DE1270217B - Manufacture of textile threads by melt spinning polyolefins containing nitrogen polycondensates - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

DOIf

German class: 29 b -3/65

Number: 1270 217

File number: P 12 70 217.9-43

Filing date: December 18, 1962

Opening day: June 12, 1968

Process for the production of basic nitrogen polycondensates by reacting primary aliphatic Amines with 3 to 30 carbon atoms or secondary aliphatic amines with 4 to 60 carbon atoms in the presence or absence of solvents and condensing agents with epichlorohydrin and, if necessary, subsequent further condensation of the product with aliphatic, aromatic or heterocyclic bis-secondary amines have already been described.

There has also already been the production of textile fibers from mixtures of these polycondensates and Crystalline polyolefins, especially polypropylene, produced with the aid of stereospecific catalysts, described.

In general, the processes for producing these textile fibers consist of the following process steps:

1. Mixing the polycondensate (1 to 25% of the total mixture) with the polyolefin in any known manner.

2. Granulate the mixture obtained after 1 at a temperature of 170 to 300 ° C, to the mixture to carry out the screw of the spinning devices (using the overall ^a5 pulverten mixture is the feed to the Schnekken and, therefore, the spinning process not sufficiently homogeneous and regular).

3. Compression of the granulate in a melt spinning device through spinnerets that have holes, whose ratio of length to diameter is preferably greater than 1, and then Winding up the spun threads.

4. Drawing and finishing of the threads obtained after 3.

Different polycondensates are used if they undergo drastic thermal treatment during granulation and in spinning (stages 2 and 3 above) are subjected to change and show a decrease their molecular weight and discoloration.

The subject of the invention is a process for the production of textile threads by melt spinning and subsequent drawing of mixtures which contain crystalline polyolefins and 1 to 25 percent by weight of basic nitrogen polycondensates, which are obtained by reaction of primary aliphatic amines with 3 to 30 carbon atoms or of secondary aliphatic amines with 4 to 60 Carbon atoms, optionally in the presence of solvents and condensing agents, with epichlorohydrin and optionally further reaction with the production of textile thread by melt-spinning polyolefins, the nitrogen polycondensates
contain

Applicant:

Montecatini Societä Generale per l'Industria

Mineraria e Chimica, Milan (Italy)

Representative:

Dr.-Ing. A. v. Kreisler, Dr.-Ing. K. Schönwald,
Dr.-Ing. Th. Meyer and Dr. JF Fues,
Patent attorneys, 5000 Cologne, Deichmannhaus

Named as inventor:

Alberto Bonvicini, Milan (Italy)

Claimed priority:

Italy of December 21, 1961 (22 811)

one or more aliphatic aromatic or heterocyclic bis-secondary amines are. The process according to the invention is characterized in that mixtures that are in one oxygen-free atmosphere have been granulated, spun in just such an atmosphere.

Nitrogen with a content of 1 to 100 parts per million oxygen has been found for the invention Method proved to be particularly suitable. It can also use noble gases such as helium, argon, and krypton Xenon can be used.

The practically oxygen-free nitrogen must be used both in granulation and in spinning can also be used on the way from the spinneret to the take-up rolls.

For this purpose, the devices used for granulating and spinning are used accordingly modified, in which essentially inlet and outlet openings for the inert gas are attached. In terms of however, the use of the inert gas between the spinneret and the winder must be used in this Zone an element can be arranged through which the gas flow can be concentrated in this zone.

The process according to the invention can in particular be applied to mixtures of polypropylene with polycondensates of octadecylamine with epichlorohydrin and piperazine can be applied.

809 559/468

The fibers are produced by adding mixtures of polyolefins and 1 to 25 percent by weight of the nitrogen polycondensates and optionally 0.1 to 5% of a solid dispersant for the nitrogen-containing condensate in the molten mass from the group of cetyl and stearyl alcohol, stearic acid, benzoin, furoin, Vinyl stearate, mono-, di- and tristearic esters of glycerol, monoethanolamine stearate, stearamide, N-diethanol lauramide, C ₆ to C ₃₀ __ aliphatic amines, condensation products of ethylene oxide with alcohols, amines and phenols, polystearamide, polyacrylic acid, polystyrene, styrene copolymers, etc. like. spun.

The threads obtained according to the invention can also be yarn and processed on staple fibers will.

The threads obtained according to the invention can be subjected to treatments which (if desired) make the basic nitrogen compounds completely insoluble in water. Are suitable for this purpose especially the usual treatments with formaldehyde, diisocyanates, diepoxy compounds or the like.

According to the invention, films, tapes and other shaped bodies can also be produced.

25th

example 1

a) Starting material, on its manufacture
no protection is claimed here

From 95 kg of polypropylene, produced with the help of stereospecific catalysts and with an intrinsic viscosity [η] of 1.45, measured in tetrahydronaphthalene at 135 ° C, a residue after the heptane extraction of 96% and an ash content of 0.010%) and from 5 kg of a A mixture is produced from polycondensate, prepared by reacting 0.3 mol of octadecylamine with 1.3 mol of epichlorohydrin and 1 mol of piperazine. The mixture is granulated by pressing under the following conditions:

40

Nitrogen pressure 0.5 atm

Extrusion temperature 240 ° C

Capacity of the screw 30 kg / hour.

b) The method according to the invention

The granulate is spun in a melt spinning device under the following conditions:

Screw temperature 250 ° C

Head temperature 255 ° C

Spinneret temperature 255 ° C

Spinneret type 192-0.2-16 mm

Nitrogen pressure in the screw .. 0.5 atm
Flow velocity of
Nitrogen in the zone between
Spinneret and winder 0.2 m / sec.

Winding speed 500 m / min.

45

55

60

c) The technical progress

The threads produced when working in the absence of oxygen have a clear color in contrast to the threads, during the production of which the granulation and spinning were carried out in the presence of atmospheric oxygen. In addition, the final intrinsic viscosity of the threads produced under a nitrogen atmosphere corresponds to 90% of the original value, while the intrinsic viscosity [η] of the threads produced in the presence of atmospheric oxygen is only 60% of the original value.

Example 2

a) From 95 kg of polypropylene, produced with the aid of stereospecific catalysts and with an intrinsic viscosity [η] of 1.6, measured in tetrahydronaphthalene at 135 ° C, a residue after the heptane extraction of 95.5% and an ash content of 0.015% and from 5 kg of a polycondensate, prepared by reacting 0.5 mol of octadecylamine with 1.5 mol of epichlorohydrin and 1 mol of piperazine, a mixture is prepared. The mixture is granulated by pressing under the following conditions:

Nitrogen pressure 5 atm

Extrusion temperature 245 ° C

Capacity of the screw 30 kg / hour.

b) The granulate is spun in a melt spinning device under the following conditions:

Screw temperature.

Head temperature

Spinneret temperature
Spinneret type

Nitrogen pressure in the screw
Flow velocity of
Nitrogen in the zone between
Spinneret and winder

Winding speed

250 ° C
260 ° C
260 ° C
Holes 192,
Diameter 0.8, length 16 mm
0.5 atm

0.2 m / sec.
500 m / min.

c) The threads produced when working in the absence of oxygen have a clear color in contrast to the threads in the production of which the granulation and spinning were carried out in the presence of atmospheric oxygen. Moreover, the final intrinsic viscosity of the filaments prepared under a nitrogen atmosphere corresponds to 92% of the original value, while the intrinsic viscosity [η] of the threads prepared in the presence of atmospheric oxygen, only 55% of ^it is the original value.

Example 3

a) From 95 kg of polypropylene, produced with the help of stereospecific catalysts and with an intrinsic viscosity [η] of 1.3, measured in tetrahydronaphthalene at 135 ° C, a residue after the heptane extraction of 95% and an ash content of 0.012%) and from 5 kg of a polycondensate, prepared by reacting 0.4 mol of dodecylamine with 1.4 mol of epichlorohydrin and 1 mol of piperazine, a mixture is prepared.

The mixture is granulated by pressing under the following conditions:

Nitrogen pressure 0.5 atm

Extrusion temperature 230 ° C

Capacity of the screw 30 kg / hour.

Claims (1)

5 6 b) The granulate is produced filaments in a melt spinning machine oxygen only 50 ° / ₀ of the spun ursprüngunter following conditions: is borrowed value. Screw temperature 240 ° C Head temperature 240 ° C claim: Spinneret temperature ^{240 0} _{C Tr} ,, _TT "_., _ ..,,, Spinneret type 192 x 0.8 x 16 mm _o Process for making textile thread by Nitrogen pressure in the screw 0.5 atm melt spinning and then drawing Flow rate of mixtures containing crystalline polyolefins and 1 to Nitrogen in the zone between 25 percent by weight of basic nitrogen poly- Spinneret and pre-winding ¹⁰ condensate! contain the reaction of direction 0 2 m / sec primary aliphatic nurses with 3 to 30 carbon Winding speed ''.'.'.'.'.'.50o'm / min. ' carbon atoms or secondary aliphatic Amines with 4 to 60 carbon atoms, c) The threads produced when working in the absence of oxygen, possibly in the presence of solvents, have a clear color in the sub-15 and condensation agents, with epichlorohydrin differentiated from the threads during their production, and possibly further reaction with granulation and spinning in the presence of or more aliphatic aromatic or atmospheric oxygen. heterocyclic bis-secondary amines are obtained. In addition, the final intrinsic viscosity has been characterized in that the filaments 20 produced under a nitrogen atmosphere are mixed with mixtures which have been granulated in an oxygen-free 88% of the original value during the limiting atmosphere, in a viscosity [ η] which spins just such in the presence of atmospheric. 809 559/468 5.68 © Bundesdruckerei Berlin