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EP1368424A1 - Flame-resistant polypropylene compounds - Google Patents

Flame-resistant polypropylene compounds

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Publication number
EP1368424A1
EP1368424A1 EP02735109A EP02735109A EP1368424A1 EP 1368424 A1 EP1368424 A1 EP 1368424A1 EP 02735109 A EP02735109 A EP 02735109A EP 02735109 A EP02735109 A EP 02735109A EP 1368424 A1 EP1368424 A1 EP 1368424A1
Authority
EP
European Patent Office
Prior art keywords
polymer
flame retardant
weight
compound
amount
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.)
Withdrawn
Application number
EP02735109A
Other languages
German (de)
French (fr)
Inventor
René Herbiet
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.)
Albemarle Corp
Original Assignee
Albemarle Corp
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 Albemarle Corp filed Critical Albemarle Corp
Priority to EP02735109A priority Critical patent/EP1368424A1/en
Publication of EP1368424A1 publication Critical patent/EP1368424A1/en
Withdrawn legal-status Critical Current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
    • 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
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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 atoms other than carbon or hydrogen
    • C08L23/0853—Ethene vinyl acetate copolymers

Definitions

  • the invention relates to a filled propylene polymer compound with improved flame retardant equipment based on magnesium hydroxide.
  • propylene polymers are used, for. B. processed according to US 4,847,317 or US 4,990,554 with inorganic fillers to form compounds. Compared to unfilled propylene polymers, the compounds are characterized by increased impact resistance and mechanical hardness.
  • the compound is also to have improved flame retardancy, flame retardant fillers which require self-extinguishing and / or crust-forming fillers such as.
  • flame retardant fillers which require self-extinguishing and / or crust-forming fillers
  • Ammonium polyphosphate incorporated.
  • Magnesium hydroxides have proven themselves in recent years as advantageous halogen-free fillers for polymer finishing with a good flame retardant effect and smoke gas suppression. Typical degrees of filling are between 30 and 80% by weight based on the
  • the object of the invention was to develop a propylene polymer compound by adding suitable additives which, with flame retardant equipment based on fillers containing magnesium hydroxide, achieved the classification according to UL94 NO and / or LOI values above 30% O 2 and still one for extrusions - or injection molding applications has sufficiently high flowability.
  • the object of the invention could be achieved by compounding propylene polymers with coated magnesium hydroxide filler and ethylene / vinyl acetate copolymer according to claim 1.
  • the combination of filler coating and vinyl acetate has a synergistic effect.
  • the new compound can be B. processed by extrusion and thus opens up new areas of application for flame-retardant polymers.
  • the compound according to the invention contains propylene polymers in an amount of 70 to 99% by weight, based on the total polymer content.
  • Suitable types of propylene polymers are, for example, isotactic propylene polymers of high or low crystallinity. Typical degrees of crystallinity are between 50 and 70%. Particularly suitable are homopolymers of different molecular weights and molecular weight distributions, and block and random copolymers and elastomer blends obtainable by modifying the polymer composition. This includes, for example, copolymers obtainable by modification with lower ⁇ -olefins, such as ethylene and butylene, and blends of propylene polymers with elastomers, such as, for. B. with ethylene / propylene / diene terpolymers (PP / EPDM blends).
  • PP / EPDM blends ethylene / propylene / diene terpolymers
  • the polymer is preferably a propylene polymer / ⁇ -olefin copolymer in the form of a block copolymer and / or a random copolymer and / or a polymer blend composed of a propylene polymer with at least one elastomer and / or at least one ⁇ -olefin polymer. Also suitable are, for. B. ethylene / styrene or ethylene / cycloolefin copolymers.
  • Propylene polymer blends can also be made by adding the appropriate polymers to the propylene polymers in one operation during compounding.
  • the compound according to the invention contains propylene polymer in an amount of 80 to 95% by weight, based on the total polymer content.
  • the compound according to the invention contains ethylene / vinyl acetate copolymer in an amount of 1 to 30% by weight, based on the total polymer content.
  • the ethylene / vinyl acetate copolymer mentioned has a vinyl acetate content of 6 to 80% by weight. In a further preferred embodiment, the ethylene / vinyl acetate copolymer mentioned has a vinyl acetate content of 12 to 80% by weight.
  • the compound according to the invention contains ethylene / vinyl acetate copolymer in an amount of 5 to 20% by weight, based on the total polymer content.
  • the compound contains synthetic or natural magnesium hydroxide in an amount of 25 to 80% by weight, based on the total amount of the compound.
  • the filler mentioned is contained in an amount of 50 to 70% by weight, based on the total amount of the compound.
  • the filler mentioned is coated.
  • the surface treatment of the filler is carried out in a preferred embodiment with a derivative from the group of polymer fatty acids, keto fatty acids, fatty alkyloxazolines or bisoxazolines and, if appropriate, a siloxane derivative or in another preferred embodiment with a fatty acid and a siloxane derivative, where appropriate both surface treatments are also combined can.
  • polymer fatty acids by oligomerization such as. B. understood by dimerization or trimerization of corresponding fatty acids.
  • Suitable representatives are e.g. B. poly stearic acid, polylauric acid or polydecanoic acid (Henkel papers 28, 1992, pp 39ff).
  • Keto fatty acids are to be understood as meaning fatty acids containing keto groups with preferably 10 to 30 carbon atoms.
  • the preferred representative of a keto fatty acid is ketostearic acid (Henkel papers 28, 1992, pp. 34ff).
  • Fatty alkyl oxazolines are taken to mean the oxazolines substituted in the 2-position alkyl or hydroxyalkyl.
  • the alkyl group preferably has 7 to 21 carbon atoms.
  • Bisoxazolines are compounds that are synthesized from the hydroxyalkyloxazolines by reaction with diisocyanates.
  • a preferred representative is e.g. B. 2-undecyl-oxazoline (Henkel papers 28, 1992 pp. 43ff).
  • a fatty acid is either a saturated or unsaturated fatty acid with preferably 10 to 30 carbon atoms, a mono- or polyunsaturated hydroxy fatty acid with preferably 10 to 30 carbon atoms, such as.
  • As hydroxynervonic acid or ricinoleic acid or a saturated hydroxy fatty acid such as. B. hydroxystearic acid, or a derivative of the above compounds understood.
  • Suitable natural fatty acids are e.g. B. stearic acid, lauric acid, myristic acid, palmitic acid, oleic acid or linoleic acid.
  • As fatty acid derivatives fatty acid salts or modified fatty acids such as. B. stearic acid glycidyl methacrylate can be used.
  • Saturated fatty acids or hydroxy fatty acids or derivatives thereof are preferably used. In order to achieve the required property profile, the siloxane component is absolutely necessary when using fatty acids alone.
  • the fatty acids or fatty acid derivatives mentioned can be used either individually or in combination in an amount of from 0.01 to 10 parts, preferably from 0.05 to 5 parts, per 100 parts of filler.
  • the addition amount of the siloxane component is 0.01 to 20 parts, preferably 0.05 to 10 parts, per 100 parts of filler.
  • Suitable siloxane derivatives are oligoalkylsiloxanes, polydialkylsiloxanes such as. B. polydimethylsiloxane, polydiethylsiloxane, polyalkylarylsiloxanes such as. B. polyphenylmethylsiloxane or polydiarylsiloxanes such. B. Polyphenylsiloxane.
  • siloxanes mentioned can with reactive groups such as. B. hydroxy, amino, vinyl, acrylic, methacrylic, carboxyl or glycidyl groups.
  • High-molecular polydialkylsiloxanes so-called silicone oils, which have optionally been functionalized with the groups mentioned are preferably used as siloxane derivatives.
  • the magnesium hydroxide can be coated with fatty acids and silicone oil, for example in accordance with WO 96/26240.
  • the compounds produced according to the invention are distinguished by a higher flame resistance in comparison to corresponding propylene polymer compounds without ethylene / vinyl acetate copolymer admixtures.
  • the compounds according to the invention achieve a limiting oxygen index of at least 25%, preferably of at least 30% (sample size 6x3x150 mm 3 ).
  • the filled compounds obtained according to claim 1 can additionally contain additives to improve the elongation at break, such as. B. maleic anhydride.
  • the filled compounds obtained according to claim 1 can additionally contain fibrous additives for reinforcement.
  • the fibrous additives include, for example, glass fibers, stone fibers, metal fibers, ceramic fibers, including the single crystals, the so-called "whiskers", and likewise all fibers originating from synthetic polymers, such as, for. B. aramid, carbon, polyamide, polyacrylic and polyester fibers.
  • the compounds according to the invention can contain other application-related additives or auxiliaries such as. B. calcium carbonate, polyethylene waxes and / or stabilizers and / or antioxidants. i
  • the compounds can also be colored with suitable pigments and / or dyes.
  • the additives and colorants mentioned can be present individually or in combination.
  • test specimens were injection molded from the compounds.
  • the fire behavior was tested according to UL94 V on test specimens with a material thickness of 3.2 mm.
  • the LOI rods have sample dimensions of 6x3x150 mm 3 .
  • Stamp loads of 5 kg at 230 ° C. were used for the melt index determinations.
  • Example 4 290 g of partially crystalline propylene polymer Novolen® 3200 H (BASF / BASELL, 29% by weight based on the compound; 82.9% by weight based on the entire polymer) and 60 g Escorene® Ultra UL00328 (EVA, 27% by weight) VA copolymer, Exxon, 6% based on the compound; 17.1% by weight based on the entire polymer), were on a rolling mill from Collin, type W150M with 650 g magnesium hydroxide filler MAGNIFIN® H 5 MV (65 % By weight based on the compound) compounded at a roller temperature of 170 ° C. The compounding time was 35 min.
  • Levapren® 700 (EVA, 70% by weight VA copolymer, Bayer, i% based on the compound; 2.9% by weight based on the entire polymer) were on a rolling mill from Collin, Type W150M compounded with 650 g magnesium hydroxide filler MAGNIFIN® H 5 MV (65% by weight based on the compound) at a roller temperature of 170 ° C. The compounding time was 35 minutes.
  • Compounding time was 35 min.
  • Example 7 290 g of partially crystalline propylene polymer Novolen® 3200 H (BASF / BASELL, 29% by weight based on the compound; 82.9% by weight based on the entire polymer) and 60 g Levapren® 700 (ethylene / vinyl acetate copolymer (EVA ), 70 wt.% VA copolymer, Bayer, 6% based on the compound; 17.1 wt.% Based on the entire polymer), were on a rolling mill from Collin, type W150M with 650 g magnesium hydroxide filler MAGNIFIN ® H 5 MV (65% by weight based on the compound) compounded at a roller temperature of 170 ° C. The compounding time was 35 min.
  • EVA ethylene / vinyl acetate copolymer

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a novel polypropylene compound based on halogen-free, flame-resistant filling materials containing magnesium hydroxide, said compound having good extrudability and improved flame protective action.

Description

Beschreibung:Description:
Gegenstand der Erfindung ist ein gefülltes Propylenpolymercompound mit verbesserter Flammschutzausrüstung auf der Basis von Magnesiumhydroxid.The invention relates to a filled propylene polymer compound with improved flame retardant equipment based on magnesium hydroxide.
Zur Nerbesserung der mechanischen und optischen Eigenschaften werden Propylenpolymere z. B. gemäss US 4 847 317 oder US 4 990 554 mit anorganischen Füllstoffen zu Compounds verarbeitet. Die Compounds zeichnen sich gegenüber ungefüllten Propylenpolymeren durch eine erhöhte Stossfestigkeit und mechanische Härte aus.To improve the mechanical and optical properties, propylene polymers are used, for. B. processed according to US 4,847,317 or US 4,990,554 with inorganic fillers to form compounds. Compared to unfilled propylene polymers, the compounds are characterized by increased impact resistance and mechanical hardness.
Wenn das Compound neben verbesserten mechanischen Materialeigenschaften auch einen verbesserten Flammschutz aufweisen soll, werden flammhemmende, die Selbstverlöschung fordernde und/oder krustenbildende Füllstoffe wie z. B. Metallhydroxide, halogenhaltige, meist bromierte Flammschutzmittel oder phosphorhaltige Flammschutzmittel, wie z. B.If, in addition to improved mechanical material properties, the compound is also to have improved flame retardancy, flame retardant fillers which require self-extinguishing and / or crust-forming fillers such as. B. metal hydroxides, halogen-containing, mostly brominated flame retardants or phosphorus-containing flame retardants, such as. B.
Ammoniumpolyphosphat, eingearbeitet.Ammonium polyphosphate, incorporated.
Magnesiumhydroxide haben sich in den letzten Jahren als vorteilhafte halogenfreie Füllstoffe zur Polymerausrüstung mit einer guten Flammschutzwirkung und Rauchgasunterdrückung bewährt. Typische Füllgrade liegen hierbei zwischen 30 und 80 Gew. % bezogen auf dieMagnesium hydroxides have proven themselves in recent years as advantageous halogen-free fillers for polymer finishing with a good flame retardant effect and smoke gas suppression. Typical degrees of filling are between 30 and 80% by weight based on the
Gesamtmenge des Compounds.Total amount of compound.
Untersuchungen zum Flammschutz von Polymeren werden z. B. nach den Underwriters • Laboratories Safety Standards 94 durchgeführt und führen beim Bestehen des Tests zu einer Einstufung der Polymere bzw. der Compounds in die Brandschutzklassen UL94 N2 bis UL94 NO. Eine weitere gängige Methode zur Bewertung der Flammwidrigkeit stellt die Messung der Sauerstoffindizes (LOI) nach ASTM D 2863 dar. Dabei wird die Sauerstoffkonzentration in einem Stickstoff/Sauerstoff-Gemisch angegeben, bei dem ein genormter Probekörper gerade noch weiterbrennt. Ein höherer Sauerstofϊϊndex stellt demnach eine Nerbesserung der Flammschutzwirkung dar.Studies on flame retardancy of polymers are e.g. B. carried out according to the Underwriters • Laboratories Safety Standards 94 and if the test is passed, the polymers or compounds are classified in the fire protection classes UL94 N2 to UL94 NO. Another common method for evaluating flame retardancy is to measure the oxygen indices (LOI) according to ASTM D 2863. The oxygen concentration is specified in a nitrogen / oxygen mixture in which a standardized test specimen is still burning. A higher oxygen index therefore represents an improvement in the flame retardant effect.
Für Spritzgussartikel wie z. B. Elektroteile oder Extrudate wie z. B. Rohre wird vielfach die höchste Einstufung nach UL94 NO gefordert. Dies lässt sich bei den gängigen Propylen- polymertypen mit Magnesiumhydroxid jedoch in der Regel nur mit Füllgraden oberhalb 65 Gew. % bezogen auf das Compound erreichen (Tabelle 1).For injection molded articles such as B. electrical parts or extrudates such. B. Pipes are often required to have the highest UL94 NO rating. In the case of the common propylene polymer types with magnesium hydroxide, however, this can generally only be achieved with fill levels above 65% by weight, based on the compound (Table 1).
Selbst durch Einsatz von Magnesiumhydroxiden hoher Oberfläche, wie z. B. MAGΝIFLΝ® H 10 oder der beschichteten Type MAGΝIFIΝ® H 10 F lässt sich bei den gängigsten Pro- pylenpolymer-Typen in der Regel nur eine Einstufung nach UL94 Nl erreichen.Even by using magnesium hydroxides with a high surface area, e.g. B. MAGΝIFLΝ® H 10 or the coated type MAGΝIFIΝ® H 10 F can usually only be achieved in accordance with UL94 Nl for the most common types of propylene polymer.
BESTÄTIGUΝGSKOPIE Um in einem Propylenpolymercompound eine Einstufung in die Brandschutzklasse UL94 NO zu erzielen, müsste das Compound mit Magnesiumhydroxid noch höher gefüllt werden. Gleiches gilt für das Erreichen von höheren LOI- Werten. Vielfach, wie z. B. bei Kabelummantelungen, ist ein LOI- Wert deutlich über 30% O2 gefordert, um gängige Brandschutznormen am fertigen Kabel zu erfüllen. Bei Füllgraden über 65 Gew. % verschlechtern sich aber sowohl die mechanische Belastbarkeit der Endprodukte als auch die Theologischen Eigenschaften der Compounds während der Verarbeitung, wodurch die Anwendungsbreite von hochgefüllten flammgeschützten Propylenpolymercompounds eingeschränkt ist.CONFIRMATION COPY In order to achieve a fire protection class UL94 NO in a propylene polymer compound, the compound would have to be filled even higher with magnesium hydroxide. The same applies to the achievement of higher LOI values. In many cases, such as B. with cable sheathing, a LOI value of well over 30% O 2 is required in order to meet common fire protection standards on the finished cable. At fill levels above 65% by weight, however, both the mechanical strength of the end products and the theological properties of the compounds deteriorate during processing, as a result of which the range of applications of highly filled flame-retardant propylene polymer compounds is restricted.
Um die Haftung zwischen Polymer und Füllstoff und damit die Theologischen und mechanischen Eigenschaften des Compounds zu verbessern, werden z. B. gemäss US 5 104 925 Maleinsäurederivate eingearbeitet oder gemäss EP-0292233-A1 die Füllstoffe mit kompati- bilitätsfordernden Hilfsstoffen beschichtet. Derartig beschichtete Füllstoffe sind z. B. MAGΝIFIΝ® H 5 GN oder MAGΝIFIΝ® H 5 KN von Martinswerk GmbH, Bergheim.In order to improve the adhesion between polymer and filler and thus the theological and mechanical properties of the compound, z. B. incorporated according to US 5 104 925 maleic acid derivatives or coated according to EP-0292233-A1, the fillers with compatibility-requiring auxiliaries. Such coated fillers are e.g. B. MAGΝIFIΝ® H 5 GN or MAGΝIFIΝ® H 5 KN from Martinswerk GmbH, Bergheim.
Aufgabe der Erfindung war die Entwicklung eines Propylenpolymercompounds durch Zugabe von geeigneten Additiven, das mit einer Flammschutzausrüstung auf der Basis von magne- siumhydroxidhaltigen Füllstoffen möglichst die Einstufung nach UL94 NO und/oder LOI- Werte oberhalb von 30% O2 erreicht und dennoch eine für Extrusions- bzw. Spritzgussanwendungen genügend hohe Fliessfähigkeit aufweist.The object of the invention was to develop a propylene polymer compound by adding suitable additives which, with flame retardant equipment based on fillers containing magnesium hydroxide, achieved the classification according to UL94 NO and / or LOI values above 30% O 2 and still one for extrusions - or injection molding applications has sufficiently high flowability.
Entgegen der Erwartung, dass Propylenpolymere mit Magnesiumhydroxid als flammhemmendem Füllstoff eine Emstufung nach UL94 NO nur mit Füllgraden über 65% erreichbar ist, konnte die erfindungsgemässe Aufgabe durch Compoundierung von Propylenpolymeren mit beschichtetem Magnesiumhydroxidfüllstoff und Eώylen/Vinylacetat-Copolymer gemäss Anspruch 1 gelöst werden.Contrary to the expectation that propylene polymers with magnesium hydroxide as a flame-retardant filler can be upgraded to UL94 NO only with fill levels above 65%, the object of the invention could be achieved by compounding propylene polymers with coated magnesium hydroxide filler and ethylene / vinyl acetate copolymer according to claim 1.
Synergistisch wirkt dabei die Kombination zwischen Füllstoffbeschichtung und Vinylacetat. Neben der gewünschten Flammhemmung lässt sich das neue Compound z. B. durch Extrusion verarbeiten und eröffnet somit für flammgeschützte Polymere neue Anwendungsbereiche. Das erfindungsgemässe Compound enthält Propylenpolymere in einer Menge von 70 bis 99 Gew. % bezogen auf den gesamten Polymeranteil.The combination of filler coating and vinyl acetate has a synergistic effect. In addition to the desired flame retardancy, the new compound can be B. processed by extrusion and thus opens up new areas of application for flame-retardant polymers. The compound according to the invention contains propylene polymers in an amount of 70 to 99% by weight, based on the total polymer content.
Geeignete Propylenpolymertypen sind beispielsweise isotaktische Propylenpolymere hoher oder niedriger Kristallinität. Typische Kristallinitätsgrade liegen dabei zwischen 50 und 70 %. Geeignet sind insbesondere Homopolymere verschiedener Molmasse und Molmassenverteilung sowie durch Modifizieren der Polymerzusammensetzung erhältliche Block- und Random-Copolymere und Elastomerblends. Hierunter fallen beispielsweise durch Modifizierung mit niederen α-Olefϊnen wie Ethylen und Butylen erhältliche Copolymere sowie Blends von Propylenpolymeren mit Elastomeren wie z. B. mit Ethylen/Propylen/Dien-Terpolymeren (PP/EPDM blends).Suitable types of propylene polymers are, for example, isotactic propylene polymers of high or low crystallinity. Typical degrees of crystallinity are between 50 and 70%. Particularly suitable are homopolymers of different molecular weights and molecular weight distributions, and block and random copolymers and elastomer blends obtainable by modifying the polymer composition. This includes, for example, copolymers obtainable by modification with lower α-olefins, such as ethylene and butylene, and blends of propylene polymers with elastomers, such as, for. B. with ethylene / propylene / diene terpolymers (PP / EPDM blends).
Vorzugsweise ist das Polymer ein Propylenpolymer/α-Olefin-Copolymer in Form eines Block-Copolymeren und/oder eines Random-Copolymeren und/oder ein Polymerblend aus einem Propylenpolymeren mit mindestens einem Elastomeren und/oder mindestens einem α-Olefin-Polymeren. Ferner geeignet sind z. B. Ethylen/Styrol- oder Ethylen/Cycloolefin-Copolymere. DieThe polymer is preferably a propylene polymer / α-olefin copolymer in the form of a block copolymer and / or a random copolymer and / or a polymer blend composed of a propylene polymer with at least one elastomer and / or at least one α-olefin polymer. Also suitable are, for. B. ethylene / styrene or ethylene / cycloolefin copolymers. The
Propylenpolymer-Blends können auch durch Zugabe der entsprechenden Polymere zu den Propylenpolymeren in einem Arbeitsgang während der Compoundierung hergestellt werden.Propylene polymer blends can also be made by adding the appropriate polymers to the propylene polymers in one operation during compounding.
In einer bevorzugten Ausführung enthält das erfindungsgemässe Compound Propylenpolymer in einer Menge von 80 bis 95 Gew. % bezogen auf den gesamten Polymeranteil.In a preferred embodiment, the compound according to the invention contains propylene polymer in an amount of 80 to 95% by weight, based on the total polymer content.
Das erfindungsgemässe Compound enthält Ethylen/Ninylacetat-Copolymer in einer Menge von 1 bis 30 Gew. % bezogen auf den gesamten Polymeranteil.The compound according to the invention contains ethylene / vinyl acetate copolymer in an amount of 1 to 30% by weight, based on the total polymer content.
Das genannte EthylenJVinylacetat-Copolymer hat einen Ninylacetat- Anteil von 6 bis 80 Gew. %. In einer weiteren bevorzugten Ausführung hat das genannte Ethylen/Ninylacetat- Copolymer einen Ninylacetat-Anteil von 12 bis 80 Gew. %.The ethylene / vinyl acetate copolymer mentioned has a vinyl acetate content of 6 to 80% by weight. In a further preferred embodiment, the ethylene / vinyl acetate copolymer mentioned has a vinyl acetate content of 12 to 80% by weight.
In einer weiteren bevorzugten Ausführung enthält das erfindungsgemässe Compound Ethylen/Vinylacetat-Copolymer in einer Menge von 5 bis 20 Gew. % bezogen auf den gesamten Polymeranteil. Das Compound enthält als Füllstoff synthetisches oder natürliches Magnesiumhydroxid in einer Menge von 25 bis 80 Gew. % bezogen auf die Gesamtmenge des Compounds. In einer bevorzugten Ausführung ist der genannte Füllstoff in einer Menge von 50 bis 70 Gew. % bezogen auf die Gesamtmenge des Compounds enthalten.In a further preferred embodiment, the compound according to the invention contains ethylene / vinyl acetate copolymer in an amount of 5 to 20% by weight, based on the total polymer content. As a filler, the compound contains synthetic or natural magnesium hydroxide in an amount of 25 to 80% by weight, based on the total amount of the compound. In a preferred embodiment, the filler mentioned is contained in an amount of 50 to 70% by weight, based on the total amount of the compound.
In einer bevorzugten Ausführung ist der genannte Füllstoff beschichtet. Die Oberflächenbehandlung des Füllstoffs erfolgt in einer bevorzugten Ausfuhrungsform mit einem Derivat aus der Gruppe der Polymerfettsäuren, der Ketofettsäuren, der Fettalkyloxazoline oder -bisoxazoline und gegebenenfalls einem Siloxanderivat oder in einer anderen bevorzugten Ausfuhrungsform mit einer Fettsäure und einem Siloxanderivat, wobei gegebenenfalls auch beide Oberflächenbehandlungen kombiniert werden können.In a preferred embodiment, the filler mentioned is coated. The surface treatment of the filler is carried out in a preferred embodiment with a derivative from the group of polymer fatty acids, keto fatty acids, fatty alkyloxazolines or bisoxazolines and, if appropriate, a siloxane derivative or in another preferred embodiment with a fatty acid and a siloxane derivative, where appropriate both surface treatments are also combined can.
Unter Polymerfettsäuren werden durch Oligomerisierung, wie z. B. durch Di- oder Trimeri- sierung von entsprechenden Fettsäuren hergestellte Verbindungen verstanden. Geeignete Vertreter sind z. B. Poly Stearinsäure, Polylaurinsäure oder Polydecansäure (Henkel Referate 28, 1992, S. 39ff).Among polymer fatty acids by oligomerization, such as. B. understood by dimerization or trimerization of corresponding fatty acids. Suitable representatives are e.g. B. poly stearic acid, polylauric acid or polydecanoic acid (Henkel papers 28, 1992, pp 39ff).
Unter Ketofettsäuren werden ketogruppenhaltige Fettsäuren mit vorzugsweise 10 bis 30 C- Atomen verstanden. Bevorzugter Vertreter einer Ketofettsäure ist die Ketostearinsäure (Henkel Referate 28, 1992, S. 34ff).Keto fatty acids are to be understood as meaning fatty acids containing keto groups with preferably 10 to 30 carbon atoms. The preferred representative of a keto fatty acid is ketostearic acid (Henkel papers 28, 1992, pp. 34ff).
Unter Fettalkyloxazolinen werden die in 2-Stellung alkyl- bzw. hydroxyalkylsubstituierten Oxazoline verstanden. Die Alkylgruppe weist dabei vorzugsweise 7 bis 21 C-Atome auf. Bisoxazoline sind Verbindungen, die aus den Hydroxyalkyloxazolinen durch Umsetzung mit Diisocyanaten synthetisiert werden. Ein bevorzugter Vertreter ist z. B. das 2-Undecyl-oxa- zolin (Henkel Referate 28, 1992 S. 43ff).Fatty alkyl oxazolines are taken to mean the oxazolines substituted in the 2-position alkyl or hydroxyalkyl. The alkyl group preferably has 7 to 21 carbon atoms. Bisoxazolines are compounds that are synthesized from the hydroxyalkyloxazolines by reaction with diisocyanates. A preferred representative is e.g. B. 2-undecyl-oxazoline (Henkel papers 28, 1992 pp. 43ff).
In den folgenden Erläuterungen werden bei Mengenangaben mit Teilen Gewichtsteile bezeichnet.In the following explanations, parts are parts by weight.
Unter einer Fettsäure wird entweder eine gesättigte oder ungesättigte Fettsäure mit vorzugs- weise 10 bis 30 C- Atomen, eine ein- oder mehrfach ungesättigte Hydroxyfettsäure mit vorzugsweise 10 bis 30 C- Atomen wie z. B. Hydroxynervonsäure oder Ricinolsäure oder eine gesättigte Hydroxyfettsäure wie z. B. Hydroxystearinsäure, oder ein Derivat der vorstehenden Verbindungen verstanden. Geeignete natürliche Fettsäuren sind z. B. Stearinsäure, Laurin- säure, Myristinsäure, Palmitinsäure, Ölsäure oder Linolsäure. Als Fettsäurederivate können Fettsäuresalze oder modifizierte Fettsäuren wie z. B. Stearinsäureglycidylmethacrylat eingesetzt werden. Bevorzugt werden gesättigte Fettsäuren oder Hydroxyfettsäuren bzw. Derivate davon eingesetzt. Um das geforderte Eigenschafitsprofil zu erzielen, ist bei der alleinigen Verwendung von Fettsäuren die Siloxankomponente zwingend erforderlich.A fatty acid is either a saturated or unsaturated fatty acid with preferably 10 to 30 carbon atoms, a mono- or polyunsaturated hydroxy fatty acid with preferably 10 to 30 carbon atoms, such as. As hydroxynervonic acid or ricinoleic acid or a saturated hydroxy fatty acid such as. B. hydroxystearic acid, or a derivative of the above compounds understood. Suitable natural fatty acids are e.g. B. stearic acid, lauric acid, myristic acid, palmitic acid, oleic acid or linoleic acid. As fatty acid derivatives, fatty acid salts or modified fatty acids such as. B. stearic acid glycidyl methacrylate can be used. Saturated fatty acids or hydroxy fatty acids or derivatives thereof are preferably used. In order to achieve the required property profile, the siloxane component is absolutely necessary when using fatty acids alone.
Die genannten Fettsäuren oder Fettsäurederivate können entweder einzeln oder in Kombination in einer Menge von 0,01 bis 10 Teilen, vorzugsweise von 0,05ι bis 5 Teilen, pro 100 Tei- len Füllstoff eingesetzt werden.The fatty acids or fatty acid derivatives mentioned can be used either individually or in combination in an amount of from 0.01 to 10 parts, preferably from 0.05 to 5 parts, per 100 parts of filler.
Die Zuschlagsmenge der Siloxankomponente liegt bei 0,01 bis 20 Teilen, vorzugsweise bei 0,05 bis 10 Teilen, pro 100 Teilen Füllstoff.The addition amount of the siloxane component is 0.01 to 20 parts, preferably 0.05 to 10 parts, per 100 parts of filler.
Geeignete Siloxanderivate sind Oligoalkylsiloxane, Polydialkylsiloxane wie z. B. Polydi- methylsiloxan, Polydiethylsiloxan, Polyalkylarylsiloxane wie z. B. Polyphenylmethylsiloxan oder Polydiarylsiloxane wie z. B. Polyphenylsiloxan.Suitable siloxane derivatives are oligoalkylsiloxanes, polydialkylsiloxanes such as. B. polydimethylsiloxane, polydiethylsiloxane, polyalkylarylsiloxanes such as. B. polyphenylmethylsiloxane or polydiarylsiloxanes such. B. Polyphenylsiloxane.
Die genannten Siloxane können mit reaktionsfähigen Gruppen wie z. B. Hydroxy-, Amino-, Vinyl-, Acryl-, Methacryl-, Carboxyl- oder Glycidylgruppen funktionalisiert sein.The siloxanes mentioned can with reactive groups such as. B. hydroxy, amino, vinyl, acrylic, methacrylic, carboxyl or glycidyl groups.
Als Siloxanderivate werden bevorzugt hochmolekulare Polydialkylsiloxane, sogenannte Sili- konöle, eingesetzt, die gegebenenfalls mit den genannten Gruppen funktionalisiert worden sind.High-molecular polydialkylsiloxanes, so-called silicone oils, which have optionally been functionalized with the groups mentioned are preferably used as siloxane derivatives.
Das Magnesiumhydroxid kann beispielsweise gemäss WO 96/26240 mit Fettsäuren und Sili- konöl beschichtet sein.The magnesium hydroxide can be coated with fatty acids and silicone oil, for example in accordance with WO 96/26240.
Die erfindungsgemäss hergestellten Compounds zeichnen sich durch eine höhere Flammbeständigkeit im Vergleich zu entsprechenden Propylenpolymercompounds ohne Ethylen/Vinylacetat-Copolymerbeimischungen aus.The compounds produced according to the invention are distinguished by a higher flame resistance in comparison to corresponding propylene polymer compounds without ethylene / vinyl acetate copolymer admixtures.
Die erfindungsgemässen Compounds erreichen einen Limiting Oxygen Index von mindestens 25%, vorzugsweise von mindestens 30% (Probenabmessung 6x3x150 mm3). In den angeführten Beispielen wurden Werte in einem Bereich von 31 bis 36%, bei einem Füllgrad von 65% bezogen auf die Gesamtmenge des Compunds ermittelt.The compounds according to the invention achieve a limiting oxygen index of at least 25%, preferably of at least 30% (sample size 6x3x150 mm 3 ). In the examples given, values in a range from 31 to 36%, with a degree of filling of 65% based on the total amount of the compound, were determined.
Die gemäss Patentanspruch 1 erhaltenen gefüllten Compounds können zusätzlich Additive zur Verbesserung der Reissdehnung wie z. B. Maleinsäureanhydrid enthalten. Die gemäss Patentanspruch 1 erhaltenen gefüllten Compounds können zusätzlich faser- förmige Additive zur Armierung enthalten. Zu den faserförmigen Additiven zählen beispielsweise Glasfasern, Steinfasern, Metallfasern, keramische Fasern, einschliesslich der Einkristalle, den sogenannten "whiskers" und ebenso alle aus synthetischen Polymeren herrührenden Fasern, wie z. B. Aramid-, Kohlenstoff-, Polyamid-, Polyacryl- und Polyesterfasern.The filled compounds obtained according to claim 1 can additionally contain additives to improve the elongation at break, such as. B. maleic anhydride. The filled compounds obtained according to claim 1 can additionally contain fibrous additives for reinforcement. The fibrous additives include, for example, glass fibers, stone fibers, metal fibers, ceramic fibers, including the single crystals, the so-called "whiskers", and likewise all fibers originating from synthetic polymers, such as, for. B. aramid, carbon, polyamide, polyacrylic and polyester fibers.
Ausser den genannten Additiven können die erfindungsgemässen Compounds weitere anwen- dungsbezogene Zusätze oder Hilfsstoffe wie z. B. Calciumcarbonat, Polyethylenwachse und/oder Stabilisatoren und/oder Antioxidantien enthalten. iIn addition to the additives mentioned, the compounds according to the invention can contain other application-related additives or auxiliaries such as. B. calcium carbonate, polyethylene waxes and / or stabilizers and / or antioxidants. i
Die Compounds können ausserdem mit geeigneten Pigmenten und/oder Farbstoffen gefärbt sein.The compounds can also be colored with suitable pigments and / or dyes.
Die genannten Additive und Färbemittel können einzeln oder in Kombination enthalten sein.The additives and colorants mentioned can be present individually or in combination.
Obwohl die vorliegende Erfindung durch die angeführten erfindungsgemässen Beispiele 1 bis 7 vollständig offenbart wird, können aufgrund der beanspruchten Variationen der Edukte noch zahlreiche weitere erfindungsgemässe Beispiele formuliert werden. Diese Beispiele, die durch Veränderungen der Zusammensetzung innerhalb der in der Beschreibung und in den Ansprüchen definierten Variationen gemacht werden, sollen als erfindungsgemässe Beispiele gelten und in den Schutzbereich dieser Patentanmeldung fallen. Although the present invention is fully disclosed by the examples 1 to 7 according to the invention, numerous further examples according to the invention can be formulated due to the claimed variations of the starting materials. These examples, which are made by changing the composition within the variations defined in the description and in the claims, are to be considered as examples according to the invention and fall within the scope of protection of this patent application.
BeispieleExamples
Alle Probekörper wurden aus den Compounds mittels Spritzguss erzeugt. Das Brandverhalten wurde gemäss UL94 V an Probekörpern mit einer Materialstärke von 3,2 mm getestet. Die LOI-Stäbe weisen nach ASTM D 2863 Probenabmessungen von 6x3x150 mm3 auf. Für die Schmelzindexbestimmungen wurden Stempellasten von 5 kg bei 230 °C verwendet.All test specimens were injection molded from the compounds. The fire behavior was tested according to UL94 V on test specimens with a material thickness of 3.2 mm. According to ASTM D 2863, the LOI rods have sample dimensions of 6x3x150 mm 3 . Stamp loads of 5 kg at 230 ° C. were used for the melt index determinations.
Die Ergebnisse der Untersuchungen zu rheologischen und mechanischen Eigenschaften, sowie des Brandverhaltens der Compounds aus den Vergleichsbeispielen VI bis V5 sind in Tabelle 1 wiedergegeben.The results of the tests on rheological and mechanical properties and the fire behavior of the compounds from comparative examples VI to V5 are shown in Table 1.
Die Ergebnisse der Untersuchungen zu rheologischen und mechanischen Eigenschaften, sowie des Brandverhaltens der Compounds aus Vergleichsbeispiel! V5 und den erfindungsgemässen Beispielen 1 bis 7 sind in Tabelle 2 wiedergegeben. Bei den Beispielen 1 bis 7 zeigt sich die synergistische Wirkung des Vinylacetats auf das Flammverhalten der Propylenpolymercompounds .The results of the investigations into rheological and mechanical properties as well as the fire behavior of the compounds from the comparative example! V5 and Examples 1 to 7 according to the invention are shown in Table 2. Examples 1 to 7 show the synergistic effect of the vinyl acetate on the flame behavior of the propylene polymer compounds.
Beispiel Nl (Vergleich)Example Nl (comparison)
350 g teilkristallines Propylenpolymer Νovolen® 3200 H (BASF/BASELL, 35 Gew. % bezogen auf das Compound) wurden auf einem Walzwerk der Fa. Collin, Typ W150M mit 650 g Magnesiumhydroxid-Füllstoff MAGΝIFIΝ® H 5 (65 Gew. % bezogen auf das Compound) bei einer Walzentemperatur von 170 °C compoundiert. Die Compoundierzeit betrug 35 min.350 g of partially crystalline propylene polymer Νovolen® 3200 H (BASF / BASELL, 35% by weight based on the compound) were placed on a rolling mill from Collin, type W150M with 650 g magnesium hydroxide filler MAGΝIFIΝ® H 5 (65% by weight based on the compound) compounded at a roller temperature of 170 ° C. The compounding time was 35 minutes.
Beispiel N2 (Vergleich)Example N2 (comparison)
350 g teilkristallines Propylenpolymer Νovolen® 3200 H (BASF/BASELL, 35 Gew. % bezogen auf das Compound) wurden auf einem Walzwerk der Fa. Collin, Typ W150M mit 650 g Magnesiumhydroxid-Füllstoff MAGΝIFIΝ® H 5 GV (65 Gew. % bezogen auf das Compound) bei einer Walzentemperatur von 170 °C compoundiert. Die Compoundierzeit betrug 35 min. Beispiel N3 (Vergleich)350 g of partially crystalline propylene polymer Νovolen® 3200 H (BASF / BASELL, 35% by weight, based on the compound) were obtained on a rolling mill from Collin, type W150M with 650 g of magnesium hydroxide filler MAGΝIFIΝ® H 5 GV (65% by weight compounded) at a roller temperature of 170 ° C. The compounding time was 35 min. Example N3 (comparison)
350 g teilkristallines Propylenpolymer Νovolen® 3200 H (BASF/BASELL, 35 Gew. % bezogen auf das Compound) wurden auf einem Walzwerk der Fa. Collin, Typ W150M mit 650 g (65 Gew. % bezogen auf das Compound) Magnesiumhydroxid-Füllstoff MAGΝIFLΝ® H 5 HV bei einer Walzentemperatur von 170 °C compoundiert. Die Compoundierzeit betrug 35 min.350 g of semicrystalline propylene polymer Νovolen® 3200 H (BASF / BASELL, 35% by weight based on the compound) were placed on a rolling mill from Collin, type W150M with 650 g (65% by weight based on the compound) magnesium hydroxide filler MAGΝIFLΝ ® H 5 HV compounded at a roller temperature of 170 ° C. The compounding time was 35 min.
Beispiel N4 (Vergleich)Example N4 (comparison)
350 g teilkristallines Propylenpolymer Νovolen® 3200 H (BASF/BASELL, 35 Gew. % bezogen auf das Compound) wurden auf einem Walzwerk der Fa. Collin, Typ W150M mit 650 g Magnesiumhydroxid-Füllstoff MAGΝIFIΝ® H 5 KN (65 Gew. % bezogen auf das Compound) bei einer Walzentemperatur von 170 °C compoundiert. Die Compoundierzeit betrug 35 min.350 g of partially crystalline propylene polymer Νovolen® 3200 H (BASF / BASELL, 35% by weight based on the compound) were obtained on a Collin rolling mill, type W150M with 650 g MAG 650IFIΝ® H 5 KN magnesium hydroxide filler (65% by weight) compounded) at a roller temperature of 170 ° C. The compounding time was 35 min.
Beispiel N5 (Vergleich)Example N5 (comparison)
350 g teilkristallines Propylenpolymer Νovolen® 3200 H (BASF/BASELL, 35 Gew. % bezogen auf das Compound) wurden auf einem Walzwerk der Fa. Collin, Typ W150M mit 650 g Magnesiumhydroxid-Füllstoff MAGΝIFIΝ® H 5 MV (65 Gew. % bezogen auf das Compound) bei einer Walzentemperatur von 170 °C compoundiert. Die Compoundierzeit betrug 35 min.350 g of semicrystalline propylene polymer olenovolen® 3200 H (BASF / BASELL, 35% by weight based on the compound) were obtained on a rolling mill from Collin, type W150M with 650 g magnesium hydroxide filler MAGΝIFIΝ® H 5 MV (65% by weight compounded) at a roller temperature of 170 ° C. The compounding time was 35 min.
Beispiel 1example 1
340 g teilkristallines Propylenpolymer Νovolen® 3200 H (BASF/BASELL, 34 Gew. % bezogen auf das Compound; 97,1 Gew. % bezogen auf das gesamte Polymer) und 10 g Εscorene® Ultra UL40028 (Ethylen/Vinylacetat-Copolymer (EVA), 28 Gew. % VA-340 g semi-crystalline propylene polymer Νovolen® 3200 H (BASF / BASELL, 34% by weight based on the compound; 97.1% by weight based on the entire polymer) and 10 g Εscorene® Ultra UL40028 (ethylene / vinyl acetate copolymer (EVA) , 28% by weight VA-
Copolymer, Exxon, 1% bezogen auf das Compound; 2,9 Gew. % bezogen auf das gesamte Polymer), wurden auf einem Walzwerk der Fa. Collin, Typ W150M mit 650 g Magnesiumhydroxid-Füllstoff MAGΝIFIΝ® H 5 MV (65 Gew. % bezogen auf das Compound) bei einer Walzentemperatur von 170 °C compoundiert. Die Compoundierzeit betrug 35 min. Beispiel 2Copolymer, Exxon, 1% based on the compound; 2.9% by weight, based on the entire polymer), were produced on a rolling mill from Collin, type W150M with 650 g of magnesium hydroxide filler MAGΝIFIΝ® H 5 MV (65% by weight, based on the compound) at a roller temperature of 170 ° C compounded. The compounding time was 35 min. Example 2
340 g teilkristallines Propylenpolymer Novolen® 3200 H (BASF/BASELL, 34 Gew. % bezogen auf das Compound; 97,1 Gew. % bezogen auf das gesamte Polymer) und 10 g Escorene® Ultra UL00328 (EVA, 27 Gew. % VA-Copolymer, Exxon, 1% bezogen auf das Compound; 2,9 Gew. % bezogen auf das gesamte Polymer), wurden auf einem Walzwerk der Fa. Collin, Typ W150M mit 650 g Magnesiumhydroxid-Füllstoff MAGNIFIN® H 5 MV (65 Gew. % bezogen auf das Compound) bei einer Walzentemperatur von 170 °C compoundiert. Die Compoundierzeit betrug 35 min.340 g partially crystalline propylene polymer Novolen® 3200 H (BASF / BASELL, 34% by weight based on the compound; 97.1% by weight based on the entire polymer) and 10 g Escorene® Ultra UL00328 (EVA, 27% by weight VA- Copolymer, Exxon, 1% based on the compound; 2.9% by weight based on the entire polymer), were on a rolling mill from Collin, type W150M with 650 g magnesium hydroxide filler MAGNIFIN® H 5 MV (65 wt. % based on the compound) compounded at a roller temperature of 170 ° C. The compounding time was 35 min.
Beispiel 3Example 3
310 g teilkristallines Propylenpolymer Novolen® 3200 H (BASF/BASELL, 31 Gew. % bezogen auf das Compound; 88,6 Gew. % bezogen auf das gesamte Polymer) und 40 g Escorene® Ultra UL00328 (EVA, 27 Gew. % VA-Copolymer, Exxon, 4% bezogen auf das Compound; 11,4 Gew. % bezogen auf das gesamte Polymer), wurden auf einem Walzwerk der Fa. Collin, Typ Wl 50M mit 650 g Magnesiumhydroxid-Füllstoff MAGNIFIN® H 5 MV (65 Gew. % bezogen auf das Compound) bei einer Walzentemperatur von 170 °C compoundiert. Die Compoundierzeit betrug 35 min.310 g partially crystalline propylene polymer Novolen® 3200 H (BASF / BASELL, 31% by weight based on the compound; 88.6% by weight based on the entire polymer) and 40 g Escorene® Ultra UL00328 (EVA, 27% by weight VA- Copolymer, Exxon, 4% based on the compound; 11.4% by weight based on the entire polymer), were rolled on a Rollin mill from Collin, type Wl 50M with 650 g magnesium hydroxide filler MAGNIFIN® H 5 MV (65% by weight) .% based on the compound) compounded at a roller temperature of 170 ° C. The compounding time was 35 min.
Beispiel 4 290 g teilkristallines Propylenpolymer Novolen® 3200 H (BASF/BASELL, 29 Gew. % bezogen auf das Compound; 82,9 Gew. % bezogen auf das gesamte Polymer) und 60 g Escorene® Ultra UL00328 (EVA, 27 Gew. % VA-Copolymer, Exxon, 6% bezogen auf das Compound; 17,1 Gew. % bezogen auf das gesamte Polymer), wurden auf einem Walzwerk der Fa. Collin, Typ W150M mit 650 g Magnesiumhydroxid-Füllstoff MAGNIFIN® H 5 MV (65 Gew. % bezogen auf das Compound) bei einer Walzentemperatur von 170 °C compoundiert. Die Compoundierzeit betrug 35 min.Example 4 290 g of partially crystalline propylene polymer Novolen® 3200 H (BASF / BASELL, 29% by weight based on the compound; 82.9% by weight based on the entire polymer) and 60 g Escorene® Ultra UL00328 (EVA, 27% by weight) VA copolymer, Exxon, 6% based on the compound; 17.1% by weight based on the entire polymer), were on a rolling mill from Collin, type W150M with 650 g magnesium hydroxide filler MAGNIFIN® H 5 MV (65 % By weight based on the compound) compounded at a roller temperature of 170 ° C. The compounding time was 35 min.
Beispiel 5Example 5
340 g teilkristallines Propylenpolymer Novolen® 3200 H (BASF/BASELL, 34 Gew. % bezogen auf das Compound; 97,1 Gew. % bezogen auf das gesamte Polymer) und 10 g340 g of partially crystalline propylene polymer Novolen® 3200 H (BASF / BASELL, 34% by weight based on the compound; 97.1% by weight based on the entire polymer) and 10 g
Levapren® 700 (EVA, 70 Gew. % VA-Copolymer, Bayer, i% bezogen auf das Compound; 2,9 Gew. % bezogen auf das gesamte Polymer), wurden auf einem Walzwerk der Fa. Collin, Typ W150M mit 650 g Magnesiumhydroxid-Füllstoff MAGNIFIN® H 5 MV (65 Gew. % bezogen auf das Compound) bei einer Walzentemperatur von 170 °C compoundiert. Die Compoundierzeit betrug 35 min.Levapren® 700 (EVA, 70% by weight VA copolymer, Bayer, i% based on the compound; 2.9% by weight based on the entire polymer) were on a rolling mill from Collin, Type W150M compounded with 650 g magnesium hydroxide filler MAGNIFIN® H 5 MV (65% by weight based on the compound) at a roller temperature of 170 ° C. The compounding time was 35 minutes.
Beispiel 6Example 6
310 g teilkristallines Propylenpolymer Novolen® 3200 H (BASF/BASELL, 31 Gew. % bezogen auf das Compound, 88.6 Gew. % bezogen auf das gesamte Polymer) und 40 g Levapren® 700 (EVA, 70 Gew. % VA-Copolymer, Bayer, 4% bezogen auf das Compound; 11,4 Gew. % bezogen auf das gesamte Polymer), wurden auf einem Walzwerk der Fa. Collin, Typ Wl 50M mit 650 g Magnesiumhydroxid-Füllstoff MAGNIFIN® H 5 MV (65 Gew. % bezogen auf das Compound) bei einer Walzentemperatur von 170 °C compoundiert. Die310 g of partially crystalline propylene polymer Novolen® 3200 H (BASF / BASELL, 31% by weight based on the compound, 88.6% by weight based on the entire polymer) and 40 g Levapren® 700 (EVA, 70% by weight VA copolymer, Bayer , 4% based on the compound; 11.4% by weight based on the entire polymer), were obtained on a Rollin mill from Collin, type Wl 50M with 650 g magnesium hydroxide filler MAGNIFIN® H 5 MV (65% by weight compounded) at a roller temperature of 170 ° C. The
Compoundierzeit betrug 35 min.Compounding time was 35 min.
Beispiel 7 290 g teilkristallines Propylenpolymer Novolen® 3200 H (BASF/BASELL, 29 Gew. % bezogen auf das Compound; 82,9 Gew. % bezogen auf das gesamte Polymer) und 60 g Levapren® 700 (Ethylen/Vinylacetat-Copolymer (EVA), 70 Gew. % VA-Copolymer, Bayer, 6% bezogen auf das Compound; 17,1 Gew. % bezogen auf das gesamte Polymer), wurden auf einem Walzwerk der Fa. Collin, Typ W150M mit 650 g Magnesiumhydroxid-Füllstoff MAGNIFIN® H 5 MV (65 Gew. % bezogen auf das Compound) bei einer Walzentemperatur von 170 °C compoundiert. Die Compoundierzeit betrug 35 min.Example 7 290 g of partially crystalline propylene polymer Novolen® 3200 H (BASF / BASELL, 29% by weight based on the compound; 82.9% by weight based on the entire polymer) and 60 g Levapren® 700 (ethylene / vinyl acetate copolymer (EVA ), 70 wt.% VA copolymer, Bayer, 6% based on the compound; 17.1 wt.% Based on the entire polymer), were on a rolling mill from Collin, type W150M with 650 g magnesium hydroxide filler MAGNIFIN ® H 5 MV (65% by weight based on the compound) compounded at a roller temperature of 170 ° C. The compounding time was 35 min.
Erläuterungen zu den Tabellen 1 und 2, sowie den Bestimmungsmethoden:Explanations to Tables 1 and 2 and the determination methods:
- Schmelzindex (MFI, Melt Flow Index) nach DIN 53 735 - n.b. nicht bestimmt- Melt index (MFI, Melt Flow Index) according to DIN 53 735 - n.b. not determined
Zugfestigkeit/Reissdehnung an gespritztenTensile strength / elongation at break on sprayed
Probekörpern für Propylenpolymercompounds nach DIN 53 455Test specimens for propylene polymer compounds according to DIN 53 455
- E-Modul nach DIN 53 457 Schlagzähigkeit (nach Charpy) nach DIN 53 453 - o.Br. ohne Bruch Brandschutzverhalten nachUL94 V n.e. Einstufung UL nicht erreicht- modulus of elasticity according to DIN 53 457 impact strength (according to Charpy) according to DIN 53 453 - o.Br. without break Fire protection behavior according to UL94 V ne UL rating not achieved
LOI (Limiting Oxygen Index) nach ASTM D 2863 LOI (Limiting Oxygen Index) according to ASTM D 2863
Tabelle 1Table 1
Tabelle 2Table 2

Claims

Ansprüche: Expectations:
1. Flammhemmendes Polymercompound, mindestens enthaltend a) ein Propylenpolymer in einer Menge von 70 bis 99 Gew. % bezogen auf den gesamten Polymeranteil, b) ein Ethylen Vinylacetat-Copolymer in einer Menge von 1 bis 30 Gew. % bezogen auf den gesamten Polymeranteil, mit einem Vinylacetat-Anteil von 6 bis 80 Gew. %, c) einen halogenfreien flaminhemmenden Füllstoff auf der Basis von natürlichem oder synthetischem Magnesiumhydroxid in einer Menge von 25 bis 80 Gew. % bezogen auf die Gesamtmenge des Compounds.1. Flame retardant polymer compound, at least containing a) a propylene polymer in an amount of 70 to 99% by weight, based on the total polymer content, b) an ethylene-vinyl acetate copolymer in an amount of 1 to 30% by weight, based on the total polymer content, with a vinyl acetate content of 6 to 80% by weight, c) a halogen-free flame retardant filler based on natural or synthetic magnesium hydroxide in an amount of 25 to 80% by weight based on the total amount of the compound.
2. Flammhemmendes Polymercompound nach Anspruch 1, dadurch gekennzeichnet, dass es Propylenpolymer in einer Menge von 80 bis 95 Gew. % bezogen auf den Polymeranteil enthält.2. Flame retardant polymer compound according to claim 1, characterized in that it contains propylene polymer in an amount of 80 to 95 wt.% Based on the polymer content.
3. Flammhemmendes Polymercompound nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass das Propylenpolymer a) ein Propylenpolymer/α-Olefin-Copolymer in Form eines Block-Copolymeren und/oder eines Random-Copolymeren und/oder b) ein Polymerblend aus einem Propylenpolymer mit mindestens einem weiteren Elastomeren und/oder mindestens einem -Olefin-Polymeren ist.3. Flame retardant polymer compound according to one of claims 1 to 2, characterized in that the propylene polymer a) a propylene polymer / α-olefin copolymer in the form of a block copolymer and / or a random copolymer and / or b) a polymer blend of one Propylene polymer with at least one further elastomer and / or at least one olefin polymer.
4. Flammhemmendes Polymercompound nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Ethylen/Vinylacetat-Copolymer einen Vinylacetat-Anteil von 12 bis 80 Gew. % enthält.4. Flame retardant polymer compound according to one of claims 1 to 3, characterized in that the ethylene / vinyl acetate copolymer contains a vinyl acetate content of 12 to 80 wt.%.
5. Flammhemmendes Polymercompound nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es ein Ethylen/Vinylacetat-Copolymer in einer Menge von 5 bis 20 Gew. % bezogen auf den Polymeranteil enthält. 5. Flame retardant polymer compound according to one of claims 1 to 4, characterized in that it contains an ethylene / vinyl acetate copolymer in an amount of 5 to 20 wt.% Based on the polymer content.
6. Flammhemmendes Polymercompound nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der flammhemmende Füllstoff in einer Menge von 25 bis 80 Gew. % bezogen auf das Compound enthalten ist.6. Flame retardant polymer compound according to one of claims 1 to 5, characterized in that the flame retardant filler is contained in an amount of 25 to 80 wt.% Based on the compound.
7. Flammhemmendes Polymercompound nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der flammhemmende Füllstoff in einer Menge von 50 bis 70 Gew. % bezogen auf das Compound enthalten ist.7. Flame retardant polymer compound according to one of claims 1 to 5, characterized in that the flame retardant filler is contained in an amount of 50 to 70 wt.% Based on the compound.
8. Flammhemmendes Polymercompound nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass der verwendete Füllstoff mit a) einem oder mehreren der Fettsäurederivate aus der Gruppe der Polymerfettsäuren, der Ketofettsäuren oder der Fettalkyloxazoline oder -bisoxazoline und gegebenenfalls einem Siloxanderivat und/oder b) einer Fettsäure und einem Siloxanderivat oberflächenbehandelt ist. 8. Flame retardant polymer compound according to any one of claims 1 to 7, characterized in that the filler used with a) one or more of the fatty acid derivatives from the group of polymer fatty acids, keto fatty acids or fatty alkyloxazolines or bisoxazolines and optionally a siloxane derivative and / or b) a fatty acid and a siloxane derivative is surface-treated.
EP02735109A 2001-03-02 2002-03-01 Flame-resistant polypropylene compounds Withdrawn EP1368424A1 (en)

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EP01105086 2001-03-02
EP01105086 2001-03-02
PCT/EP2002/002226 WO2002079320A1 (en) 2001-03-02 2002-03-01 Flame-resistant polypropylene compounds
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