US3839496A - Manufacture of filaments or fibers of polyamides - Google Patents

Manufacture of filaments or fibers of polyamides Download PDF

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Publication number
US3839496A
US3839496A US00290321A US29032172A US3839496A US 3839496 A US3839496 A US 3839496A US 00290321 A US00290321 A US 00290321A US 29032172 A US29032172 A US 29032172A US 3839496 A US3839496 A US 3839496A
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US
United States
Prior art keywords
filaments
polyamide
fibers
polyamides
alkoxylated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US00290321A
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English (en)
Inventor
G Becht
K Matthias
J Kunde
H Pohlemann
G Ramlow
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BASF SE
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BASF SE
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Publication date
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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • This invention relates to a process for the manufacture of filaments or fibers containing alkoxylated polyamides.
  • This object is achieved by a method of making filaments or fibers of filament-forming synthetic linear polyamides containing alkoxylated polyamides in an amount of from 2 to 15%, on the weight of the filaments or fibers, Wherein a molten mixture of the filament-forming synthetic linear polyamides and alkoxylated polyamides is subjected to thorough mixing so that the alkoxylated polyamides are present in the finished filaments in the form; of particles having a diameter of not more than 0.1,u., and the molten mixture is filtered at least once through a filter having a pore width of not more than 2071, the mixture is converted to chip form if desired, and the mixture is melt spun, the molten mixture being maintained at temperatures of up to not more than 290 C. for a total period of not more than 30 minutes.
  • filament-forming synthetic linear polyamides of high molecular weight we mean those having recurring amide groups in the backbone.
  • Suitable filament-forming or fiber-forming synthetic linear polyamides are, for example, the polycondensates of lactams having from 4 to 12 carbon atoms, such as e-caprolactam, octolactam, dodecanolactam or mixtures of said lactams, and the polycondensates of salts of diamines and dicarboxylic acids having from 4 to 12 carbon atoms, such as the salts of adipic acid, suberic acid or sebacic acid, and hexamethylene diamine, octamethylene diamine or dodecamethylene diamine or mixed condensates of said polyamide-forming materials.
  • Particularly suitable are polycaprolactam; and polyhexamethylene adipamide.
  • the filament-forming or fiber-forming polyamides may contain an excess of Basic groups or they may have a content of sulfo groups or alkali metal sulfonate groups. Conveniently, the polyamides to be modified ha've relative viscosities in the range 1.5 to 2.9.
  • Polyamides alkoxylated with 1,2-alkylene oxides may be manufactured by known processes, for example by the method described in Belgian Pat. 665,018 comprising the reaction of 1,2-alkylene oxides, for example ethylene oxide and/ or 1,2-propylene oxide, with polyamides under pressure and at elevated temperatures, in particular at temperatures ranging from 60 to C.
  • the reaction may be carried out in the presence or absence of organic solvents and/or reducing or oxidizing agents, the alkylene oxides being reacted with the polyamides preferably in a ratio of from 2 to 5:1 by weight. It has been found advantageous to use alkoxylated polyamides having a total molecular weight of at least 10,000 and in particular from 20,000 to 80,000.
  • Suitable polyamides from which the alkoxylated polyamide antistatic agents may be manufactured are for example conventionally produced polycondensates of lactams having from 4 to 12 carbon atoms, such as e-caprolactam, octolactam, dodecanolactam or mixtures of said lactams, the polycondensates of salts of diamines and dicarboxylic acids having from 4 to 12 carbon atoms, such as the salts of adipic acid, suberic acid or sebacic acid, and hexamethylene diamine, octamethylene diamine or dodecamethylene diamine or copolyamides of said polyamide-forming materials.
  • Particularly suitable are all those polyamides which have low crystallinity, for example copolyamides or polyamides which have been prepared by quenching the polymer melt, for example molten polycaprolactam.
  • the amount of alkoxylated polyamides used is conveniently from 2 to 15% and in particular from 4 to 10% w./w. of the weight of the filaments or fibers. It is possible to use larger proportions, but this leads to changes in the properties of the filaments or fibers.
  • the solid components i.e. the filament-forming polyamides and the alkoxylated polyamides, may be melted separately or together.
  • the components may be mixed in a conventional single-worm or twin-worm extruder, of which one or both of the worms may be axially displaceable if desired.
  • Static mixers having stationary conducting elements may also be used to advantage. Adequate mixing is usually obtained using static mixers having 15 or more elements. Static mixers of this kind are described for example in US. Pats. 3,286,992 and 3,404,689 and German Published Application 1,178,404.
  • Conditions should be such as to achieve such thorough mixing that the alkoxylated polyamides, which form a separate phase in the filaments after cooling and drawing, have a particle diameter of not more than 0.1 4.
  • the degree of mixing required to achieve this end may be previously found by simple experiment.
  • the length of the separate particles of alkoxylated polyamides in the filaments after drawing is generally a multiple of their diameter, for example about 111 or more. It is an important feature of the process of the invention that filtration of the molten mixture of components is carried out at least once through filters having pore widths or not more than 201L- Examples of suitable filters are metal sieves or, in particular, sintered metal filters such as sintered metal plates or sintered metal tubelets.
  • the molten mixture may, if desired, be converted to chips and subsequently melt-spun to filaments or fibers.
  • the molten mixture may be thoroughly mixed and filtered and immediately melt-spun to filaments or fibers without intermediate conversion to chip form.
  • Another alternative is to carry out mixing and filtration in the spinning apparatus by using a spinning extruder capable of providing thorough mixing and placing a filter having a pore width of less than 20g immediately downstream of the spinning nozzle, which filter is advantageously an appropriate sintered metal filter.
  • the molten mixture of filamentforming polyamide and alkoxylated polyamide is maintained at temperatures of not more than 290 C. and generally at from 250 to 290 C. for a total period of not more than 30 minutes including the melt-spinning time.
  • the time during which the mixture may be in chip form in a colder state is, of course, not included.
  • the filaments are made using conventional spinning systems wherein, of course, the conditions usually observed in the manufacture of polyamide filaments, such as the exclusion of oxygen and the use of certain low moisture contents, must be met.
  • the filaments or fibers produced by melt-spinning may have a round crosssection or a profiled cross-section such as a trilobate or tetralobate cross-section.
  • the filaments may be in the form of two-component filaments with other filamentforming materials.
  • the filaments or fibers of the invention are stretched, for example at a draw ratio of from 1:2.5 to 1:4.5.
  • the filaments or fibers may also be texturized, for example by the false-twist or stutter-box method or by texturizing in moving gas media.
  • the filaments or fibers may incorporate conventional additives such as pigments, for example titanium dioxide, or light stabilizers, heat stabilizers, and stabilizers to prevent the degradation of polyether chains.
  • pigments for example titanium dioxide, or light stabilizers, heat stabilizers, and stabilizers to prevent the degradation of polyether chains.
  • the filaments or fibers produced by the method of the invention are distinguished by their greatly reduced tendency to build up electrostatic charges. This good antistatic behavior remains after repeated washing.
  • Electrostatic build-up on textile articles may be determined by the method proposed by Heyl & Liittgens (Kunststoife, Vol. 56, 1966, p. 51).
  • a suitable method as regards carpets is the stroll test (Test Method for Determining the Static Propensity of Carpets, Report American Carpet Institute, Aug. 19, 1968).
  • the process of the invention is distinguished in that the yields produced in spinning and drawing are high as compared with unmodified polyamides, which means that the number of defects found in the subsequent stages of warping and knitting is low.
  • the quality of the filaments is tested by the conventional technological tests on mechanical properties and dyeability.
  • the values found for the filaments produced by the invention hardly differ from those provided by the corresponding unmodified polyamides. Indeed, the filaments modified by the present invention can usually by dyed deeper and more level shades a frequently desirable feature. Since the streak-free dyeing of conventional polyamides remains a problem, the above improvement as concerns dyeability is particularly advantageous.
  • the filaments made in accordance with the present invention may be woven or knitted to textile articles such as underwear and shirts with advantageous results.
  • the quality required in such articles is particularly high and the measures of the invention are therefore especially efiective for this application.
  • Filaments made in the manner proposed by the present invention may also be used successfully in carpets, both in the form of continuous filaments and as staple fibers. A distinct improvement in the quality of the filaments is achieved as compared with prior art modifying processes for the manufacture of twophase antistatic fibers.
  • a filter unit which is heated at 25 0 C. and is fitted with metal sieves of 17 mesh.
  • the filtered molten mixture is extruded in four strands which are cooled in a water bath and then granulated.
  • the granules are dried to a water content of less than 0.1% and then melt-spun to filaments 144 f 10 dtex. using an extruder provided with a sintered metal filter having an average pore width of about 18
  • the residence time of the molten mixture in the spinning system is about 15 minutes.
  • the resulting filaments are then stretched at a draw ratio of 113.28 to form filaments 44 f 10 dtex.
  • the drawing yield is 96% based on cops weighing 1 kg.
  • the ethoxylated polycaprolactam is present in the filaments as a separate phase in the form of very small rods having a diameter of not more than 0.1 4.
  • knitted material made from the filaments of the invention and which has been washed five times has a field strength of only 60 volts/ cm. when measured at 50% relative humidity after being rubbed for 4 minutes against a knitted fabric of unmodified polycaprolactam.
  • Unmodified polycaprolactam in the form of knitted fabric which has been washed five times shows a field of strength of 2,400 volts/cm. when measured under similar conditions.
  • Knitted fabric made from the filaments of the invention shows very uniform affinity for acid dyes as well as disperse dyes and also shows a distinctly higher color yield than unmodified polycaprolactam material.
  • a process for the manufacture of antistatic polyamide filaments which comprises: forming a molten mixture of (a) a. filament-forming synthetic linear aliphatic polyamide having recurring amide groups in the backbone and having a relative viscosity in the range of 1.5 to 2.9, measured as a 1% w./w. solution in 98% H 80 at 20 C.,
  • an alkoxylated polyamide manufactured by reaction of a polyamide selected from the group consisting of the polycondensates of lactams of 4 to 12 carbon atoms and polycondensates of the salts of diamines and dicarboxylic acids of 4 to 12 carbon atoms with a 1,2-alkylene oxide in a weight ratio of from 1:2 to 1:5 and to provide a total molecular weight of 10,000 to 80,000,

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polyamides (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
US00290321A 1971-09-20 1972-09-19 Manufacture of filaments or fibers of polyamides Expired - Lifetime US3839496A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2146885A DE2146885B2 (de) 1971-09-20 1971-09-20 Verfahren zum Herstellen von Fäden oder Fasern aus Polyamiden

Publications (1)

Publication Number Publication Date
US3839496A true US3839496A (en) 1974-10-01

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ID=5820059

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Application Number Title Priority Date Filing Date
US00290321A Expired - Lifetime US3839496A (en) 1971-09-20 1972-09-19 Manufacture of filaments or fibers of polyamides

Country Status (7)

Country Link
US (1) US3839496A (xx)
BE (1) BE789019A (xx)
CH (1) CH530480A (xx)
DE (1) DE2146885B2 (xx)
GB (1) GB1394835A (xx)
IT (1) IT963885B (xx)
NL (1) NL7212728A (xx)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3932340A (en) * 1973-08-21 1976-01-13 Daicel Ltd. Nylon coating composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2217527C3 (de) * 1972-04-12 1980-02-14 Basf Ag, 6700 Ludwigshafen Aus der Schmelze geformte, ein Antistatikum enthaltende Fäden oder Fasern aus Polyamiden sowie ein Verfahren zu deren Herstellung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3932340A (en) * 1973-08-21 1976-01-13 Daicel Ltd. Nylon coating composition

Also Published As

Publication number Publication date
GB1394835A (en) 1975-05-21
NL7212728A (xx) 1973-03-22
IT963885B (it) 1974-01-21
BE789019A (fr) 1973-03-20
CH530480A (de) 1972-11-15
DE2146885A1 (de) 1973-03-29
DE2146885B2 (de) 1974-01-17

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