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DE1277513B - Process for the production of fibers or threads from poly-ª ‡ -olefins - Google Patents

Process for the production of fibers or threads from poly-ª ‡ -olefins

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Publication number
DE1277513B
DE1277513B DEJ24622A DEJ0024622A DE1277513B DE 1277513 B DE1277513 B DE 1277513B DE J24622 A DEJ24622 A DE J24622A DE J0024622 A DEJ0024622 A DE J0024622A DE 1277513 B DE1277513 B DE 1277513B
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DE
Germany
Prior art keywords
poly
stabilizer
olefins
metal
threads
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.)
Pending
Application number
DEJ24622A
Other languages
German (de)
Inventor
Alan Ryton Caverhill
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from GB2004762A external-priority patent/GB972934A/en
Priority claimed from GB4056362A external-priority patent/GB1013948A/en
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of DE1277513B publication Critical patent/DE1277513B/en
Pending legal-status Critical Current

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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79Polyolefins
    • D06P3/795Polyolefins using metallisable or mordant dyes, dyeing premetallised fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91Polymers modified by chemical after-treatment
    • C08G63/914Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G67/00Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/10Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/10Metal compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0091Complexes with metal-heteroatom-bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/02Polyacetals containing polyoxymethylene sequences only
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • 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
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • 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
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • 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
    • D01F6/28Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/39General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79Polyolefins
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79Polyolefins
    • D06P3/791Polyolefins using acid dyes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • 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
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Coloring (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. Cl.:Int. Cl .:

Nummer:
Aktenzeichen;
Anmeldetag:
Auslegetag:
Number:
File number;
Registration date:
Display day:

DOIfDOIf

Deutsche KI.: 29 b-3/65German KI .: 29 b-3/65

P 12 77 513.2-43 (J 24622)P 12 77 513.2-43 (J 24622)

24. Oktober 1963October 24, 1963

12. September 1968September 12, 1968

Die Erfindung betrifft ein Verfahren zur Herstellung von färbbaren Fasern und Fäden aus PoIy-K-olefinen, die eine verbesserte Beständigkeit gegen frxydätive Zerstörung aufweisen.The invention relates to a method of manufacture of dyeable fibers and threads made from poly-k-olefins, which have an improved resistance to oxidative destruction.

In der deutschen Auslegeschrift 1 201 296 ist ein Verfahren zur Herstellung von gefärbten Fasern aus Poly-a-olefinen vorgeschlagen worden, wobei eine basische Substanz oder eine anionische Austauschsubstanz, die ein Metall der Gruppe II a, II b oder IV a fies Periodensystems enthält, dem Polyolefin beigemischt wird, und zwar vor dem Färben mit einem Farbstoff, der eine oder mehrere saure Gruppen mit einem niedrigen Ionisationsgrad enthält, wodurch ein Salz oder eine Gleitverbindung des Metalls mit dem !Farbstoff hergestellt wird.The German Auslegeschrift 1 201 296 describes a method for producing colored fibers from Poly-α-olefins have been proposed, with a basic substance or an anionic exchange substance which is a metal from group II a, II b or IV a contains nasty periodic table, mixed with the polyolefin before dyeing with a dye containing one or more acidic groups contains a low degree of ionization, whereby a salt or a sliding compound of the metal with the ! Dye is produced.

Gemäß der französischen Patentschrift 1235 806 werden die Eigenschaften von Polyolefin durch die Einarbeitung gewisser Metallseifen verbessert. Insbesondere ergibt sich hierdurch eine Verbesserung der Färbeeigenschaften. Die in dieser französischen Patentschrift beschriebenen Massen enthalten jedoch keine Stoffe zur Stabilisierung des Polyolefins gegen Abbau. Die der vorliegenden Erfindung zugrunde liegende Aufgabe wird deshalb von dieser Patentschrift nicht berührt.According to French patent 1235 806 the properties of polyolefin are improved by the incorporation of certain metal soaps. In particular This results in an improvement in the coloring properties. The one in this French However, the compositions described in the patent contain no substances to stabilize the polyolefin against Dismantling. The object on which the present invention is based is therefore addressed by this patent specification not touched.

Es wurde nun festgestellt, daß die Metallseifen die schützende Wirkung der Substanzen, die zur Verminderung der Zersetzungsneigung zu der Poly-a-olefinjnasse zugegeben werden, in nachteiliger Weise beeinflussen.It has now been found that the metallic soaps reduce the protective effect of the substances used the tendency to decompose to the wet poly-α-olefin are added, adversely affect.

Es wurde auch festgestellt, daß diese durch Metallreifen hervorgerufene nachteilige Beeinflussung der Wirkung der stabilisierenden Substanzen in hohem Maße durch die Verwendung von Metallseifen organische Säuren mit verzweigten Kohlenstoffketten herabgesetzt werden kann.It was also found that this was caused by metal hoops caused adverse influence on the effect of the stabilizing substances to a high degree Reduced levels of organic acids with branched carbon chains through the use of metallic soaps can be.

Gegenstand der vorliegenden Erfindung ist daher till Verfahren zum Herstellen von Fasern oder Fäden durch Schmelzspinnen von Poly-a-olefinen, die eine Beimischung von Metallsalzen und wenigstens einen üblichen, die Zersetzung verhindernden Stabilisator enthalten, welches dadurch gekennzeichnet ist, daß man als Metallseifen 1 bis 10 Gewichtsprozent des Salzes einer organischen Monocarbonsäure oder einer Mischung von Monocarbonsäuren mit einem Metall der Gruppella, Hb oder IVa des Periodensystems verwendet, wobei die Carboxylgruppe an ein Atom einer verzweigten Kohlenstoffkette gebunden ist sowie 0,1 bis 5 Gewichtsprozent des Stabilisators oder Stabilisatorgemisches beimischt.The present invention therefore relates to a method for producing fibers or threads by melt spinning of poly-a-olefins, which is an admixture of metal salts and at least one conventional, the decomposition preventing stabilizer, which is characterized in that as metal soaps 1 to 10 percent by weight of the salt of an organic monocarboxylic acid or a Mixture of monocarboxylic acids with a metal from Gruppella, Hb or IVa of the periodic table used, wherein the carboxyl group is bonded to an atom of a branched carbon chain and 0.1 to 5 percent by weight of the stabilizer or stabilizer mixture admixed.

Die nach dem erfindungsgemäßen Verfahren hergestellten Fasern und Fäden werden besonders Verfahren zum Herstellen von Fasern oder Fäden aus Poly-a-olefinenThe fibers and filaments produced by the process of the invention become special Process for the production of fibers or filaments from poly-α-olefins

Anmelder:Applicant:

Imperial Chemical Industries Ltd., LondonImperial Chemical Industries Ltd., London

Vertreter:Representative:

Dr.-Ing. H. Fihcke, Dipl.-Ing. H. Bohr
und Dipl.-Ing. S. Staeger, Patentanwälte,
8000 München 5, Müllerstr. 31
Dr.-Ing. H. Fihcke, Dipl.-Ing. H. Bohr
and Dipl.-Ing. S. Staeger, patent attorneys,
8000 Munich 5, Müllerstr. 31

Als Erfinder benannt:
Alan Ryton Caverhill,
Harrogate, Yorkshire (Großbritannien)
Named as inventor:
Alan Ryton Caverhill,
Harrogate, Yorkshire (UK)

Beanspruchte Priorität:Claimed priority:

Großbritannien vom 26. Oktober 1962 (40 563),
vom 4. Oktober 1963
Great Britain of October 26, 1962 (40 563),
dated October 4, 1963

leicht gefärbt durch die Farbstoffe des britischen Patents 935 125, die eine oder mehrere saure Gruppen mit einem niedrigen Dissoziationsgrad, wie anschließend erläutert, aufweisen, durch die ein Salz oder eine Chelatverbindung des Metalls mit dem Farbstoff hergestellt wird.lightly colored by the dyes of British Patent 935 125 containing one or more acidic groups with a low degree of dissociation, as explained below, have a salt or chelating the metal with the dye.

Eine einen niedrigen Dissoziationsgrad aufweisende saure Gruppe ist z. B. eine phenolische Hydroxyl- oder eine Carboxylgruppe, die in Wasser bei 20° C eine Dissoziationskonstante von weniger als 10~2 besitzt. Farbstoffe dieser Art sind in Form ihrer freien Säure in normaler wäßriger Lösung bei 2O0C zu weniger als 10% ionisiert. Erfindungsgemäß verwendete Metallseifen, die Metalle der Gruppella, Hb und IVa des Periodensystems enthalten, sind z. B. die aliphatischen carbonsauren Salze von Mg, Ca, Sr, Ba, Cd, Zn, Sn und Pb.An acidic group having a low degree of dissociation is e.g. B. having a phenolic hydroxyl group or a carboxyl group which in water at 20 ° C a dissociation constant of less than 10 ~. 2 Dyes of this type are ionized their free acid in normal aqueous solution at 2O 0 C to less than 10% in the form. Metal soaps used according to the invention which contain metals from Gruppella, Hb and IVa of the periodic table are, for. B. the aliphatic carboxylic acid salts of Mg, Ca, Sr, Ba, Cd, Zn, Sn and Pb.

Die organische Säure, von der sich die Metallseife ableitet, hat vorzugsweise wenigstens 8 Kohlenstoffatome in der Kette, damit die Metallseife im PoIya-olefin löslich und mit ihm verträglich ist. Es wurde festgestellt, daß die organischen Monocarbonsäuren sehr geeignet sind, die die Carboxylgruppe an verzweigten Kohlenstoffketten mit 8 bis 20 Kohlenstoff-The organic acid from which the metallic soap is derived preferably has at least 8 carbon atoms in the chain so that the metal soap in the poly-olefin is soluble and compatible with it. It was found that the organic monocarboxylic acids are very suitable that the carboxyl group on branched carbon chains with 8 to 20 carbon

809 600/546809 600/546

atomen gebunden enthalten und die vorzugsweise wenigstens einen Alkylsubstituenten enthalten, der an das der Carboxylgruppe benachbarte Kohlenstoffatom gebunden ist. Derartige Säuren sind im Handel leicht erhältlich, und zwar sowohl als einzelne Verbindungen als auch als Mischungen verwandter Säuren, wie z.B. als Mischung verzweigter Fettsäuren, die 9 bis 11 Kohlenstoff atome enthalten.Atoms contain bonded and which preferably contain at least one alkyl substituent on the carbon atom adjacent to the carboxyl group is bonded. Such acids are commercially available readily available both as individual compounds and as mixtures of related ones Acids, such as a mixture of branched fatty acids containing 9 to 11 carbon atoms.

Das erfindungsgemäße Verfahren ist auf die Herstellung von Fasern und Fäden aus stereoregulären Polyolefinen, z.B. aus stereoregulärem PoIy-(4-methylpenten-l) oder isotaktischem Polypropylen geeignet.The inventive method is based on the production of fibers and threads from stereoregular Polyolefins, e.g. from stereoregular poly (4-methylpentene-1) or isotactic polypropylene.

Von den vielen Arten chemischer Verbindungen, die für die Stabilisierung von Poly-a-olefinen gegen Licht oder oxydativen Abbau vorgeschlagen wurden, haben vergleichsweise nur wenige eine weite Anwendung gefunden, z. B. Thiobisphenole, Dialkylester der Thiodialkansäuren, substituierte Phenylendiamine, Benzophenonderivate, Organophosphorverbindungen und die Kondensationsprodukte von Aldehyden und Phenolen oder deren Mischungen (s. »Atmospheric Oxydation and Antioxidants«, G. Scott, Elsevier, 1965).Of the many types of chemical compounds used for the stabilization of poly-a-olefins against Light or oxidative degradation have been suggested, comparatively few have wide application found, e.g. B. Thiobisphenols, dialkyl esters of thiodialkanoic acids, substituted phenylenediamines, Benzophenone derivatives, organophosphorus compounds and the condensation products of Aldehydes and phenols or their mixtures (see »Atmospheric Oxydation and Antioxidants«, G. Scott, Elsevier, 1965).

Es wurde festgestellt, daß Metallseifen von Fettsäuren mit linearen Kohlenstoffketten, wie Zinkstearat, die Wirkung einiger Stabilisatoren derart stören, daß die Stabilisatoren beinahe vollständig unwirksam werden.It has been found that metal soaps of fatty acids with linear carbon chains, such as zinc stearate, interfere with the action of some stabilizers in such a way that the stabilizers are almost completely become ineffective.

Damit die verbesserte Affinität gegen Farbstoffe vom obenerwähnten Typ einen angemessenen Wert aufweist, muß eine ausreichende Menge der erfindungsgemäß verwendeten Metallseifen dem Polyolefin beigemischt werden. Es wurde festgestellt, daß 1 bis 10%, vorzugsweise 2 bis 6%, bezogen auf das Polyolefingewicht, geeignete Mengen darstellen. Die Stabilisatorenmenge muß gleichfalls für eine angemessene Stabilisierung ausreichen. Es wurde festgestellt, daß 0,1 bis 5% Stabilisator oder Stabilisatorengemisch genügt. Die Zugabe der Metallseife und der geeigneten Stabilisierungssubstanzen zu dem Polyolefin kann unmittelbar vor dem Verformungsprozeß erfolgen oder bei jeder Verfahrensstufe während der Herstellung des Polyolefins beigegeben werden.So that the improved affinity for dyes of the above-mentioned type is an adequate value has, a sufficient amount of the metal soaps used in the invention must be the polyolefin be added. It has been found that 1 to 10%, preferably 2 to 6%, based on the Polyolefin weight, represent suitable amounts. The amount of stabilizer must also be adequate Stabilization is sufficient. It was found that 0.1 to 5% stabilizer or stabilizer mixture enough. The addition of the metal soap and the appropriate stabilizing substances to the Polyolefin can take place immediately before the deformation process or during each process step be added to the manufacture of the polyolefin.

In den folgenden Beispielen wird die Stabilität gegen oxydative Zerstörung (angegeben als Lebensdauer) durch Ermittlung der Zeit gemessen, die schmelzgesponnene Fäden brauchen bis sie spröde werden, wenn sie in einem Luftofen einer Temperatür von 140° C ausgesetzt werden. In diesen Beispielen sind Teile und Prozente jeweils als Gewichtsteile und Gewichtsprozente zu verstehen.In the following examples, the stability against oxidative destruction (given as service life) measured by determining the time it takes for melt-spun filaments to become brittle when exposed to 140 ° C in an air oven. In these examples parts and percentages are to be understood as parts and percentages by weight.

Beispiel 1example 1

100 Teile isotaktisches Polypropylen, 0,1 Teil Kondensationsprodukt aus Crotonaldehyd und 3-Methyl-6-tert-butyl-phenol, 0,5 Teile DÖauryl-thio-dipropionat und 3 Teile Zink-2-äthylhexoat wurden in Form ihrer Pulver sorgfältig gemischt. Das Produkt wurde hierauf unter Anwendung einer Spinndüsentemperatur von 180° C mit einer herkömmlichen Vorrichtung schmelzversponnen. Die daraus hergestellten Fäden wurden über einer geheizten Platte und einem Dorn auf das Mehrfache ihrer ursprünglichen Länge gestreckt und daraus Fäden mit einem Gesamttiter von etwa 700 den hergestellt.100 parts isotactic polypropylene, 0.1 part condensation product from crotonaldehyde and 3-methyl-6-tert-butyl-phenol, 0.5 parts of DÖauryl thio-dipropionate and 3 parts of zinc 2-ethylhexoate were in Form their powder carefully mixed. The product was then applied using a spinneret temperature melt-spun at 180 ° C with a conventional device. The ones made from it Threads were placed over a heated plate and a mandrel at several times their original Stretched length and made from it threads with a total denier of about 700 den.

Probestücke von diesen Fäden wurden zur Bestimmung der Oxydationsanfälligkeit der Masse verwendet und ergaben eine Lebensdauer von 44 Stunden.Samples of these threads were used to determine the susceptibility of the mass to oxidation used and gave a lifespan of 44 hours.

Beispiel 2Example 2

Es wurden wie im Beispiel 1 hergestellt, und zwar aus einem Gemisch, das neben isotaktischem Polypropylen und denselben beiden stabilisierenden Verbindungen in den gleichen Mengen zusätzlich noch 4%, bezogen auf das Polypropylen, des Zinksalzes eines Gemisches verzweigter Fettsäuren mit 9 und 11 Kohlenstoffatomen enthielt.It was prepared as in Example 1, from a mixture that, in addition to isotactic polypropylene and the same two stabilizing compounds in the same amounts 4%, based on the polypropylene, of the zinc salt of a mixture of branched fatty acids with 9 and Contained 11 carbon atoms.

Das Produkt hatte eine Lebensdauer von 96 Stunden.The product had a lifespan of 96 hours.

Beispiel 3Example 3

Es wurden wie im Beispiel 1 Fäden hergestellt, und zwar aus einer Mischung, die neben den im Beispiel 1 aufgezählten Verbindungen zusätzlich noch 4% des Zinksalzes von Isodecansäure enthielt. Das Produkt hatte eine Lebensdauer von 43 Stunden.As in Example 1, threads were produced from a mixture which, in addition to the im Example 1 listed compounds additionally contained 4% of the zinc salt of isodecanoic acid. The product had a lifespan of 43 hours.

Vergleichende BeispieleComparative examples

Es wurden wie im Beispiel 1 isotaktische Polypropylenmassen hergestellt, wobei jedoch das Zink-2-äthylhexoat durch 5 %, bezogen auf das Polyolefin, Zinkstearat oder Zinkcaprylat ersetzt wurde.As in Example 1, isotactic polypropylene compositions were produced, except that the zinc 2-ethylhexoate was used was replaced by 5%, based on the polyolefin, zinc stearate or zinc caprylate.

Die aus diesen Massen entsprechend dem Beispiel 1 hergestellten Fäden hatten eine Lebensdauer von weniger als 3 Stunden.The threads produced from these compositions according to Example 1 had a service life of less than 3 hours.

Claims (1)

Patentanspruch:Claim: Verfahren zum Herstellen von Fasern oder Fäden durch Schmelzspinnen von Poly-a-olefinen, die eine Beimischung von Metallsalzen und wenigstens einen üblichen, die Zersetzung verhindernden Stabilisator enthalten, dadurch gekennzeichnet, daß man als Metallseifen 1 bis 10 Gewichtsprozent des Salzes einer organischen Monocarbonsäure oder einer Mischung von Monocarbonsäuren mit einem Metall der Gruppe Π a, lib, oder IVa des Periodensystems verwendet, wobei die Carboxylgruppe an ein Atom einer verzweigten Kohlenstoffkette gebunden ist sowie 0,1 bis 5 Gewichtsprozent des Stabilisators oder Stabilisatorgemisches beimischt.Process for producing fibers or filaments by melt spinning poly-a-olefins, which contain an admixture of metal salts and at least one customary one which prevents decomposition Contain stabilizer, characterized in that the metal soaps are 1 to 10 percent by weight the salt of an organic monocarboxylic acid or a mixture of monocarboxylic acids used with a metal from group Π a, lib, or IVa of the periodic table, wherein the carboxyl group is bonded to an atom of a branched carbon chain and 0.1 up to 5 percent by weight of the stabilizer or stabilizer mixture. In Betracht gezogene Druckschriften: Französische Patentschrift Nr. 1235 806.Documents considered: French Patent No. 1235 806.
DEJ24622A 1962-05-24 1963-10-24 Process for the production of fibers or threads from poly-ª ‡ -olefins Pending DE1277513B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB2004762A GB972934A (en) 1962-05-24 1962-05-24 Shaped articles of polyoxymethylenes
GB4056362A GB1013948A (en) 1962-10-26 1962-10-26 Modified polyolefines

Publications (1)

Publication Number Publication Date
DE1277513B true DE1277513B (en) 1968-09-12

Family

ID=26254402

Family Applications (3)

Application Number Title Priority Date Filing Date
DEJ21373A Pending DE1201296B (en) 1962-05-24 1962-02-28 Process for dyeing textiles made from poly-alpha-olefins
DEJ23756A Pending DE1234919B (en) 1962-05-24 1963-05-22 Process for the production of shaped articles from modified polyoxymethylene or mixed polyoxymethylene
DEJ24622A Pending DE1277513B (en) 1962-05-24 1963-10-24 Process for the production of fibers or threads from poly-ª ‡ -olefins

Family Applications Before (2)

Application Number Title Priority Date Filing Date
DEJ21373A Pending DE1201296B (en) 1962-05-24 1962-02-28 Process for dyeing textiles made from poly-alpha-olefins
DEJ23756A Pending DE1234919B (en) 1962-05-24 1963-05-22 Process for the production of shaped articles from modified polyoxymethylene or mixed polyoxymethylene

Country Status (5)

Country Link
BE (4) BE632796A (en)
CH (1) CH429162A (en)
DE (3) DE1201296B (en)
GB (2) GB935125A (en)
NL (4) NL299439A (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1241922B (en) * 1963-01-11 1967-06-08 Bayer Ag Process for the preparation of monoazo dyes
DE1267657C2 (en) * 1963-01-11 1968-12-05 Bayer Ag Dyeing and printing of polypropylene fibers
DE1259833B (en) * 1963-12-18 1968-02-01 Basf Ag Use of naphthazarin for dyeing and printing synthetic textile material
NL6414527A (en) * 1963-12-31 1965-07-02
GB1038915A (en) * 1964-03-11 1966-08-10 Toyo Rayon Co Ltd Process for colouring a polyolefinic shaped article containing a metal compound
GB1072491A (en) * 1964-04-17 1967-06-14 Sumitomo Chemical Co Improvements in or relating to the dyeing of polyolefin materials
DE1240033B (en) * 1964-04-20 1967-05-11 Basf Ag Process for dyeing and / or printing textile materials made of polypropylene
DE1258819B (en) * 1964-07-25 1968-01-18 Hoechst Ag Process for dyeing and printing textile material made of nickel-containing polypropylene
DE1257092B (en) * 1964-07-30 1967-12-28 Basf Ag Process for dyeing or printing moldings made from synthetic macromolecular substances that contain metal compounds
US3433861A (en) * 1966-01-12 1969-03-18 Celanese Corp Production of dyed,shaped oxymethylene polymers

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1235806A (en) * 1957-01-30 1960-07-08 Eastman Kodak Co Process for improving the dyeing properties of a crystallizable polymeric hydrocarbon and new products obtained

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BE639135A (en) 1964-04-24
BE632796A (en)
CH429162A (en) 1967-01-31
DE1201296B (en) 1965-09-23
NL293124A (en)
NL293021A (en)
NL299439A (en)
BE632697A (en)
DE1234919B (en) 1967-02-23
GB935125A (en) 1963-08-28
GB1013042A (en) 1965-12-15
NL275465A (en)
BE614566A (en)

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