DE2025914A1 - Thermoplastic compsn prodn - from polyamides and - ethylene-vinyl acetate and/or vinyl alcohol copolymers, mixed in melt - Google Patents

Thermoplastic compsn prodn - from polyamides and - ethylene-vinyl acetate and/or vinyl alcohol copolymers, mixed in melt

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Publication number
DE2025914A1
DE2025914A1 DE19702025914 DE2025914A DE2025914A1 DE 2025914 A1 DE2025914 A1 DE 2025914A1 DE 19702025914 DE19702025914 DE 19702025914 DE 2025914 A DE2025914 A DE 2025914A DE 2025914 A1 DE2025914 A1 DE 2025914A1
Authority
DE
Germany
Prior art keywords
ethylene
vinyl acetate
vinyl alcohol
polyamides
vinyl
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
DE19702025914
Other languages
German (de)
Inventor
Eduard Dipl.-Chem.Dr. 4150 Krefeld; Stukenbrock Karl-Heinz 4051 Hinsbeck Barthell
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.)
Stockhausen GmbH and Co KG
Original Assignee
Chemische Fabrik Stockhausen GmbH
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
Application filed by Chemische Fabrik Stockhausen GmbH filed Critical Chemische Fabrik Stockhausen GmbH
Priority to DE19702025914 priority Critical patent/DE2025914A1/en
Publication of DE2025914A1 publication Critical patent/DE2025914A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C08L23/0861—Saponified vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)

Abstract

In the preparation of thermoplastic compsns. from one or more polyamides and an ethylene-vinyl acetate copolymer and/or an ethylene-vinyl alcohol copolymer and/or an ethylene-vinyl acetate-vinyl alcohol terpolymer, the components are combined by melting them together or mixing them intimately in the plastic state. A synergistic effect is obtained and compsns. have good resistance to solvents and to ageing. The compsns are used as coatings and adhesives.

Description

"Thermoplastische Masse" Es ist bekannt, athylenvinylacetatcopolymerisate oder Derivate hiervon fiir Beschichtungen oder als thermoplastische Schmelz.-kleber einzusetzen. (DP 1 222 887) Sie haben aber den Nachteil, nicht ausreichend beständig gegen Lösungsmittel, wie z.l3. Chlorkohlenwasserstoffe, zu sein."Thermoplastic mass" It is known, ethylene vinyl acetate copolymers or derivatives thereof for coatings or as thermoplastic hot melt adhesives to use. (DP 1 222 887) However, they have the disadvantage of not being sufficiently resistant against solvents such as 13. Chlorinated hydrocarbons, to be.

Weiterhin ist es bekannt, Polyamide als Beschichtungsmaterial oder als thermoplastische Sclimelzkleber zu verwenden ( DAS 1 253 449). Wegen ihrer mangelnden Beständigkeit gegen Alterung bzw. Abbau ist ilir Einsatz erheblich eingeengt. Ausserdem sind textile Verbundstoffe, die mit Hilfe von Polyamiden hergestellt wurden, nicht hochwaschbeständig.It is also known to use polyamides as a coating material or to be used as thermoplastic glue (DAS 1 253 449). Because of their lack of Resistance to aging or degradation is considerably restricted for use. Besides that Textile composites made with the help of polyamides are not highly washable.

Es wurde versucht, diese Nachteile zu eliminieren, indem man Gemische aus Polyamidpulvorn und Pulvern anderer Thermoplaste, wie PVC, Polyäthylen etc. (OS 1 469 367) verwendete.Attempts have been made to eliminate these disadvantages by using mixtures made of polyamide powder and powders of other thermoplastics such as PVC, polyethylene etc. (OS 1 469 367) was used.

Da es sich hier aber um diskrete Partikel handelt, treten bei den einzelnen Partikelchen die gleichen Nachteile auf, wie sie von den einheitlichen, vorstehend beschriebenen Thermoplasten bekannt sind.However, since these are discrete particles, the individual particles have the same disadvantages as those of the uniform, thermoplastics described above are known.

Pulvermischungen haben ausserdem den Nachteil, daß sie sich während des Verarbeitungsprozesses durch unterschiedliche Dichte der Körner entmischen und dadurch auf dem zu beschichteten oder zu verklebenden Material in verstärktem Masse Qualitätsunterschiede hervorrufen.Powder mixtures also have the disadvantage that they are during of the processing process due to the different density of the grains and as a result, on the material to be coated or bonded to a greater extent Cause quality differences.

Es wlrfie nun überraschenderweise gefunden, daß man ein thermoplastisches Material mit hervorragenden Beständigkeitseigen- "Thermoplastische Masse" schaften erhält, wenn man Polyamide mit einem Erweichungsbereich von 80 - 130°C und einem Schmelzindex von 15 - 230 mit Copolymerisaten aus Äthylen und Vinylacetat und/oder Äthylen und Vinylalkohol und/oder Terpolymerisaten aus Äthylen und Vinyl alkohol und Vinylacetat zusammenschmilzt oder im plastischer Zustand innig miteinander vermengt.It has now surprisingly been found that a thermoplastic Material with excellent resistance properties "Thermoplastic Mass "properties are obtained when polyamides with a softening range of 80 - 130 ° C and a melt index of 15-230 with copolymers of ethylene and vinyl acetate and / or ethylene and vinyl alcohol and / or terpolymers of ethylene and vinyl alcohol and vinyl acetate melt together or intimately with one another in the plastic state mixed up.

Solcherart gewonnenn "Legierungen" lassen sich auf gewünschte Korngrößen zerkleinern oder zu Drähten oder Fasern verspinnen, je nach dem gewünschten Verwendungszweck."Alloys" obtained in this way can be reduced to desired grain sizes shredded or spun into wires or fibers, depending on the intended use.

Die Eigenschaften dieser Legierungen gehen über die Eigenschaften der Einzelkomponenten hinaus, d.h., es tritt ein synergistischer Effekt ein.The properties of these alloys go beyond the properties the individual components, i.e. there is a synergistic effect.

Das Vermischen der Komponenten kann in einem Schmelzkessel vorgenommen werden. Zweckmäßig ist aber die Verarbeitung in einem geheizten Kneter oder in einem Extruder.The components can be mixed in a melting kettle will. However, processing in a heated kneader or in one is expedient Extruder.

Die als Legierungsbestandteile verwendeten Äthylenvinylacetat-und Äthylenvinylalkohol-Copolymerisate und Äthylen-Vinylacetat-Vinylalkohol-Terpolymerisate müssen einen Äthylenanteil von mindestens 50% bzw. 66% und im letzten Falle von 58% besitzen.The ethylene vinyl acetate and used as alloy components Ethylene vinyl alcohol copolymers and ethylene vinyl acetate vinyl alcohol terpolymers must have an ethylene content of at least 50% or 66% and in the latter case of 58% own.

Die Ilerstellung der Legierungskomponenten n kann auf beliebige Weise erfolgen und ist nicht Gegenstand dieser Anmeldung.The alloy components can be produced in any desired manner take place and is not the subject of this application.

Der Anteil an Polyamiden in den beanspruchten Legierungen soll mindestens t5°h und höchstens 85% betragen.The proportion of polyamides in the claimed alloys should be at least t5 ° h and a maximum of 85%.

Man hat es in der Hand, durch Variationen des Mischungsverhältnisses der Legierungsbestandteile thermoplastische Massen herzustellen, die sich entweder für das Wirbelsintern, flir K«schierungen, für Klebzwecke oder dgl. besonders eignen.You have it in your hand by varying the mixing ratio of the alloy components to produce thermoplastic masses that are either Particularly suitable for whirl sintering, for laminating, for adhesive purposes or the like.

"Thermoplastische Masse" Beispiel 1 3n einem fiir die Kunststoffverarbeitung üblichen Extruder wird eine Granulatmischung aus 50 Gewichtsteilen eines Polyamides mit dem Erweichungsbereich 110-120°C und einem Schemelzindex von 200 und 50 Teilen eines Äthylen-Vinylalkohol-Copolymerisates (Äthylen zu Vinylalkohol 82:18) bei einer Extruderkopftemperatur von 90°C ui einen Kabel von 5 mm Durchmesser verarbeitet und in einer angeschlossenen Granuliervorrichtung zu einem Granulat der Zylinderlänge von 5 mm zerkleinert. Das so erhaltene Granulat wird mittels einer Trichtennühle unter Kühlung ZU einem Pulver der Korngröße 0,3-0,5 mm gemahlen. Dieses Pulver kann zur punktförmigen Heiß-Verklebung von Flächengebil den, insbesondere Textilien, verwendet werden."Thermoplastic Compound" Example 1 3n one for plastics processing The usual extruder is a granulate mixture of 50 parts by weight of a polyamide with a softening range of 110-120 ° C and a Schelelzindex of 200 and 50 parts an ethylene-vinyl alcohol copolymer (ethylene to vinyl alcohol 82:18) at a Extruder head temperature of 90 ° C and processed a cable of 5 mm diameter and in a connected granulating device to form granules of the length of a cylinder crushed by 5 mm. The granulate obtained in this way is made using a funnel mill ground into a powder with a grain size of 0.3-0.5 mm while cooling. This powder can for point-like hot bonding of flat structures, especially textiles, be used.

Die Verklebungen sind in kaltem und heißem Wasser sowie een Lösungsmittel beständig.The bonds are in cold and hot water and a solvent resistant.

Beispiel 2 In einem Kondensationsreaktor werden auf 50 Teile der Schnelze des im Beispiel 1 verwendeten polyamids 50 Teile eines Äthylen Vinylacetat-Copolymerisates (Äthylen zu Vinylacetat 70:30) zugesetzt, geschmolzen und vermischt. Die Schmelze wird in der iiblichen Weise aus dem Reaktor ausgetragen und granuliert. Nach dem Mahlen des Granulates auf eine Korngröße von 0,06-0,1 mm kann das Pulver zum Heiß-Verkleben von Flächengebilden, insbesonderte aus Metallfasern (Metallfaservliese), verwendet werden.Example 2 In a condensation reactor, 50 parts of the melt of the polyamide used in Example 1, 50 parts of an ethylene vinyl acetate copolymer (Ethylene to vinyl acetate 70:30) added, melted and mixed. The melt is discharged from the reactor in the usual way and granulated. After this Grinding the granulate to a grain size of 0.06-0.1 mm can be used to hot-glue the powder of flat structures, in particular made of metal fibers (metal fiber fleeces) will.

Beispiel 3 Eine Mischung aus 50 Teilen des in Beispiel 1 genannten Polyamid-Granulates und 50 Teilen eines granulierten Äthylen-Vinylacetat-Vinylalkohol-Terpolymerisates (Äthylen zu Vinylacetat zu Vinylalkohol 75:16:9 ) wird mit einem Kunststoffextruder, dermit einem Spritzkopf ausgerüstet ist, welcher die Herstellung feiner Fasern ermöglicht, extrudiert. Die Fascrn können zu einem Vlies weiterverarheitet werden,das zur Herstellung von Flächengebilden unter Hitze und Druck benutzt werden kann.Example 3 A mixture of 50 parts of that mentioned in Example 1 Polyamide granules and 50 parts of a granulated ethylene-vinyl acetate-vinyl alcohol terpolymer (Ethylene to vinyl acetate to vinyl alcohol 75: 16: 9) is made with a plastic extruder, which is equipped with a spray head, which enables the production of fine fibers, extruded. The fibers can be further processed into a fleece, which is used for production can be used by fabrics under heat and pressure.

"Thermoplastische Masse" Beispiel 4 In einem Extruder wird, wie in Beispiel 1 beschrieben, eine Granulatmischung aus 50 Gewichtsteilen eines Polyamides mit dem Erweichtungsbereich von 110-120 C und einem Schmelzindex von 200 und iG,5 Teilen eines Äthylen-Vinylallçoholcopolymerisates (Äthylen zu Vinylalkohol 82:18) und 1615 Teilen eines Äthylen-Vinylacetatcopolymerisates (Äthylen zu Vinylacetat 70:30) und 1G,5 Gewichtsteilen eines Äthylen-Vinylacetat Vinylalkoholterpolymerisates (Äthylen zu Vinylacetat zu Vinylalkohol 75:16:9) bei einer Pritzkopftemperatur von 950C legiert, zu einem Strang von 5 mm Durchmesser ausgezogen, granuliert und wie in Beispiel 1 vermahlen."Thermoplastic Compound" Example 4 In an extruder, as in Example 1 described, a granulate mixture of 50 parts by weight of a polyamide with a softening range of 110-120 C and a melt index of 200 and iG, 5 Share an ethylene-vinyl alcohol copolymer (ethylene to vinyl alcohol 82:18) and 1615 parts of an ethylene-vinyl acetate copolymer (ethylene to vinyl acetate 70:30) and 1G, 5 parts by weight of an ethylene-vinyl acetate vinyl alcohol terpolymer (Ethylene to vinyl acetate to vinyl alcohol 75: 16: 9) at a pressure head temperature of 950C alloyed, drawn into a strand of 5 mm diameter, granulated and how mill in Example 1.

Die Legierung eignet sich besonders zur Beschichtung von Eletallen nach dem Wirbelsinterverfahren, wozu sie in eine geeignete Korngrößenverteilung von etwa 0,08 - 0,2 mm zu bringen ist.The alloy is particularly suitable for the coating of eletals according to the fluidized bed sintering process, for which they are converted into a suitable grain size distribution from about 0.08 - 0.2 mm is to be brought.

Claims (6)

"Thermoplastischen MAss3"Thermoplastic MAss3 P a t e n t a n s p r $u c h e 1.) Thermoplastiche Masse (Legierung) aus einem oder mehreren Polyamid(en) und einem Äthylen-Vinylacetat-Copolymerisat und/oder einem Äthylen-Vinylalkohol-Copolymerisat und/oder einem Athylen-Vinylacetat-Vinylalkohol-Terpolymerisat, dadurch gekennzeichnet, daß man die Komponenten vor der Weiterverarbeitung bzw. Benutzung zusammenschmilzt oder im plastischen Zustand innig vermengt. P a t e n t a n s p r $ u c h e 1.) Thermoplastic mass (alloy) of one or more polyamides and an ethylene-vinyl acetate copolymer and / or an ethylene-vinyl alcohol copolymer and / or an ethylene-vinyl acetate-vinyl alcohol terpolymer, characterized in that the components are processed prior to further processing or Use melts together or intimately mixed in the plastic state. 2.)Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man Polyamide mit Erweichungsbereichen von 80-130 C und einem Schmelzindex von 15 bis 230 (vorzugsweise 140-200) verwendet.2.) Process according to claim 1, characterized in that one polyamides with softening ranges of 80-130 C and a melt index of 15 to 230 (preferably 140-200) is used. 3.)Vcrfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß Äthylen Vinylacetat-Copolymerisate mit einem Verhältnis Äthylen zu Vinylacetat von 95: 5 bis 50 : 50 verwendet werden.3.) Vcrfahren according to claim 1, characterized in that ethylene Vinyl acetate copolymers with an ethylene to vinyl acetate ratio of 95: 5 up to 50:50. 4.)Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß Äthy len-Vinylalkohol-Copolymerisate mit einem Verhältnis von Äthylen zu Vinylalkohol von 97:3 bis 66:34 verwendet werden.4.) Process according to claim 1, characterized in that ethylene-vinyl alcohol copolymers with an ethylene to vinyl alcohol ratio of 97: 3 to 66:34 can be used. 5.)Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß Äthylen-Vinylacetat-Vinylalkohol-Terpolymerisate mit einem Äthylenanteil von mindestens 58% verwendet werden.5.) Process according to claim 1, characterized in that ethylene-vinyl acetate-vinyl alcohol terpolymers with an ethylene content of at least 58% can be used. 6.)Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß der Anteil an Polyamid(en) in der Legierung mindestens 15% und höchstens 85% beträgt.6.) The method according to claim 1, characterized in that the proportion of polyamide (s) in the alloy is at least 15% and at most 85%.
DE19702025914 1970-05-27 1970-05-27 Thermoplastic compsn prodn - from polyamides and - ethylene-vinyl acetate and/or vinyl alcohol copolymers, mixed in melt Pending DE2025914A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2425989A1 (en) * 1973-05-30 1974-12-19 Daicel Ltd HOT-MELT ADHESIVES, IN PARTICULAR FOR GLUING METALS
DE2454770A1 (en) * 1974-11-19 1976-05-26 Basf Ag THERMOPLASTIC MOLDING COMPOUNDS WITH INCREASED TOUGHNESS
FR2523143A1 (en) * 1982-03-11 1983-09-16 Ato Chimie Ethylene!-vinyl! ester, pref. acetate, hot melt adhesive compsn. - contg. co:polyether ester-amide to improve temp. resistance
WO1996020979A1 (en) * 1994-12-29 1996-07-11 Elf Atochem S.A. Pulverulent polyamide composition for the coating of metal substrates

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2425989A1 (en) * 1973-05-30 1974-12-19 Daicel Ltd HOT-MELT ADHESIVES, IN PARTICULAR FOR GLUING METALS
DE2454770A1 (en) * 1974-11-19 1976-05-26 Basf Ag THERMOPLASTIC MOLDING COMPOUNDS WITH INCREASED TOUGHNESS
FR2523143A1 (en) * 1982-03-11 1983-09-16 Ato Chimie Ethylene!-vinyl! ester, pref. acetate, hot melt adhesive compsn. - contg. co:polyether ester-amide to improve temp. resistance
WO1996020979A1 (en) * 1994-12-29 1996-07-11 Elf Atochem S.A. Pulverulent polyamide composition for the coating of metal substrates
FR2731005A1 (en) * 1994-12-29 1996-08-30 Atochem Elf Sa POLYAMIDE-BASED POWDER COMPOSITION FOR COATING METAL SUBSTRATES
AU706987B2 (en) * 1994-12-29 1999-07-01 Elf Atochem S.A. Polyamide-based powder composition for coating metal substrates
US6027814A (en) * 1994-12-29 2000-02-22 Elf Atochem S.A. Pulverulent polyamide composition for the coating of metal substrates

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