DE1469110A1 - Improved Textile Threads and Methods of Making Them - Google Patents

Description

Improved Textile Threads and Processes for Their Manufacture Addition to patent ......... (patent application P 14 69 105.5) Subject of the main patent ........... (Patent application P 14 69 105. 5) is a process for the production of polyolefin or Polyacrylonitrile threads by spinning mixtures containing crystalline polypropylene or polyacrylonitrile and 1 to 25 wt .-%, based on the polymer weight, one basic polymeric nitrogen compound that has a water solubility less than 0.1% by weight, drawing of the threads and subsequent customary treatment, to make the threads water-insoluble, which is characterized by the fact that one Spun mixtures that contain reaction products as nitrogen compounds a) epichlorohydrin and primary or secondary aliphatic mono- or polyamines, b) epichlorohydrin, primary or secondary aliphatic monoamines and primary or secondary aliphatic polyamines, c) epichlorohydrin, aliphatic primary or secondary monoamines and aliphatic imines or d) epichlorohydrin, aliphatic polyamines and alkyl or aryl halides.

It has now surprisingly been found that one can use textile threads A special affinity for dyes is obtained when using mixtures. spun that as Nitrogen compounds Reaction products of discrete amines with epichlorohydrin and halogen derivatives.

As disecondary amines, aliphatic, aromatic, cycloallphatlsche or heterocyclic disecondary amines having 4 to 20 carbon atoms, in particular Piperazine can be used; instead of disecondary amines, polyamines, the two primary amino groups on tert. Contain bonded carbon atoms (e.g. 1, 8-para-menthane diamine) are used, which as a result of steric hindrance such as disecondary amines react.

According to the invention, the halogen derivatives are mono- or dihalogen derivatives of aliphatic or cycloaliphatic compounds with 8 to 20 carbon atoms or of aromatic compounds suitable.

The production of the invention in a mixture with the polyolefin to be used nitrogen compounds can in the presence of solvents and Condensation agents are carried out.

According to a particular embodiment of the invention, the one to be added Nitrogen compound by reacting 1 to 1.2 moles of polyamine with only two mobile hydrogen atoms that are bound to different nitrogen atoms, with 0.1 to 0.9 moles of epichlorohydrin and with 0.9 to 0.1 moles of the halogen derivative continuous.

The mixture of the nitrogenous product with the polyolefin or the polyolefins by mixing these products at room temperature in Henschel or Werner mixers, manufactured in ball mills or similar devices.

The mixture is then melted in a snake device and granulated and then in a Sohmelz spinner, preferably in the absence by air and under an inert gas.

The spinning of the mixtures can conveniently take place in the presence a small amount of a "solid dispersant", whereby facilitates the homogeneous dispersion of the nitrogenous product in the polymer mass will. This solid dispersant is preferably used among the following compounds selected cetyl and stearyl alcohol, stearic and terephthalic acid, benzoin, furoin, Vinyl stearate, mono-, di- and ristearic esters of glyderine monoethanolamine stearate, Stearamide, N-diethanol-laurylamide, C6 - C30 aliphatic amines, condensation products of ethylene oxide with alcohols, amines and phenols, polystearamide, polyacrylic acid, Polystyrene and styrene copolymers, terpene polymers, etc.

Monofilaments or plurifiles can be produced from the mixtures according to the invention used for the production of continuous filaments or staple fibers of bulky threads or bulky staple fibers are suitable.

The monofilaments or plurifiles obtained according to the invention are suitable for Treatments to convert the basic ingredient compound into water-insoluble ones State; In particular, treatments with formaldehyde and diisocyanates are suitable for this purpose three-dimensional structures resulting in monomers such as divinylbenzene, Vlnylaoetylen and. dergleiohen or with diepoxy compounds.

These treatments are carried out before or after the Yerstreoken, the latter is with ratios between 1: 2 and 1:10, at temperatures between 80 and 150 ° in Streokvorriohtungen carried out with hot air, steam or liquid be heated or in which a hot plate is arranged.

The spinning of the looms according to the invention is preferably carried out by pressing out through spinning nozzles, whose Hole punches have a length to diameter ratio greater than 1. According to the invention The fibers obtained show a remarkable ink absorption capacity for acidic, metallized ones and disperse dyes. They also show one for basic and vat dyes good affinity.

The duroh pressing of the mixtures according to the invention obtained Fibers also show increased stability, especially against light. The invention Example 1 illustrated in the following examples is 94.6 g (1.1 moles) of anhydrous Piperazine, 300 ml of ethanol and 40.5 g (0.2 mol) of dodecenyl chloride (1-chloro-5,5,7,7-tetramethyl-2-ooten) are placed in a 1 l three-necked flask with a mercury stirrer, thermometer and reflux cooler is provided. The mixture is boiled for 12 hours on the RUoktluß, Then 8 g of NaOH and, after 1 hour, 92.5 g (1 mol) of epiochlorohydrin are added. The whole thing is kept for 1 hour at 30 to 40 °, then 10 hours on the RUok -lußkUhler boiled, 40 g NaOH added in small portions during the last 5 hours will. The sodium chloride is filtered off while warm.

The filtrate is poured into 1 l kilts of Aoeton with stirring. The so The white precipitate obtained is filtered off and placed in a heating cabinet at 100 ° Dried for 3 hours.

The product melts at 160 to 171 ° and has a sticky content by 16, 52%.

In a Henschel mixer, a mixture of, Polypropylene 38,400 kg Stioketoffpolykondeneate 1,600 kg produced.

The polypropylene used has the following properties: [#] 1.32 Ash content 0.025% residue after heptane extraction 95.6% The mixture is granulated and then pressed in a Sohmeltspinning device under the following conditions: Soneokentemperature 2300 Spinneret temperature 220 ° Spinneret temperature 220 ° Spinneret type 60 / 0.8 x 16 mm maximum pressure 45 kg / cm2 winding speed 250 mu nuie the veins are stretched in a steam-heated furnace at 130 ° in a ratio of 1: 5. They then undergo dimensional stabilization for 10 minutes under free shrinkage conditions submerged at 105 ° The cross-linked and thermostable yarn has the following Serimetric properties! * Tensile strength 5.1 g / elongation 24% of the Paden then curled and cut into a stack 6 om in length.

The stapal obtained in this way is colored with the following dyes: Alizarin yellow 2G (C.I. mordant yellow 1) (sour) wool red B (C.I. acid red 115) (") alizarin red S (C.I. mordant red 3) ") Alizarin blue SE (0 '$ Ii aoid blue 43) (") Acid black JVS (C. I. acid black 1) (sour) Lanasyngelb GIN (C.I. acid yellow 112) (metallized) Lanasyn red 2GL (C. I. aoid red 216) (") Lanasyn brown 3RL (CI. Acid brown 30) (dispersion) Setacylgelb 3G (C.I.disperse yellow 20) (dispersion) Cibacet scarlet BR (0.1. disperse red 18) (dispersion) setaoyl brilliant blue BG (C. I. disperse blue 3) (") The dyeing is done at the boiling point for 1 1/2 hours in baths with 2.5% dye to the weight of the speeder, carried out with a ratio of fiber to bath of 1:40.

The dyeing with acidic and metallized dyes is done in the presence of 3% ammonium acetate (based on the weight of the fiber) and 1% of a surface-active Means, namely the condensation product of ethylene oxide with an alkylphenol performed 30 minutes after the start of boiling, 2% (based on the fiber weight) 10% acetic acid solution added to improve the depletion of the dye.

The dyeing with disperse dyes is carried out in the presence of 2% (of fiber weight) of surfactant j.

The fibers are felt after the pressure with running water. They show in all cases, especially after staining with acidic, metallized or dispersion dyestuffs, intensive staining.

The authenticity of the dyeings against light, wax and rubbing is completely satisfactory * A further improvement in the color flatness is achieved if you treat the fibers for 5 minutes with a 3% before staining aqueous solution of ethylene glycol diglyzidyl ether at 120 °.

Example 2 94.6 g (1.1 mole) anhydrous piperazine, 200 ml isopropanol and 57.7 g (0.2 moles) are brewed into a 11 three-necked flask, which is equipped with a Queokailber stirrer, a thermometer and a reflux condenser is provided.

The mixture is refluxed for 36 hours. Then 8 g NaOH and after 1 hour 92/5 g (1 mol) of epichlox hydrin and 200 ml of isopropanol were added.

The whole is stirred for 1 hour at 30 to 40 ° and then for 10 hours on the Rd [kSlußkUhler boiled, during the last 5 hours 40 g of NaOH in small Portions are supplied. The sodium chloride is filtered off warm.

The filtrate is duroh heating, evaporated to 200 ° under vacuum. A yellow resinous product is obtained which melts at 192 to 196 ° and has a nitrogen content of 15.18%.

In a Henschel mixer at room temperature a.

Mixture of: 43,, 200 K polypropylene and 1,800 kg nitrogen condensa manufactured.

The polypropylene used has the following properties: lut32 ash content t 0.025% residue after heptane extraction 95.6% The mixture is granulated and then pressed in a melt spinning device under the following conditions: Son corner temperature 230 0 spinning head temperature 220 ° spinneret temperature 220 ° spinneret type 60 / 0.8 x 16 mm maximum pressure 44 kg / cm2 winding speed 250 m / minute The threads are stretched in a steam-heated device at 130 ° in a ratio of 1: 5. she are then under free shrinkage conditions for 10 minutes of dimensional stabilization subjected at 105 °. The drawn and thermally stabilized yarn has the following Serimetric properties: tensile strength 5.2 g / elongation 25% per thread is then crimped and cut in a pile to a length of 6 cm, where the Dyestuffs from Example 1 intense and genuine colorations eklialtoil. Don example 3 430 g (5 moles) of anhydrous piperazine and 304.5 g (1.5 moles) of diohlomethyl-m-xylene, suspended in 2500 ml of ethanol, are brewed into a 6 l three-necked flask, equipped with a mercury stirrer, thermometer and reflux condenser. The mixture is stirred for 2 hours at 20 to 30 ° and then refluxed for 4 hours. During the last 2 hours, 120 g of NaOH are added in small portions.

The whole is then cooled to 20 ° and 324 g (3t5 moles) of epichlorohydrin added. After standing for one hour at 30 to 50 °, the mixture is 10 hours heated to 80 °, 140 g of NaOH are added in small portions during the last 5 hours added The sodium chloride is filtered off warm and d. The solvent duroh Heating removed under vacuum.

A white resinous product is obtained which melts at 63 to 71 ° and has a nitrogen content of 16.72%. In a Henschel Miaoher is at room temperature a mixture of 9.6 kg polypropylene 0) 400 kg nitrogen condensate produced '' The polypropylene used has the following properties: [# 2% 7 1. 42 ash content 0.031% residue after heptane extraction 96.7% The mixture is granulated and then squeezed in a melt spinning machine under the following conditions: Son corner temperature 230 ° spinning head temperature 220 ° spinneret temperature 220 ° spinneret type 60 / 0.8 x 16 mm Maximum pressure 47 kg / cm2 Winding speed 250 minutes The pads are in a steam-heated device at 130 ° in a ratio of 1: 5 veratreekti you will then dimensional stabilization for 10 minutes under free shrinkage conditions subjected at 105 °. The pre-drawn and thermally stabilized yarn has the following Serimetric properties: tensile strength 5.2 g / den Elongation'25% The thread will then curled and cut in a pile in a length of 6 cm, at which with the dyes of Example 1, intense and true colorations can be obtained.

Example 4 172 g (2 moles) anhydrous piperazine and 105 g (0.6 moles) p-Xylilene dichloride, suspended in 800 ml of ethanol, are placed in a 2 l three-necked flask introduced, which is provided with a mercury stirrer, thermometer and reflux condenser is. The mixture is stirred for 2 hours at 20 to 30 ° and then for 4 hours on the reflux condenser Boiled 48 g of NaOH are added in small portions over the last 2 hours. The whole thing is then set to 20 ° cools and 129.6 g (1.4 moles) Epichlorohydrin added.

After standing for one hour at 30 to 40 °, the mixture is 10 hours cooked on the reflux cooler. During the last 5 hours, 56 g of NaOH are used in small Proportions added.

The solution is filtered and the solvent by heating under Vacuum removed.

A white resinous product is obtained which is 106 to 114 ° melts and has a nitrogen content of 17.74% in a Henachel mixer at room temperature a mixture of us s.,. ' 5.760 kg polypropylene 0.240 kg nitrogen condensate manufactured.

The polypropylene used has the following properties: 1.42 Aohe content 0.031% residue after heptane extraction 96.7% The mixture is granulated and then squeezed in a melt spinning machine under the following conditions: son eoke temperature 230 ° spinneret temperature 220 ° spinneret temperature. 220 ° spinneret type 60 / 0.8 x 16 mm maximum pressure 41 kg / cm2 winding speed 250 m / minute the Veins are streoed in a steam-heated device at 130 in a ratio of 1: 5. They then undergo dimensional stabilization for 10 minutes under free shrinkage conditions Subjected at 105 °, the drawn and thermally stabilized yarn has the following Serimetric properties: tensile strength 5t5 g / elongation 22% of the thread then crimped and cut in a pile to a length of 6 µm, at which intense and true colorations can be obtained with the paraffins of Example 1.

Example 5 172 g (2 moles) anhydrous piperazine, 84.4 g (0.4 moles) 1, 10-dichlorodecane and 400 ml of isopropanol are brewed into a 2 l three-necked flask the one with a mercury stirrer, thermometer and. The reflux cooler is provided. The mixture g is refluxed for 24 hours. Then 32 g of NaOH and Naoh 1 hour 148 g (1.6 moles) of epiohlorohydrin and 400 ml of isopropanol were added at 20 °.

The mixture is kept at 30 to 45 ° for 1 hour and then for 10 hours Boiled on the reflux cooler with 64 g of NaOH in small amounts during the last 5 hours Portions are added, the sodium chloride is filtered off and the solvent removed by heating under vacuum.

A mixture of: 4,800 kg of polypropylene and 0.200 kg of nitrogen condensate produced.

The polypropylene used has the following properties: [#] 1.42 Ash content 0.031% residue after heptane extraction 96.7% The mixture is granulated and then in a melt-spinning machine under the following conditions 230 ° spinning head temperature 220 ° spinning nozzle temperature 220 ° spinning nozzle type 60/0, 8 x 16 mm maximum pressure 40 kg / cm2 winding speed 250 minutes The threads are stretched in a steam-heated device at 130 in a ratio of 1: 5. she are then dimensionally stabilized for 10 minutes under free shrinkage conditions subjected at 105 °. The pre-drawn and thermally stabilized yarn has the following serimetric properties: tensile strength 5, 1 g / elongation 21% of the thread then crinkled and cut in a pile in a length of 6 om, on which with the dyes of Example 1, intense and true colorations can be obtained

Claims (3)

P a t e n t a n s p r U c h e 1) Process for the manufacture of polyolefin or Polyacrylonitrifladen by spinning mixtures that contain crystalline polypropylene or polyacrylonitrile and 1 to 25 wt .-%, based on the polymer weight, one basic polymeric nitrogen compounds that have a water solubility less than 0.1% by weight, drawing of the thread and subsequent treatment, to make the threads water-insoluble, according to patent .......... (patent application P 14 69 105.5), characterized in that mixtures are spun as nitrogen compounds Reaction product of disecond amines with epichlorohydrin and halogen derivatives contain. 2) Method according to claim 1, characterized in that one mixes spins the reaction products of piperazine with epichlorohydrin as nitrogen compounds and dodecenyl chloride, octadecenyl chloride, dichloromethyl-m-xylene, p-xylene dichloride or 10-dichlorodecane. 3) Textile threads based on polyolefins, especially polypropylene, or polyacrylonitrile, which in a known manner by spinning the polymers, Stretching and treatment of the fibers to increase the water insolubility produced have been characterized by a content of 1 to 25 wt .-%, based on the polymer, a basic polymeric nitrogen compound that is the reaction product of disecondary amines, especially piperazine, with epichlorohydrin and halogen derivatives, especially Dode. cenyl chloride, octadecenyl chloride, dichloromethyl-m-xylene, p-xylene dichloride or 1, 10-dichlorodeoane, and optionally by a retention of customary Additives such as dispersants, fillers and / or stabilizers.