0.072 "■ hydroxyd 0.200 0.225 ... 0.001 0.001

The values given in the table are the mean values from 3 determinations:

sample Melting point 1 52 ° C 2 52 ° C 3 51 ° C 4th 52 ° C - ■ - ■ 5 52 ° C 6th 52 ° C

Determination of the specific viscosity

The value of the specific viscosity (η sp.) Was determined in a 5 ° / _o solution of the condensation product in benzene at 25 ° C. Fenske type 100 viscometers were used.
_ao The following values were found:

sample η spec. 1 0.338 2 0.338 3 0.333 4th 0.297 5 0.298 6th 0.305

Cryoscopic determination of the molecular weight

The molecular weight was determined by cryoscopy in an apparatus with a Beckmann thermometer. It was only possible to determine the molecular weight of sample 1 (molecular weight approximately 4000) rend that the other samples could not be determined, probably because their molecular weight outside the sensitivity limits of the equipment used. In fact, none could handle that Beckmann thermometer detectable freezing point depression can be observed. :

example 1

- The following substances are good solvents at the boiling point: benzene, petroleum ether, heptane, methyl alcohol, Ethyl alcohol, cyclohexanol, cyclohexanone, methyl ethyl ketone, dioxane, ethyl acetate, chloroform, Tetrachlorethylene, carbon tetrachloride, trichlorethylene, acrylonitrile, acetic acid, pyridine and carbon disulfide. . '

Determination of the melting point

The melting point was determined under a microscope fitted with a hot plate.

18.5 g (0.1 mol) n-dodecylamine, 18.5 g (0.2 mol) Epichlorohydrin and 30 ml of ethyl alcohol are placed in a 200 ml three-necked flask with a stirrer, thermometer and reflux condenser is provided. The mixture is at about 80 ° C refluxed with stirring for 6 hours.

7.4 g (0.1 mol) of 1,2-propylenediamine are then added added and heating continued for 3 hours.

To isolate the condensation resin, the solvent is distilled off under reduced pressure.

Its water solubility is 0.03 ° / _0th '■ ..

To produce the fibers, the obtained

Ethanol solution of the condensation product (44.4 g dry substance) mixed with 399.6 g (90%) polypropylene. The polypropylene was produced with the help of stereospecific catalysts and had an intrinsic viscosity [η] of 1.4 (determined in tetrahydro-?

naphthalene at 135 ° C), a residue after the heptane extraction of 94 ° / ₀ and an ash content of 0.055%. The mixture is heated in a drying cabinet to remove the ethyl alcohol.

7 8

Then it is spun in a laboratory melting device in a laboratory melting device under the spinning device under the following conditions: The following conditions: ■. _:

_c . ■ ..:, .. _Λ , - Spinneret: l / 0.8-16mm

Spinneret ... 1/0 8-16 mm extrusion temperature 200 ⁰ C -

Auspreßtemperatur 190 C 5 _Dru ^ _k ....;. 6,4kg / cm ^":

. 'V ™ ^cl 5; ·; ·· ■ ·· ■ ·. · · · ·; ': * · · *' , E ^Cm winding speed .. 380 m / min.

: Winding speed .. 38Om / min.

. '' On the obtained fibers, which are in a laboratory

.: On. the fibers obtained, which in a laboratory device with a ratio of 1: 5 at 130 ° C torium devices with a stretch ratio (i.e., one io stretched, are mixed with the dyes of the

Ratio of the length of the unstretched fiber to the previous example, dyeings with good

Length of the stretched fiber) of 1: 4.5 at 130 ° C. intensity and fastness. . . .,. _{; :}

The stains are even truer when the

intensity and fastness with the following dyes were prepared: fibers prior to dyeing with a 5 ° / _o by weight hexa-

: '.-.'...' ■ 15 methylene diisocyanate solution at room temperature

CI Direct Yellow 11 (C. L No. 40,000) and then dried.
CI Acid Red 115 (C. L-No. 27 200)

C. I. Acid Blue 40 (C. L No. 62 125) Example 3 "·

C. L Acid Black 1 (C. L No. 20470); .., ..-., ....., : ....: C. I. Acid Red 2L6, (C. L-Nr. 1182) 20 185 g (1 mol) n-dodecylamine, 185 g (2 mol) epi-

CI. Disperse Yellow 20 (C. L-No. 1 667) chlorohydrin and 300 ml of ethyl alcohol are in one

CI. Disperse Red 18 (C. L-Nr. 1 695) 2-1 three-necked flask introduced, which is operated with a stirrer,

C. I. Disperse Blue 2 (C. L No. 1 713) thermometer and reflux condenser is provided. ;

The mixture is below ^{at about 8O 0 C}

The colorations obtained are truer when the stirring is refluxed for 6 hours. Then 189 g (1 mole) of tetraethylene pentamine are added to fibers prior to dyeing with formaldehyde, by boiling for 10 minutes and heating continued for 3 hours. After a 5 ° / _o subsequent aqueous formaldehyde solution, and cooling the ethanol solution of the product obtained by drying. ■ (559 g dry product, water solubility 0.018%): Another mixture is made with the same poly- 30 this is mixed with 7.427 g (93 ° / q) polypropylene, propylene is produced, but in an amount of 93 ° / ₀ The polypropylene was prepared with the aid of stereospecific 7% of the above-described condensation fish catalyst, had a marginal product. Viscosity [η] of 1.00, a residue after the The mixture thus obtained is in a laboratory heptane extraction of 92.8 ° / "and an ash content ratoriums melt spinning machine under the following 35 of 0.095 ° / ₀ . The mixture is spun in a drying condition: heated and cupboard to remove the ethyl alcohol

finally in a laboratory melt spinning machine

Spinneret 1 / 0.816 mm spun under the following conditions:

Extrusion temperature ....... 190 ⁰ C screw temperature 240 ⁰ C

............ pressure 7.8 kg / cm "40 head temperature 210 ⁰ C.

Winding speed .. 380 m / min. Spinneret temperature 200 ° C

_. ,, ^, ,,,, ·, spinneret type 60 / 0.8 · 16 mm.:

The fibers obtained, after drawing, have a pressure of 20 kg / cm ²

colored; there are stains with good intensity winding speed "'.'. 250 m / min.

and authenticity with the aforementioned dyes 45

obtained .. The yarns obtained are at 160 ° C with a

Draw ratio of 1: 5.3 drawn. The received

B e i s ρ i e 1 2 fibers show the following serimetric properties:

18.5 g (0.1 mol) n-dodecylamine, 18.5 g (0.2 mol) 50 Defnunf T .. '.'. '.'. '.'. '.'. '.'. ' . '.' /. '.'. '.'. 28 $ "/ ⁸ ^

Epichlorohydrin and 30 ml of ethyl alcohol are used in ''

placed a 200 ml three-necked flask, which is marked on the fibers obtained with the help of the im

a stirrer, thermometer and reflux condenser Example 1 mentioned dyes stains with good

is provided. Preserved intensity and authenticity. ··. · _:

The mixture is stirred at about 80 ° C 55 The colorations are even more real when the fibers

Refluxed for 6 hours. in a 10 ° / ₀ ige for 10 minutes before staining

Then 10.3 g (0.1 mol) of diethylenetriamine aqueous solution of ethylene glycol diglycidyl ether are added

added and heating continued for 3 hours. Immersed in room temperature and then dried

After cooling the ethanol solution of the obtained.

Product (47.3 g dry product, which is a water 60.

solubility of 0.015 ° / ₀ ) this equates to 628.4g aeispiei 4

Polypropylene (93 ° / ₀ ) mixed. The polypropylene 26.9 g (0.1 mole) n-octadecylamine, 18.5 g (0.2 mole)

was made with the help of stereospecific catalysts epichlorohydrin and 40 ml of ethanol in a

had an intrinsic viscosity [η] of 1.4, placed a 200 ml three-necked flask fitted with a

Arrears after the heptane extraction from 94 ° / ₀ 65 provided stirrer, thermometer and reflux condenser

and an ash content of 0.055 ° / _0th is.

The mixture is at about 8O ⁰ C in a drying cabinet to the mixture with stirring

Removal of the ethyl alcohol heated and finally refluxed for 8 hours. Be on it

9 10

18.9 g (0.1 mol) of tetraethylpentamine were added and a spinneret 1 / 0.8 × 16 mm

heating is continued for 3 hours. Extrusion temperature 210 ° C

The solvent is pressure 6.4 kg / cm ^{2 by vacuum distillation}

removed; the product (64.3 g, water solubility 0.02%)

is powdered and with 854.3 g (93 ° / ₀ ) polypropylene 5 winding speed .. 360 m / min,

mixed. The polypropylene was made with the help of The fibers obtained are in a laboratory

Stereospecific catalysts produced had a torium device with a ratio of 1: 3 at 95 ° C

Intrinsic viscosity [η] of 1.4, a residue after the stretched. With acidic dyes and acetate dyes

Heptane extraction of 94 ° / ₀ and an ash content are then stains with good intensity

of 0.055%. ίο and authenticity preserved. . ■

The mixture is in a melt spinning device ...

spun under the following conditions: Example /

_c ·, .. ι mo - \ f. ™ into a 6-liter three-necked flask fitted with a stirrer,

spinneret 1 / U, o 16 mm _,, _, .., _ _n . .. '. ,. , '

Pressing temperature 200 ⁰ C thermometer and reflux cooler is provided

Pressure 6,4kg / cm ^{2 x5 the fol} i ^compounds introduced:

Winding speed .. 380 m / min. Octadecylamine 1345 g

'. ,,. _ j,,., epichlorohydrin 925 g

The fibers thus obtained were determined by the comparison _{950 /} j ethyl alcohol 1300 g

stretch with a ratio of 1: 6 at 12O ⁰ C in toe jb

stained a laboratory device; with acidic and 20 The mass is ^{heated to approximately 8O 0} C and

Acetate dyes, in particular with the dyes, stirred for 4 hours; 580 g of hexamethylene are then

which are mentioned in Example 1, stains were added to leniamine. It will continue for 2 hours

received with good intensity and authenticity. heated and then under ordinary pressure a '

Part of the alcohol (500 g) distilled off. The rest

Example 5 ² S alcohol is in a vacuum dryer at 6O ⁰ C at

a pressure of 5 to 10 mm away.

18.5 g (0.1 mol) n-dodecylamine, 18.5 g (0.2 mol) It becomes a solid product (water solubility

Epichlorohydrin and 30 ml of ethyl alcohol are obtained in 0.025%), which is ground and sieved,

placed a 200 ml three-necked flask marked With the analysis, the product shows a nitrogen

a stirrer, thermometer and reflux cooler 30 content of 6.93%. A mix of 7% of this

is provided. Condensate and 93% polypropylene (with a limit

The mixture is at about 75 ° C under a viscosity [η] of 1.15, a residue after

Stir refluxed for 6 hours. Heptane extraction of 94.01% and an ash content

11.6 g (0.1 mol) of hexamethylene of 0.12%) are then prepared,
diamine was added and heating was spun 3 hours 35 The mixture is The melt spinning ethanol solution of the product obtained (48.6 g apparatus at 150 ⁰ C in a screw is continued, extruder and then granulated in a under the following conditions:

Dry product water solubility 0.034%) with screw temperature 200 ° C

645.7 g (93%) mixed polypropylene. The poly head temperature 180 ° C

Propylene was obtained using a stereospecific 4 ° spinneret temperature of 170 ° C

Catalysts made had an intrinsic viscosity spinneret style 60/0 8 x 16

[η] of 1.4, a residue after the heptane pressure 22 kg / cm ²

extraction of 94% and an ash content of winding speed ''.' 250 m / min.
0.055%. The mixture will eventually become m one

Drying oven to remove the ethyl alcohol 45 The fibers obtained are at 15O ⁰ C in Mounted and then in a laboratory melting essence of steam with a distance ratio spin apparatus under the following conditions spun: 1: stretched 6.3. The fibers show the following

Spinneret 1 / 0.816 mm serimetric properties:

Auspreßtemperatur 19O ⁰ C tensile strength of 4.98 g / den

Pressure ,, · 6.4 kg / cm ^{2 ö} elongation ... 24 ° /

Winding speed .. 380 m / min. , ",» »- ■,

The fibers are stained with good

The fibers obtained in this way, which have been tested in a laboratory for intensity and authenticity by means of acidic and acetate

ratoriumsgerät at 130 ° C in a ratio of 1: 7.5 dyes, especially those mentioned in Example 1

were stretched, 55 dyes are obtained with acidic dyes,

and acetate dyes, especially those in R ^-1 Is

Example 1 mentioned dyes, colorations with e 1 s ρ 1 e

preserved under intensity and authenticity. Into a 6 liter three-necked flask fitted with a stirrer;

. Is provided with a thermometer and a reflux condenser,

^{a e} * ^s P * ^{e l 6} 60 the following substances are introduced:

An ethanol solution of 1345 g according to the previous octadecylamine

Example obtained condensation product with a Eoichlorhvdrin 925 g

Content of 48.6 g dry product is with 645.7 g ₉ J ₀ / _iser Äthvlalkohol 1300 ε

(93%) low-pressure polyethylene with a molecular weight of ^ '° ^{lgei Am} y ^{lalKOÜO1 uw ε}

of about 50,000 mixed. The solvent 65 The mass is stirred for 4 hours to un-

is then removed in a drying cabinet. The heated to about 80 ° C; 290 g of hexamethylene are then

Mixture is added in a laboratory fused diamine and 365 g of triethylenetetramine, and

spinning device spun under the following conditions: heating is continued for 2 hours. Closing

A part of alcohol (500 g) is borrowed under ordinary Distilled pressure. The remaining alcohol is in a vacuum dryer at 60 ° C and a pressure from 5 to 10 mm away, the solid product obtained is ground and sieved.

From 5 ° / ₀ of this condensate and 95% polypropylene (having an intrinsic viscosity [η] of 1.5, a rear stand after heptane extraction of 94.01% and an ash content of 0.12%), a mixture is prepared containing granulated at 15O ⁰ C in a screw extruder and is then spun in a melt spinning apparatus under the following conditions:

Screw temperature ...... 200 ° C

Head temperature 200 ° C

.. Spinneret temperature 19O ⁰ C

Spinneret type 60 / 0.816

Pressure 20 kg / cm ²

Winding speed .. 250 m / min.

The fibers obtained become in-essence at 150.degree stretched by DampFithit to a stretching ratio of 1: 5.3.

They then show the following serimetric properties:

^15th

7nsjfestiV1 <-eit · 4 79 σ / rien

Elongation "" "22» /

³⁵

These fibers are exposed to the UV rays of a 100 watt mercury vapor lamp, which are at a distance of 10 cm was exposed. After 40 hours of exposure, the tensile strength fell to 25% their initial value from; analog fibers from the same polymer, but without the addition of the condensate, suffer a reduction of 25% of their origin Tensile strength after exposure to the mercury vapor lamp for ten hours under the same Conditions.

These fibers are dyed with good intensity and fastness with acidic and with acetate dyes, in particular with the dye "h ™ _g e" _ta .

Example 1 9

1508 g of hexamethylene diamine are dissolved in 2500 g 95o / _o sodium ethyl alcohol at room temperature in a 6-1 flask under stirring. After cooling to 2 to 3 ° C, 925 g of epichlorohydrin are added. Stirring is continued for 2 hours at 5 to 1O ⁰ C, and the temperature is then increased slowly to 80 ° C. At this temperature the reaction is continued for 4 hours. Now 400 g of sodium hydroxide followed by 1 hour, heated at 8O ⁰ C for be added in the form of cookies. The reaction mixture is then introduced into a pressure-tight 5 l autoclave according to the H ofer method, which is equipped with a stirrer, electric heating, manometer and thermometer.

Now Oktadecylchlorid 1,150 g are added, and the mixture is heated for 12 hours at 150 to 170 ⁰ C. After cooling to 6O ⁰ C, 160 g of sodium hydroxide are added in the form of cookies. After lstündigem heating to 80 ⁰ C while stirring the sodium chloride formed in "the heat is removed by filtration of the alcoholic solution to be 48 kg -. Polypropylene (intrinsic viscosity [η] 1.3, ash content 0.03%, residue after heptane extraction 94.7 ° / added to _0). the alcohol is removed by drying at 60 ° C in a connected to a vacuum pump mixer, and the product is granulated by explosion in a screw extruder at 160 ⁰ C. the granules are in a device such as "it in the previous examples has been described, under ^the conditions follow * from the melt spun:;

Spinneret type 60 / 0.8 -16

Screw temperature ^{230 0 C}

Head temperature. 220 ⁰ C ■

Spinneret temperature 210 ° C

highest pressure 22 kg / cm ²

Winding speed .. 312 m / min.

The yarn exiting the spinneret as described in the preceding examples, with a l0 ° / ₀ aqueous ethylene glycol Diglycidylätherlösung (which also 1 g per liter of a condensation product of 10 mol of ethylene oxide with ^{1 Mo1} octylphenol contains) moistened. It is then stretched (in the presence of steam) at a stretch ratio of 1: 6.3 and then crimped and cut. The yarn has the following serimirical properties:

Tensile strength 3 24 g / den

Elongation 28 ⁰ I '

The yarn is dyed with the following acidic, metallized, plasto-soluble and vat dyes, whereby Dyeings with high intensity and good fastness to washing, rubbing and light are obtained:

£. I. Direct YeI ow 11 (C. L-No. 40 000)
C., Ac.d gto «(CI No. 62 1 ₂ 5,

C.I. Acid Red 216 (C.I. No. 1182)

£ I. Mordant Yellow 10 (C I.-Nr 14 010)

£ I. Disperse Yellow 20 (C I -Nr 1 667)

£. I. Disperse Red 18 (C.I. No. 1 695)

£ L Disperse Blue 2 (C.I. No. 1713)

£ I. Vat Yellow 2 (C. I. No. 67 300)

£ · J- ™ 1 £ f ^d \ £; · ™ · ^ 36Q),

^{CL Yat Blue 4} (° ^L - ^{No. 69 800} >

Example 10

According to the procedure described in Example 9, four condensation products are prepared, wherein the molar ratios and spinning conditions given in the table are observed. To the so The fibers obtained are colored very intensely with the dyes described in Example 9 obtained with good fastness to washing, rubbing and light.

Synthesis of the condensation resin epichlorohydrin 925 g (1 mol) 925 g (1 mol) 925 g (1 mol) 925 g (1 mol)

Polyamine hexamethylene diamine hexamethylene diamine hexamethylene diamine hexamethylene diamine

1508 g (1.3 mol) 1392 g (1.2 mol) 1572 g (1.35 mol) 1508 g (1.3 mol)

Alkylating agent cetyl chloride lauryl chloride octadecyl chloride benzyl chloride

1303 g (0.5 mole) 1023 g (0.5 mole) 1443 g (0.5 mole) 633 g (0.5 mole).

13 14

Manufacture of yarns from blends of polypropylene and 6% condensation product;

Polypropylene ... 1.3 1.3 1.3 1.3

Ash content 0.067 '. 0.067 0.067 0.067

Residue after the heptane extract ..

■ tion .............. 95.5 95.5 95.5 95.5;

Spinneret .... 60 / 0.8 16 60 / 0.8 -16 60 / 0.8 -16 60 / 0.8 16 '

Screw temperature .... 230 ⁰ C 23O ⁰ C - 23O ⁰ C- .. ■. 23O ⁰ C.

Head temperature ................ 22O ⁰ C 220 ° C 220 ⁰ C 220 ° C

Spinneret temperature 210 ° C 210 ⁰ C 210 ° C 21O ⁰ C

highest pressure (kg / cm ² ) 22 17 28 21 _:

Winding speed (m / min.) 270 230 250 220

Sizing ethylene glycol diglycidyl ether in a 10 ° / ₀ aqueous solution (in the presence of 1 g / l surfactant of Example 16)

Distance ratio (in presence.. ■

of steam) 1: 6.2 1: 6 1: 6.3 1: 5.3 _:

Yarn tensile strength g / Üen 3.21 3.78 3.83 3.21 ',,

Elongation 28 25 22 21 '■' ■ '

Similar results are obtained from polyethylene and poly- 25 1: 6; they then have the following serimetributes 1 made with hooves of stereospecific see properties: Catalysts obtained.

; Tensile strength 4.07 g / den

Example 11 Elongation 22%.

108 g (0.4 mol) of octadecylamine are in a. These fibers are made with the following dyes

Brought 1-1 three-necked flask, stained with agitator, with good intensity and fastness: Thermometer and reflux condenser is provided. The

Amine is kept at 70 ^° C .; for the formation of the amine CI Direct Yellow II (C. L-No. 40 000)

salt, 24 g (0.4 mol) of glacial acetic acid are added. 35 C. I. Acid Red 115 (C. I. No. 27 200)

Immediately afterwards 37 g (0.4 mol) Epi-CL Acid Blue (C. L-Nr. 62 125)

chlorohydrin added. The mass then becomes 90 Mi C. I. Acid Black (C. L No. 20 470);

Heated to 110 ° C for a long time. After cooling to C.I. Acid Red 216 (C. L-No. 1182)

40 ^° C., 300 ml of methanol are added. Now CI Disperse Yellow 20 (CI No. 1667)

86 g (2 mol) of anhydrous ethyleneimine added, and 40 C.I. Disperse Red 18 (C.I. No. 1695)

the mixture is refluxed for 6 hours. C. I. Disperse Blue 2 (C. I. No. 1713) cooks. Then it is cooled to 30 ° C, there will be

44.9 g (0.8 mol) of potassium hydroxide were added, and according to Example 12

After boiling under reflux for 2 hours, the solution is:

medium distilled off in vacuo, and the formed 45 108 g (0.4 mol) of octadecylamine and 100 ml of metha-

The condensation product is extracted with n-heptane. nol are placed in a 1-1 three-necked flask,

The condensate is removed by distilling off the with stirrer, thermometer and reflux condenser

Solvent in vacuo as a solid waxy sub-is provided.

substance in a yield of 83 ° / ₀ of the now used is heated to the solution of the amine, then

Products received. (Water solubility 0.028 ° / ₀ ). 50 37 g (0.4 mol) of epichlorohydrin are slowly added

From 150 g of the condensate prepared as described above sets, and the mixture is 2 hours at 6O ⁰ C

and 2850 g of polypropylene (made with the help of heated. Now the mass is cooled to 30 ° C, and it

stereospecific catalysts, with a limit, 86 g (2MoI) of anhydrous ethyleneimine are added

viscosity of 1.42, determined in tetrahydronaphthalene, and the whole thing is for 4 hours on the back

boiled at 135 ⁰ C, a residue after the heptane extract 55 flow. After cooling to 30 ⁰ C are

tion of 93.4 ° / ₀ and an ash content of 0.026 ° / "), 22.45 g (0.4 mol) of potassium hydroxide was added, followed

a mixture is prepared, which in a melting the mixture is refluxed for 2 hours

spinning device is spun under the following conditions. _: .:

will: :; The chloride formed is filtered off warm,

^{Screw temperature} 230 ° C. 6o ™ ^d the solvent is distilled off in vacuo;

the yield, based on the starting substances,

SEndSempe; atuV V / .V. mC ^? ζ ' ff ^ _v " _t

c »; _nn ^ .-. r. _Ann ^ tnin ο ΐί From 150 g of the condensate prepared as above

bpmndusenart 60 / 0.8 · Io, " _o ""_^{.." 6} ". .....

. Pressure 22 kg / cm ^{2 and 2850} S polypropylene (made with the help of

Winding speed '.'. 250 m / min. ⁶ S stereospecific catalysts, with a limiting vis-

'kositat of 1.3, a residue after the heptane

The fibers obtained are in the presence of extraction of 97.5% and an ash content of

Steam at 150 ⁰ C with a stretching ratio of 0.059%) a mixture is produced that in one

15 16

Melt-spinning device is provided under the following conditions; the mass is up to its melting point is used: heated, and then 18.5 g (0.2 mol) of epichloro

·. Screw ^{temperature 230 0} C ^ fiV ^ u'L ^ T ^ Z ^ i ³ w? ** ! F ^Dg

Head temperature 220 ^{0 C.? 5} ^ ^rm * ' ^a _o f · ^{30 1} ^ ⁴⁰ ? ^ J? ^lt >, ™ £ f,

Spinneret temperature 200 ° C ⁵ to 95 ° 200ml / _o sodium ethanol and 86g (2MoI)

Spinneret type 60 / 0.8 x 16 ethyleneimm added. After boiling for 4 hours

Pressure 27 ke / cm ^{2 on the Ruc} ™ ^u " ^Wlf d the solvent in the vacuum

Winding speed! '. 270 m / min. distilled; it becomes a solid, waxy condensate

■ ^: - ^: - ° .... m a yield of 98 ° / ₀ obtained. ; ^; -

The fibers obtained are stretched in the presence of steam at 150 ^° C. with a ratio of 1: 5.3 and 2850 g of polypropylene (produced with the aid of; they show the following serimetric stereospecific catalysts, with a limit properties: viscosity ^] of 1.4, a residue according to the Hep-

. - ■ Tensile strength 3.81 g / den JS ⁸ ^ V? ^{11 93} / Λ ^and ^ ^han ash content of

Elongation 26 ° / ¹⁵ 0.026 ° / ₀ ) a mixture is produced that in one

^{/ o>} Melt-spinning device under the following conditions

On these fibers, the following are used in Example 11::. ·;:, · R

listed dyes staining with good screw temperature .. V ΐ 230 ° C ''

Preserved intensity and authenticity. .. Head temperature !! ^ '. 220 ⁰ C .: V "'.;

Example 13 ■ ²⁰ Spinneret temperature .. '. ". *',." 210 ° C.

• 74g (0.4 mol) dodecylamine and 100 ml methanol -: ^ ^dozenart ■ ^ X ^ *

^are placed in a 1-1 three-necked flask, the winding speed . . ' 230 m / min. '

with agitator, thermometer and Ruckfiußkuhler . ,,: ■■■.,

see is. 25 The fibers obtained are in the presence of

Now 37 g (0,4MoI) epichlorohydrin long steam at 150 ⁰ C with a ratio of 1: 5.3

sam is added and the mixture is stretched for 2 hours; they show the following serimetric

heated to 60 ° C. Now the mass is cooled to 30 ° C, properties: · ■ ··· ■ '

and there are 86 g (2 mol) of anhydrous ethyleneimine tensile strength .... ,. , ....:, ... 3.12 g / den

added, and the whole thing is done for 4 hours on 30 _n ? ° :: ■■■ oco /

Refluxed. After cooling to 36 ⁰ C, the guild -..- · · · · <«/ 0 ·

22.45 g (0.4 mol) of potassium hydroxide are added, whereupon these fibers are used in Example 11

the mixture refluxed for 2 hours with the dyes listed. Staining with good will. The chloride formed in the process is warm abfil- intensity and authenticity.,
trated, and the solvent is removed in vacuo. . r. v <

distilled. The yield based on the starting.? ^{eisp ie} ■ · ■

substances, is 91%. The product has a mixture of 150 g? of the condensate and

.Water solubility of 0.032 ° / ₀ . 2850 g polypropylene, both loaded as in Example 12

Aüs 120 g of the condensate prepared as above is written in a melt spinning device under and 2880 g of polypropylene (made using 40 spun conditions:

stereospecific catalysts, with a ^ limit .. screw temperature ..... '. 230 ° C

viscosity of 1.3, a residue after heptane - _K opftemperatur _.....; .... 220 ° C ';

Α "Τ · 'λ! ° Γ t ^mem ^ ff ^VCn ' spinneret temperature.,.,. 200 ° C '^

0.059 ·,) a mixture is produced which in a spinneret type! .7 .. 60 / 0.8 -16

Melt spinning machine under the following conditions «pressure 27 kg / cm * ■ '

will be able to: .-... ' winding speed'. '. 270 m / min.

Screw temperature · .. 230 ⁰ _{C TT} - "-r '..."

■ Kopftemoeratur 22O ⁰ C. Immediately before winding the yarn Spinndüsentemperätür "is. '.'. '.'. 200 ° C ^{mi}, 6} ^ ₁ .. ¹⁵ ° / o" p? Aqueous ethylene glycol Digly-

Spinneret type 60 / 0.8-16 50 cidylate solution humidified - -

-Q _n J ₀ J,. 25 Whom ² It is then in the steam with a stretching behavior

^; . Winding speed '.'. 280 m / min. , ^nis J ^{on l} : ⁵ I ³ stretched. An dm fibers obtained

... ■ are used with the color schemes described in example 11

• \ The fibers obtained are obtained in the presence of fabrics particularly real (against wet washing and steam at 150 ⁰ C with a ratio of 1: 5.3 55 rubbing) colorations. - 'stretched ;; they show the following serimetric “. . , - '■ "'
Properties: .... - Example 16 ....-

• Tensile strength ^: 3 7 g / den The following products are packed in a 6-1 three-necked

Expansion 28 ° / flask introduced, the one with stirrer, thermometer

60 and reflux condenser is provided:

• The octadecylamine shown in Example 11 is used on these fibers. / ..... .1345g

led dyes staining with good intensity epichlorohydrin 925 2

and maintain authenticity. ₉₅ <y _oiger ethyl alcohol ''.'.'.'.'.'.'.'.'.'.'.'. 2270 g

B eis ρ ie 1 14 _{6g The mass is brought to about 85} ° _C while stirring

104.2 g (0.2 mol) of dioctadecylamine, (C ₁₈ H ₃₇ ) ₂ NH, heated for 8 hours and then 580 g of hexa- ¹

are placed in a 1-1 three-necked flask to which methylenediamine is added. The heating is 4 hours

long continued with stirrer, thermometer and reflux condenser, whereupon part of the alcohol

Claims (1)

17 18 (approx. 1200 g) passed distilled off at ordinary pressure and thereby converted into a spinning solution; will. The remaining alcohol is in a vacuum - it is then dry spun at 80 ° C, dryer at 60 ⁰ C under a pressure of 5 to 10 mm The fibers are over a hot plate at 150 to removed. The solid obtained is ground and stretched at 160 ° C. with a stretching ratio of 1: 5, sifted. When analyzed, it gives a nitrogen content of 5 They have the following properties: of 7.03%. : 7usfestii »keit"? 12 ff / den From -10% of the above condensate and 90% poly- elongation 21 ° / acrylonitrile with a molecular weight of 71,500 is now "" "' a mixture prepared, of which 10 kg in 32 kg Di- With those described in the previous example methylformamide dispersed at room temperature. will. The dispersion is then colored by the pipes. a heat exchanger, which at 100 to 12O ⁰ C ". hold, passed through and thereby in an example 18 Transformed into a spinning solution, which finally at 80 ° C. At 60 ° C, a solution of 5 kg of the condensate is dry spun. 15 sats from Example 17 in 400 kg of dimethylformamide The resulting fibers are manufactured at 150 to 16O ⁰ C. with a stretching ratio of 1: 5 in the steam. The solution is cooled to room temperature, stretched. You will then BE-- with water at 100 ⁰ C and there are 95kg acrylonitrile-ethyl acrylate copoly acts (to stabilize the dimension of the fibers) mer (ratio 98: 2, molecular weight 67,300) therein di- and finally mechanically crimped, split at 105 ° C for 20. The dispersion is through the pipes of a 1 hour ~ steamed, sizing, cutting and heat exchanger at 100 to 120 ° C and then dried. They show the following serimetric Eigen- converted into a spinning solution. She will be at shafts: 80 ° C dry spun. ZnpfestiVkeit 1 2 ff / den ^{The chamfer} m are made in the presence of steam: Defmual '27 ° / ^{25 ° 16 ° C with a ratio} of 1: 5 stretched. she then show the following properties: With the following dyes, intense and tensile strength will be 3.01 g / den real staining obtained: elongation 23%. CI Direct Yellow 11 (C. L-No. 40 500Ϊ _A .. "''."".'.°' -. _{H £} CI Acid Red 115 (C. L-No. 27 200) ³ ° ^An ? ^l ? ^{sm fiber W} 5 ^{den with} . ^{the in the example} P iel l ^e C I Acid Blue 40 (C I Nr 62 125) described dyes intense and genuine C. L Acid Black 1 (C L-Nn 20 470) stains.
CI Acid Red 216 (C. L-No. 1182) C. I. Disperse Yellow 20 (C. L-No. 1667) Claims: CI Disperse Red 18 (C. L-No. 1695) ³⁵ , _. "... , _. . CI Disperse Blue 2 (C. L No. 1713) ^L J «tdfaden or fibers from a mixture CI Basic Green 1 (C. L-No. 42 040) ^au . ^s plefinpolymeren or Acrylnitnlpolymerer CI Basic Violet 14 (C L-Nr 42 510) ¹ ^ * ^emer basic polymeric nitrogen compound as well as other customary additional . . ₁ 40 means, characterized in that: Ά e 1 s ρ ι ell / _{the threads x up to 2} 5 percent by weight, based on aui The following compounds are put into a 2-1-three-weight polymer, stick-necked basic polymeric flask introduced, the with agitator, thermo-substance compounds with a water solubility before meter and reflux condenser: contain less than 0.1%, namely on n-dodecylamine 185 g ⁴⁵ _{a) a} condensation product of epichloro Epichlorhydnn 185 g _{h in it and a primary} aliphatic 95% ethyl alcohol 370 g monoamine with 3 to 30 carbon atoms The mixture is stirred or secondary aliphatic monoamine mi for 8 hours boiled at 75 to 8O ⁰ C to reflux, then 50 ^{4 to} 60 carbon atoms, which nachträg 60 g of ethylenediamine added, and the heating is still borrowed with a polyamine or an ali Continued for 4 hours. Now a 30% phatic imine has been implemented, or ai Aqueous sodium hydroxide solution is added to avoid the reaction b) a condensation product of epichloro to neutralize the hydrochloric acid formed and the gehydrin and a primary aliphatic poly Sodium chloride is formed by decanting 55 amine with 2 to 30 carbon atoms or respectively separated from the solution. Almost all of the available _e j _nem secondary aliphatic polyamine mi Alcohol is distilled off at ordinary pressure, 4 to 60 carbon atoms, which after and drying is carried out in a vacuum dryer with an alkylating or arylyl ended at 6O ⁰ C under a pressure of 5 to 10 mm. funds have been implemented, The solid product obtained is ground and ground sifts. It contains 10.7% nitrogen. and that the threads optionally with Wasserunlöt 300 g of the condensate obtained in this way have been aftertreated in light-making agents 9.5 kg of dimethylformamide dissolved at 60 ° C. The solution 2. textile thread or fibers according to claim 1, dt is brought to room temperature, and it is characterized in that the olefin polymer ir 2.7 g copolymer of acrylonitrile with methyl methacrylate 65 is essentially crystalline polypropylene. (in a ratio of 95: 5 with a molecular weight of 3. Process for the production of textile threads 70 500) added. The dispersion is made by the or fibers by spinning a mixture of Tubes of a heat exchanger at 100 to 120 ⁰ C olefin polymers or acrylonitrile polymers m a basic polymeric nitrogen compound and, if necessary, other customary additives, characterized in that a mixture is used which is 1 to 25 percent by weight, based on the polymer weight of a basic polymeric nitrogen compound having a water solubility of less than 0.1 weight percent contains the a) by condensation of epichlorohydrin and a primary aliphatic monoamine with 3 to 30 carbon atoms or a secondary aliphatic monoamine with 4 to 60 Carbon atoms, which subsequently still has been reacted with a polyamine or an aliphatic imine, or
b) has been obtained by condensation of epichlorohydrin and a primary aliphatic polyamine with 2 to 30 carbon atoms or a secondary aliphatic polyamine with 4 to 60 carbon atoms, which has subsequently been reacted with an alkylating or arylation agent, Drawing the threads and, if necessary, post-treating the drawn threads with a water-insolubilizing agents.