DE1469107B - Textile fibers made from basic modified homopolymers or copolymers !! of ethylene, propylene or acrylonitrile - Google Patents

Description

1 2

It is known that fibers can be dyed from the reaction of 1 mol of a primary amine with

Olefin or acrylonitrile polymers by adding 3 to 30 carbon atoms or a secondary one

to improve basic agents. For example, amines with 4 to 60 carbon atoms are 1 to 3 moles

according to French patent 1190 703 epichlorohydrin and subsequent reaction with

Polyalkylenimines, polyesters, polyamides, mixtures 5 0.1 to 10 mol of a disecondary aliphatic, aromatic

of polyalkyleneimines and polyamides, as well as geometric or heterocyclic amines

mixtures of polyalkylenimines and ethoxy resins have been considered. ".:

Color modifiers used for polyolefins. The production of the basic condensation pro-

German Auslegeschrift 1 013 830 relates to a product that is not the subject of the invention

Process for improving the dyeability of io by reacting the corresponding amines or

Polymers based on acrylonitrile using their salts with epichlorohydrin in addition or from

of a basic nitrogen-containing polyester as an entity of solvents or condensation

Color modifier. ■ - ■ average. Suitable aliphatic amines are N-Dode-

The German Auslegeschrift 1 004 767 relates cylamine, hexadecylamine, octadecylamine, diocta to a process for improving the colorability 15 decylamine, dioctylamine or their salts. Particularly suitable as hetero of acrylic fibers by adding a copolymer, cyclic amines, are piperazine, dipipedas made of acrylonitrile, a salt of an amine of an unidyl and their derivatives. Disecondary maleic anhydride with ammonium derivatives or diamines which are suitable for the direct saturated acid and the reaction product of the reaction of epichlorohydrin and which consist of NH groups or NH ₂ with morpholine in the molecule, the ammonium derivatives having 20 groups which contain hydrogen due to steric hindrance. Such a coloring act as secondary groups are piperazine, but modifier shows only a very low up-1,8-p-methanediamine, Ν, Ν'-diisopropylhexamethylene ability to accept dye. The poor Auf- diamine, 1,3 - bis - (n - Dodecylamine) - 2 - propanol, nabmefähigkeit is due to the nitrogen of the amidine 4,4'-bis- (methylamine) -diphenylmethane and N, N'-digroups or Attributed to morpholine groups. 25 butylhexamethylenediamine suitable.
In addition, morpholine derivatives are extremely expensive, so that, from an economic point of view, the extrusion of mixtures of polyolefins or the use of such color modifiers has a limit of 1 to 25 percent by weight of acrylonitrile polymers. basic condensation products produced, where

It is also already a dispersant for dispersing by melt spinning or optionally 30

Pressing out in a warm state, if necessary after the basic condensation product in the

Division in a spinning solvent, deformable, molten mass, optical fillers or others

Easily dyeable polymeric mass, consisting of common additives, can be used. As a dispersing

a resin-like condensation product, the watering agents of which are preferably the following solid dispersion

water solubility below 0.1% heg *! ^{made of} epichlorohydrin 35 medium suitable: cetyl and stearyl alcohol, stearic

with at least one amine with at least 3 carbon atoms and terephthalic acid, benzoin, furoin, vinyl stearate,

men or a corresponding amine salt in a mixture of mono-, di- or tristearic acid esters of glycerol,

with a thread-forming polymer or mixed poly- monoethanolamine stearate, stearylamine, aliphatic

mers of an olefin, such as polyethylene, polypropylene, C ₆ - to C ₃₀ amines, condensation products of ethylene

Polybutene, acrylonitrile, have been proposed. 40 lenoxide with alcohols, amines or phenols, poly-

The use of multifunctional amines in stearamide, polyacrylic acid, polystyrene, styrene copoly-

in some cases to a partial formation of merers, terpene polymers, etc.

branched and cross-linked structures, the sion agent when spraying is 0.1 to 5 ° / ₀ .

of the blends cause certain difficulties by spraying the blends of polyolefin

can, because by increasing the branching and 45th or polyacrylonitrile and basic condensation

Degree of crosslinking the meltability of the condensed product obtained fibers can be mono- or

sate is generally decreasing. Branching and connecting be plurifile and become sequential to manufacture

Networking very often include undesirable phenomena of threads or staple fibers or for manufacture

thermal decomposition. bulky yarns or staple yarns are used.

The subject of the invention is now textile fibers made of 50 basic modified homo- or copolymers 1190 703. The color modifiers of ethylene, propylene or acrylonitrile differ from the products of the French patent specification 1190 703, which according to the present application are characterized by the fact that they contain tertiary dispersants, optical fillers or quaternary nitrogen atoms contain, which contain a better or different conventional additives, characterized by a dye absorption capacity than the amidine groups by a content of 1 to 25 percent by weight of 55-containing or basic secondary nitrogen-basic condensation products, the by react (imines) containing modifiers of the frenchition of epichlorohydrin with primary aliphatic see patent effect. Compared to the product C _{3 to} C ₃₀ amines or secondary aliphatic th of the German Auslegeschrift 1 013 830, the C ₄ to C ₆₀ amines or their salts and other color modifiers of the present invention have the setting of the reaction products obtained with a 60 Advantage of giving the fiber a hydrophilic character or lending more disecondary aliphatic aromatics and thus giving away the dyeability of the fiber or improving heterocyclic amines or by improving them. The color modifiers of the German straight reaction of epichlorohydrin with disecondary legeschrift 1 013 830 do not contain any hydroxyl groups. Diamines which have NH groups or two in the molecule. The color modifiers of the German interpretative publication NH ₂ groups, which react as secondary groups, 65 1 004 767 show only a very low uptake. ability for dye compared to the modifiers

Textile fibers according to the invention preferably receive gates of the present invention, the tertiary or

basic nitrogen condensation products represented by quaternary amines. In addition, mor-

3 4

pholine derivatives are very expensive, so that the following serimetric properties

related to the use of such coloring modifications:

a limit is set. . Tensile strenght '-; 42g / den

Since the state of the art has a rule that elongation 25 ° /

how good color modifiers must be, 5 '

can not be deduced, the subject of the invention for After stretching, the fiber with a 5 ° / ₀ igen

not close to the specialist. , aqueous solution of ethylene glycol diglycidyl ether

The textile fibers according to the invention can be moistened and then dried. U--,.: - ■ - ■

A suitable way of a treatment to achieve the on these fibers are with the following dyes

Water-insolubility of the basic condensation colors of good intensity and fastness:.: products are subject to. Particularly useful

For this task, the treatments with Form C. I. Direct Yellow 11, C. L-No. 40,000 (acid

aldehyde, diisocyanates, diepoxy compounds or dyes)

Crosslinking agents, such as divinylbenzene or ahn-C-I. Acid Red 115, C. L-No. 27 200 (acidic ^colors . 15 substances)

This treatment is given before or after stretching C.I. Acid Blue 40, C. L-No. 62125 (acidic color

carried out, the stretching in proportions substances)

between 1: 2 and 1:10 at temperatures between 80 C. I. Acid Black 1, C. L-No. 20 470 (acidic color

and 150 ° C in with hot air or steam or similar substances)

Medium heated stretchers carried out ao C. I. Acid Red 216, C. L-No 1182 (metallic

will. Dye)

The fibers obtained in this way are given a dyeing with C. I. Disperse Yellow 20, C. L-No. 1667 (plasto-

subjected to acidic or plastic-soluble dyes. soluble dye)

They also have a good affinity for basic coloring C. I. Disperse Red 18, C. L-No. 1695 (plastol-free

fabrics. 25 licher dye)

C. I. Disperse Blue 2, C. L-No. 1713 (plastoless)

B e i s ρ i e 1 1 'icher dye)

486 grams (1.8 moles) of n-octadecylamine, 333 grams (3.6 moles) of Example 2
Epichlorohydrin and 900 ml of ethanol are poured into a 30

with a mercury stirrer, thermometer and return 108 g (0.4 mol) octadecylamine, 74 g (0.8 mol) epi-

6-1 three-necked flask equipped with a flow cooler. chlorohydrin and 300 ml of ethanol are in one with

The mass is refluxed for 8 hours; A mercury stirrer, thermometer and back is then cooled to 20 ° C. and 543 g (6 mol) of a 2-1 three-necked flask equipped with a flow cooler are introduced. 95 ° / _o sodium piperazine, 388.5 g (4.5 mol) of epichlorohydrin 35 The mass is heated for 8 hours a reflux condenser, and 900 ml of ethanol was added. The mixture is cooled to 20 ° C and 95 ° / oiges Piperbei stirred for 30 to 40 ⁰ C 90.5 g (1 mole) and azine 15 hours reflux, 55.5 g (0.6 mol) of epichlorohydrin and 200 ml of heated cooler. Ethanol is added in the last 5 hours.

312 g (7.8 mol) of sodium hydroxide in small portions. The mixture is added at 30 to 40 ° C. for 1 hour. After filtering warm, the 4 ° was stirred and then under reflux solvent for 14 hours distilled off. heated cooler. In the last 4 hours of heating

The residue will be under a residual pressure of 56 g (1.4 mol) of sodium hydroxide in small amounts

5 mm by heating to 140 to 146 ° C for 1 hour in full proportions. It is filtered warm and that

constantly dried. A solid resinous pro-solvent is distilled off.

obtained product, which is then ground and produced. The residue is heated up by heating for 1 hour

is sieved. 140 to 160 ° C under a residual pressure of 5 mm fully

A mixture of 1.030 kg of the above is dried continuously. It becomes a solid, resinous one

written condensate produced and 19.570 kg of product obtained, which is then ground and

one is obtained with the help of stereospecific catalysts. '. _: ...; ··.-.-

made of polypropylene, which has a limit 50 A mixture of 0.345 kg of the above

viscosity [η], determined in tetrahydronaphthalene described in the case of the condensate produced and

135 ⁰ C, of 1.37, a residue after the heptane 6.555 kg with the help of stereospecific catalysts

extraction of 96.3 ° / ₀ and an ash content of polypropylene obtained, which has a limiting viscosity

0.024. tat fr?] (determined in tetrahydronaphthalene at 135 ° C)

The mixture is in a melt spinning device 55 of 1.37, a residue after the heptane extraction

spun under the following conditions: 96.3 ° / ₀ and an ash content of 0.024 ° / ₀ has produced.

Screw temperature 24O ⁰ C The mixture is in a melt spinning device

Spun head temperature 230 C under the following conditions:

Spinneret temperature ... 220 ° C 60

Spinneret type 60 holes, through screw temperature 240 ° C

knife 0.8 mm, head temperature 220 ° C

Length 16 mm spinneret temperature ... 220 ° C

Pressure 45 kg / cm ² spinneret type 60 holes, through

Winding speed 250 m / minute. 65 knife 0.8 mm,

• ■ Length 16 mm

The fibers obtained show a pressure of 42 kg / cm ^{2 after stretching}

at 13O ⁰ C and a draw ratio of 1: 5.3 m in take-up speed 250 / min

5 6

After stretching, the fibers obtained show at The fibers obtained show in the presence of 130 ^° C. in the presence of steam in a stretching steam at 130 ^° C. with a stretching ratio of

ratio of 1: 5.3 following serimetric properties 1: 5.3 following serimetric properties:

shafts: tensile strength 4.03 g / den

Tensile strength 4.5 g / den ⁵ elongation 25 ° / ₀

Immediately after stretching, the fibers are

Immediately after stretching, the fiber is treated with a 25% aqueous solution of ethylene

moistened with a 5% aqueous solution of ethylene glycol glycol diglycidyl ether and then dried.

diglycidyl ether moistened and then dried. io The following dyes are used on these fibers

Dyes of good intensity and fastness are obtained on these fibers with the following dyes:

Dyeings of good intensity and fastness

- ",. ". C.I. Direct Yellow, C. L No. 40,000

keep: , _ , . , J

(acidic dye)

C. I. Acid Red 115, C. L-No. 27 200 C. I. Acid Red 115, C. L-No. 27 200

(acidic dye) (acidic dye)

C. I. Acid Blue 40, C. L No. 62 125 C. I. Acid Blue 40, C. L-No. 62 125

(acidic dye) (acidic dye)

C. I. Acid Black 1, C. L-No. 20 470 C. I. Acid Black 1, C. L-No. 20 470

(acidic dye) (acidic dye)

C. I. Acid Exot 216, C. L No. 1182 C. I. Acid Red 216, C. L No. 1182

(metallic dye) (metallic dye)

C. I. Disperse Yellow 20, C. L-No. 1667 C. I. Disperse Yellow, C. L-No. 1667

(plasto-soluble dye) (plasto-soluble dye)

C. I. Disperse Red 18, C. L-No. 1695 C.I.-Disperse Red 18, C. L-No. 1695

(plasto-soluble dye) (plasto-soluble dye)

C. I. Disperse Blue 2, C. L-No. 1713 C. I. Disperse Blue 2, C. L-No. 1713

(plasto-soluble dye) (plasto-soluble dye)

^. . , "Example4

Example3 30

92.5 g (0.5 mol) n-dodecylamine, 92.5 g (1 mol) epi-

540 g (2 mol) of octadecylamine, 370 g (4 mol) of epichlorohydrin and 250 ml of ethanol are in one with

chlorohydrin and 1000 ml of ethanol are poured into a with a mercury stirrer, thermometer and back

a 1-1 three-necked flask fitted with a mercury stirrer, thermometer and reflux condenser,

6-1 three-necked flask equipped with a flow cooler. 35 The mass is refluxed for 8 hours.

The mass is heated on the reflux condenser for 8 hours, then cooled to 20 ° C and 10.5 g (1 mol)

heated, then cooled to 20 ° C. and added 181 g (2 mol) of 95% strength piperazine, 46.3 g (0.5 mol) of epichlorohydrin

95 ° / _o sodium piperazine and 500 ml of ethanol was added. and 150 ml of ethanol added.

It is stirred for 1 hour at 30 to 40 ° C and stirred for 1 hour at 30 to 40 ⁰ C, the mixture is then heated for 14 hours Rückfiußkühler 40 mixture 14 hours a reflux condenser. In heated. In the last 4 hours of heating, 60 g of 160 g (4 mol) of sodium hydroxide in small portions (1.5 mol) of sodium hydroxide in small portions are added to the last 4 hours of heating.

It is then filtered warm and the solution. It is filtered warm and the solvent is removed.

distilled off medium. The residue is distilled through 1 hour 45 minutes.

Heating at 140 to 160 ⁰ C unte pure residual pressure The residue mm completely dried by 1 hour of heating to the fifth There is obtained a solid 140 to 160 ⁰ C under a residual pressure of 5 mm full resinous product, the overall then continuously dried. A solid resinous grind and sieve are obtained. Product that is then ground and sifted

It becomes a mixture of 0.894 kg of the 50 above.

described obtained condensate and 16.985 kg There is a mixture of 150 g of the as above

of a condensate obtained using stereospecific catalysts and 2.850 kg of one

holding polypropylene produced, the limit obtained with the help of stereospecific catalysts

viscosity [η] (determined in tetrahydronaphthalene for polypropylene produced, which has an intrinsic viscosity [η]

135 ° C) of 1.37, a residue according to the heptane 55 (determined in tetrahydronaphthalene at 135 ° C) of

extraction of 96.3% and an ash content of 1.37, a residue after the heptane extraction of

0.024 ° / ₀ . 96.3 ° / ₀ and an ash content of 0.024 ° / ₀ has.

The mixture is in a melt spinning device The mixture is in a melt spinning device

spun under the following conditions: spun under the following conditions:

Screw temperature .... 240 ° C Screw temperature .... 240 ° C

Head temperature 230 ° C head temperature 23O ⁰ C

Spinneret temperature ... 220 ° C Spinneret temperature ... 220 ° C Spinneret type 60 holes, through-spinneret type 60 holes, diameter 0.8 mm, 65 knife 0.8 mm, Length 16 mm length 16 mm

Pressure 45 kg / cm ² pressure 38 kg / cm ²

Winding speed 250 m / minute Winding speed 250 m / minute

The fibers obtained in this way show, when they are in opposition, intense solid colorations on these fibers

was obtained from steam at 130 ⁰ C with a stretching ratio with the following dyes:

IZ ^ IZT ^{corner Will 'fOlSende serimetric.} CI Direct Yellow 11, C. L no. 40,000

Properties. (acidic dye)

Tensile strenght. :.; , 3.98 g / den ° _C. I. Acid Red 115, C. L No. 27 200

Elongation ..:.: .......... 22% (acidic dye)

Immediately after stretching, the ^C -. ^L Acid Blue 40 C. L no. 62 125

Fibers with a 6% aqueous solution of Ethy-: - ^ 'vY ^ / ff, ° f >" _T ^ - - _n J _n ^ '""'=:"

Lenglycol diglycidyl ether moistened and dried. ■ io C I. Acid Black 1 C. L no. 20 470

The following dyes are used on these fibers _:

Colorings of good intensity and fastness obtained: ^u , ^Ac ' ^d *> ^εα ± ^l \ ^u ^'

(metallic dye)

C. I. Direct Yellow 11, C. L No. 40,000 C. I. Disperse Yellow 20, C. L-No. 1667

(acidic dye) (plasto-soluble dye) -

CI Acid Red 115, C; L no. 27 200 ⁵ CI Disperse Red 18, C. L-No. 1695

(acidic dye) (plasto-soluble dye)

C. I. Acid Blue 40, C. L No. 62 125 C. I. Disperse Blue 2, C. L-No. 1713

(acidic dye) (plasto-soluble dye)

CI Acid Black 1 ^ C. L no. 20 470 ₂₀ CI Basic Green 1, C. L-No. 42 040

(acidic dye) "(basic dye)

C. I. Disperse Red 18, C. L-No. 1695 C. I. Basic Violet 14, C. L-No. 42 510

(plastosoluble dye) (basic dye)
CI Disperse Blue 2, C. L-No. 1713

'(plastosoluble dye) ₂₅ B eis ρ ie 1 6

Example 5 ¹⁸⁹ ' ^{2 g pereazine} ( ² > ^{2 moles} )> 185 g epichlorohydrin

(2 mol) and 600 ml of ethanol are in a stirrer,

486 g (1.8 mol) n-octadecylamine, 333 g (3.6 mol) thermometer and reflux condenser equipped 2-1-

Epichlorohydrin and 900 ml of ethanol are poured into a three-necked flask. The crowd is taking

stirred with a mercury stirrer, thermometer and re-cooling for 90 minutes and then (at approx

6-1 three-necked flask equipped with a flow cooler. 8O ⁰ C) with stirring for 10 hours on the re-nut condenser

The mass is heated on the reflux condenser for 8 hours.

heats and after cooling to 20 ° C 543 g (6 mol) in the last 3 hours of heating are 80 g

95 ° / _o sodium Pipejazin, 388.5 g (4.5 mol) of epichlorohydrin (2 mol) of NaOH added in small portions,

and added 900 ml of ethanol. 35 NaCl is filtered off in the heat and the filtrate

The whole is stirred for 1 hour at 30 to 40 ° C, precipitated by pouring into acetone (1500 ml),

and then heated under the reflux condenser for 15 hours. The white precipitate is deposited in a heating cabinet

In the last 5 hours, 312 g (7.8 mol) of Na 100 to 110 ⁰ C are dried. The nitrogenous thus obtained

trium hydroxide added in small portions. The resin it contains is ground and sieved. It is a

warm solution is filtered off and the solvent 40 powder with a softening point of approximately

distilled off. 200 ° C.

The residue is heated by heating for 1 hour. In a Henschel-type mixer, at room temperature

140 to 150 ⁰ C under a residual pressure of 5 mm Hg temperature produced a mixture consisting of:

completely dried. It becomes a solid resinous polypropylene (96 ° /) 5 76 ka

Obtain product that is ground and sifted. 45 ^ ti / vstnffhnit; ^ WarV '' '

T ~ · ι · τ * κ · ι 1 ι ι Λ Λ η ι 1 L} Ll * ^ ivoL \ JllllnlLliiG & ίΧαΐ £ *

It becomes a mixture consisting of 10 ^u / ₀ des (4 ⁰ I) 0 24ka

condensation pro- 'obtained as described above '

ductile and 90 ° / ₀ polyacrylonitrile, with one molecule The properties of the polypropylene used

lar weight of 71,500 manufactured. 10 kg of these Mi- are the following:

at room temperature in 32 kg di- 50 limiting viscosity 137 ° /

methylformamide dispersed. Arrears after the hep

The Dispers.on is then passed through tan extraction 96.3 ° / ₀

a dissolver of the heat exchanger type, Δ, Λ- ^ ι ,,, η nmko /

which is kept at 100 to 120 ⁰ C, in a spinning Ascnegenait ............ 0.024 / ₀

solution converted and then dry-spun. 55 The mixture is granulated and under the following

The fibers thus obtained are sprayed in the presence of conditions:

of steam at 150 to 160 ° C with a draw screw temperature .... 240 ° C ^:

ratio of 1: 5 stretched. They are then Cor> ftemperatur 25O ⁰ C

a treatment in water at 100 ⁰ C (to the damsel spinneret temperature '.'. ''. 250 ° C

sionstabil.s.erung of the fibers) a mechanical 60 _{spinneret type 60} holes, through-

Curling for 1 hour in the autoclave of a steam measuring 0 8 mm

treatment at 105 ° C and further finishing, length 16 mm '

Cutting and drying subjected to a maximum pressure of 60 kg / cm *

The fibers obtained in this way show the following winding speed of 470 m / minute
see features: 65

The yarn is at a temperature of 130 ⁰ C.

Tensile strength 3.7 g / den with a stretch ratio of 1: 5.5 in a steam

Elongation 26.2 ° / ₀ heated device stretched.

9 10

Then it is poured into a 2-1 three-necked flask equipped with a stabilizing flow cooler for 15 minutes.

treatment treatment at HO ⁰ C under the conditions The mass is stirred for 14 hours on the back

subject to free shrinkage. flow cooler (at about 85 ° C) heated. In the last

The serimetric properties of the extended 4 hours of heating become 80 g (2 moles) of NaOH

and heat-stabilized yarn are as follows: 5 added in small proportions.

₇ ,, "f -, *:" I · - + ₄ τ "ij." Sodium chloride is filtered off in the heat and

Elongation 21 ° / solvent removed by distillation.

The residue is by heating to 140 bis

The yarn is then crimped and made into staple fibers at 150 ° C under reduced pressure (5 to 10 mm Hg)

cut to a length of 9 cm. io completely dried in 2 hours. The thus obtained

The nitrogenous resin obtained in this example and in example 7 is ground and sieved. It

Staple fibers were given a coloration with the following is a powder with a softening point of 85

Subject to dyes: up to 87 ° C.

CI Beizgelb ICI -Nr 14 025 * ^A mixer of the Henschel type is used in

(acidic dye) ^'15 R ^aumtem P ^er ature made a mixture, consisting

CI Acid Red 115, C. L-No. 27 200 ^from:

(acidic dye) polypropylene (95 ° / ₀ ) 7.6 kg

C. I. Stained red 3, C. L-No. 58 005 containing nitrogen

(acidic dye) resin (5%) 0.4 kg

CI Acid Blue 43, C. L-No. 63,000 ² ° _. _,

(acidic dye) ^The properties of the polypropylene used

CI Acid Black 1, C. L-No. 20 470 ^{are fol} S ^end =

(acidic dye) intrinsic viscosity 1.37

C. I. Acid Yellow 112, C. L-No. 1049 ash content 0.024%

(metallic dye) ²⁵ residue after

CI Acid Red 216, C. L-No. 1,182 heptane extraction of 96.3 ° / ₀

(metallic dye) _n . ...,.,,. ,, ..

CI Acid Brown 30 CI -Nr 1341 ^{The mixture is} granulated and then in one

'(metallic dye)' melt spinning device under the following conditions

CI Dispersrot 18, C. L-No. 1695 ³ ° ^s P ^ntzt:

(plastosoluble dye) screw temperature .... 240 ° C

C. I. Disperse Blue 3, C. L-No. 61 505 head temperature 230 ° C

(plastosoluble dye) spinneret temperature ... 230 ° C

_. ".., j. _Λ j. _c . , ucj ι. ·. Spinneret type 60 holes, through

The dyeing was ^{done in I 1} Z ₂ hours at the boiling point 35 meters 0 8 mm

in baths containing 2.5 ° / ₀ by weight of the fiber length to 16 mm dyes'

contained fabric, with a fiber-bath ratio of maximum pressure 48 kg / cm ^

1:40 executed. Winding speed 450 m / minute

The dyeing with acidic and metallized dyes was in the presence of 3 ° / ₀ ammonium acetate 40 The fiber is held in a top to a temperature of (the weight of the fiber) and of l ° / ₀ a 130 ° C steam-heated apparatus having surface-active Means, consisting of the condensa- a stretching ratio of 1: 5.5 stretched,
tion product of ethylene oxide with an alkylphenol, it is then carried out for 15 minutes at 110 ° C. Stabilization treatment under the conditions of

30 minutes after the start of boiling 2 ° / ₀ 45 were subjected to free shrinkage,

from the weight of the fiber in glacial acetic acid added to the serimetric properties of the stretched

to improve the utilization of the baths. and heat stabilized fibers are as follows:

The staining with plastosoluble (dispersed)

Dyes was the in the presence of 2 ° / ₀ g from the overall tensile strength of 5.2 /

weight of the fiber in surface-active agent is increased. Elongation 22 ° / ₀

leads.

After dyeing, the fibers have flowed- The fiber is then crimped and stacked in a pile

Rinsed off the water and showed in all cases, length of 9 cm cut; the received stacks

d. H. with acidic, metallized and plastosoluble ones are colored with the dyes of Example 1,

Dyes, intense colors. The color fastness 55, whereby intense, solid colorations are obtained,

to light, washing and abrasion turned out to be a further improvement in color fastness

fully satisfactory. obtained when the fibers are

A further improvement of the color fastness is treatment with a 3 ° / _o aqueous Äthylenglykolerhalten when the fibers are subjected (before dyeing) of a diglycidylätherlösung and then 15 Mi-treatment with a 3 ° / _o aqueous solution of ethylene 60 grooves 110 to 120 ° C are heated,
Glykoldiglycidylätherlösung and then the addition of the resinous basic product are heated to 110 to 120 ° C for 15 minutes. according to the invention gives the fibers a high

Lightfastness. After 200 hours in the sun

Example 7 light (actual exposure) and in accordance with

65 mung with the variations of the seventh stage of the

340 g 1,8-p-menthandiamine (2 mol), 185 g epichlor blue standard scale (Unitex definitions for light hydrin (2 mol) and 600 ml of isopropanol are measured in fastness) was on fibers of polypropylene one with a stirrer, thermometer and back or polyacrylonitrile, containing various pro

cent content of resinous condensation products, the following residual fastness measured:

° / o of condensate Residual authenticity 5
1
0.2
0 75 ° / _{0 of} the initial value
65 / ° _{0 of} the initial value
58 ° / o of the initial value
39 ° / _{0 of} the initial value

Example 8

86 g of anhydrous piperazine (1 mol), 170 g of p-menthane diamine (1 mol), 600 ml of isopropanol and 185 g of epichlorohydrin (2 moles) were placed in one equipped with a stirrer, thermometer and reflux condenser 2-1 three-necked flask filled.

The mass is heated for 1 hour with stirring at 50 to 60 ⁰ C and then further heated for 10 hours with stirring Rücknußkühler. In the last 5 hours of heating, 80 g (2 mol) of NaOH are added in small portions.

Sodium chloride is filtered off in the heat and that Solvent removed by distillation.

The residue is completely dried by heating to 150 ^° C. under reduced pressure (5 to 10 mm Hg) for 2 hours. The nitrogen-containing resin thus obtained is ground and sieved. It is a powder with a softening point of 78 to 80 ° C.

In a mixer of the Henschel type is at room temperature made a mixture consisting of:

Polypropylene (95 ° / ₀ ) 5.7 kg

Nitrogenous
Resin (5%) 0.3 kg

The properties of the polypropylene used are as follows:

Intrinsic viscosity 1.37 ° / ₀

Ash content 0.024% / ₀

Backlog after the

Heptane extraction of 96.3 ° / ₀

The mixture is granulated and then injected in a melt spinning machine under the following conditions:

Screw temperature ^{240 0 C}

Head temperature 230 ⁰ C

Spinneret temperature ... 230 ^{0 C}

Spinneret type 60 holes, diameter 0.8 mm,
Length 16 mm

Maximum pressure 52 kg / cm ²

Winding speed 430 m / minute

The fiber is drawn in a steam-heated device maintained at 130 ° C. at a draw ratio of 1: 5.5. It is then subjected to a treatment for dimensional stabilization under the conditions of free shrinkage ^{at 110 ° C. for 15 minutes.}

The serimetric properties of the gas-drawn and heat-stabilized yarn are as follows:

Tensile strength 5.1 g / den

Elongation 23 ° / ₀

The fiber is then crimped and cut into 9 cm staple fibers; with the dyes of Example 1, intense solid dyeings are obtained on these staple fibers.

Example 9

400 g Ν, Ν'-diisopropylhexamethylenediamine (2 mol), 185 g of epichlorohydrin (2 mol) and 400 ml of isopropanol are in a with stirrer, thermometer and Filled 2-1 three-necked flask equipped with a reflux condenser. The mass is refluxed at ίο 85 ° C for 23 hours while stirring.

During the last 2 hours, 80 g (2 mol) of NaOH are added in small portions.

Sodium chloride is filtered off while hot and the solvent is removed by distillation.
The residue is completely dried by heating at 150 ^° C. under reduced pressure (residual pressure of 5 to 10 mm Hg) for 2 hours. This residue is a thick and viscous liquid.

In a mixer of the Henschel type, a mixture is prepared at room temperature, consisting out:

Polypropylene (95%) 6.58 kg

Nitrogenous
Resin (6 ° / ₀ ) 0.42 kg

The properties of the polypropylene used are as follows:

Intrinsic viscosity 1.37 ° / ₀

Ash content 0.024% / ₀

Backlog after the

Heptane extraction of 96.3 ° / ₀

The mixture is granulated and then injected in a melt spinning machine under the following conditions:

Screw temperature .... 240 ° C

Head temperature 240 ⁰ C

Spinneret temperature ... 23O ⁰ C

Spinneret type 60 holes, diameter 0.8 mm,
16 mm long

Maximum pressure 55 kg / cm ²

Winding speed 450 m / minute

The fiber is drawn with a draw ratio of 1: 5.3 in a steam-heated device in which a temperature of 130 ^° C. is maintained.

It is then ^{subjected to a dimensional stabilization treatment at 110 °} C. for 15 minutes under conditions of free shrinkage.

The serimetric properties of the drawn and thermally stabilized yarn are as follows:

Tensile strength 5.3 g / den

Elongation 22 ° / ₀

The fiber is then crimped and cut into staple fibers with a length of 9 cm; on These staple fibers are obtained with the dyes of Example 1, intense, solid dyeings.

Example 10

137.6 g anhydrous piperazine (1.6 mol), 170.4 g 1,3-bis (n-dodecylamine) -propanol-2 (0.4 mol), 185 g Epichlorohydrin and 600 ml of methanol are placed in a equipped with a stirrer, thermometer and reflux condenser 2-1 three-necked flask filled.

The mass is heated to 50 to 60 ^° C. for 1 hour while stirring. The heating is continued on the reflux condenser with stirring for 14 hours. In the last 4 hours, 80 g (2 mol) of NaOH are added in small portions. Sodium chloride is filtered off while hot and the solvent is removed by distillation.

The residue is completely dried by heating for 2 hours at 140 to 15O ⁰ C under reduced pressure (residual pressure of 5 to 10 mm Hg).

The residue is a soft, waxy product.

In a mixer of the Henschel type, a mixture is prepared at room temperature, consisting out:

Polypropylene (95%) 5.7 kg

Nitrogenous
Resin (5%) 0.3 kg

The properties of the polypropylene used are as follows: ~~ "

Intrinsic viscosity 1.37%

Ash content 0.024%

Backlog after the

Heptane extraction 96.3%

The mixture is granulated and then injected in a melt spinning machine under the following conditions :

Screw temperature ^{230 0 C}

Head temperature 23O ⁰ C

Spinneret temperature ... 230 ^{0 C}

Spinneret type 60 holes, diameter 0.8 mm,
Length 16 mm

Maximum pressure 47 kg / cm ²

Winding speed 420 m / minute

The fiber is in a steam-heated device in which a temperature of 130 ° C is maintained is stretched with a stretching ratio of 1: 5.3.

It is then ^{subjected to a dimensional stabilization treatment at 110 °} C. for 15 minutes under conditions of free shrinkage.

The serimetric properties of the drawn and thermally stabilized yarn are as follows:

Tensile strength 5.3 g / den

Elongation 21.5%

The fiber is then crimped and cut into staple fibers with a length of 9 cm ;, Intense solid dyeings are obtained on these staple fibers with the dyes of Example 1.

Example 11

86 g of anhydrous piperazine (1 mole), 226 g of 4,4'-bis (methylamine) diphenylmethane (1 mol), 185 g of epichlorohydrin (2 mol) and 600 ml of isopropanol are poured into one with a stirrer, thermometer and reflux condenser equipped 2-1 three-necked flask.

The mass is heated to 30 to 50 ^° C. for 1 hour while stirring. The heating is continued on the reflux condenser with stirring for 14 hours. In the last 4 hours, 80 g (2 mol) of NaOH are added in small portions. Sodium chloride is filtered off while hot and the solvent is removed by distillation.

The residue is completely dried by heating at 140 to 150 ^° C. under reduced pressure (residual pressure 5 to 10 mm Hg) for 2 hours.

The nitrogen-containing resin thus obtained is milled and sifted. It is a powder with a softening point of 106 ° C.

In a mixer of the Henschel type, a mixture is prepared at room temperature, consisting out: . . .

Polypropylene (95%) ..... 5.7 kg
Nitrogenous
Resin (5%) 0.5kg

The properties of the polypropylene used are as follows:

Intrinsic viscosity 1.37%

Ash content 0.024%

Backlog after the

Heptane extraction 96.3%

The mixture is granulated and then injected in a melt spinning machine under the following conditions:

Screw temperature 24O ⁰ C

Head temperature 23O ⁰ C

Spinneret temperature ... 230 ° C
Spinneret type 60 holes, diameter 0.8 mm,
Length 16 mm

Maximum pressure 45 kg / cm ²

Winding speed 410 m / minute

The fiber is at a draw ratio of 1: is maintained in a steam-heated apparatus, in which a temperature of 13O ⁰ C 5.3, stretched.

It is then subjected for 15 minutes under conditions of free shrink to a treatment for Dimensionally stable at 110 ⁰ C; the serimetric properties of the drawn and heat-stabilized yarn are as follows:

Tensile strength 5.4 g / den

Elongation 24%

45

55 The fiber is then crimped and cut into staple fibers 9 cm in length; The staple fiber obtained shows intense and solid dyeings with the dyes of Example 1.

Example 12

103.2 grams of anhydrous piperazine (1.2 moles), 182.4 grams of N, N'-dibutylhexamethylenediamine (0.8 moles), 185 grams of epichlorohydrin (2 mol) and 300 ml of methanol are in a with stirrer, thermometer and reflux condenser equipped 2J three-necked flask.

The mass is heated to 30 to 40 ° C. for 1 hour while stirring. The heating is under reflux Stirring continued for 10 hours. In the last 5 hours, 80 g (2 mol) of NaOH are added in small portions added. Sodium chloride is filtered off while hot and the solvent is removed by distillation.

The residue is completely dried by heating at 140 to 150 ^° C. under reduced pressure (residual pressure 5 to 10 mm Hg) for 2 hours.

The nitrogen-containing resin thus obtained is ground and sieved.

Claims (1)

15 16 In a mixer of the Henschel type, the properties of the stretched and thermostable A mixture is produced at room temperature, the following are the following: ^{based on:} tensile strength 5.1 g / den Polypropylene 5.7 kg elongation 20 ° / ₀ Resin (5 ⁰ I) 0 3 ^ ks' ^{e w} i ^fd fiber and then crimped in staple fibers 'Cut to a length of 9 cm; on the so received The properties of the polypropylene tenen product used will be related to the dyes of the case the following: Spiels I get intense solid colorations. Limiting viscosity 1 37 ⁰ I ^{10 A further} improvement in the strength of the color Aschesehalt o'o24 ^o ° / ^s ^ ^{w 'rd} erbalten characterized in that the fibers before Fär- Residue after the ' ψ ^ a treatment with a 3% aqueous Heotanextraction 96 3 ° / Ethyleneglykoldiglycidylatherlosung and subjected Heptane extraction 96.3 / _{0 15 minuteQ au {nQ big UQ0 c are heated>} The mixture is granulated and then in a 15 Melt spinning device under the following conditions. Claim: splashes: Screw temperature .... 230 ⁰ C Textile fibers from base modified homo head temperature 240 ° C ° of ^the copolymers! of ethylene propylene or Spinneret temperature ... 230 ° C ²⁰ acrylic nitnls, which may contain dispersion Spinneret type 60 bores, diameter included, g e k en η is characterized by knife 0 8 mm has a content of 1 to 25 percent by weight of basic _T3l , _mU '_,' see condensation products produced by reaction Long Io mm. ". ,,,,". ...,.,., Maximum pressure 53 kg / cm * tion of epichlorohydrin with primary a ipatic 25 C ₃ to C ₃₀ amines or secondary aliphatic Winding speed 430 m / minute C ₄ - to C ₆₀ amines or their salts and others The fiber is with a draw ratio of reaction of the reaction products obtained with 1: 5.3 in a steam-heated device in which one or more disecondary aliphatic a temperature of 130 ⁰ C is maintained, ge aromatic or heterocyclic amines or stretches. 30 by direct reaction of epichlorohydrin with It is then 15 minutes under the conditions of disecondary diamines, which are in the molecule NH group- the free shrinkage of a treatment to measure and two NH ₂ groups as secondary subjected to stabilization at 110 ^{0 C;} the serimetri- groups react have been obtained.