DE202008014218U1 - Thermoplastic elastomers - Google Patents

Thermoplastic elastomers Download PDF

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DE202008014218U1
DE202008014218U1 DE200820014218 DE202008014218U DE202008014218U1 DE 202008014218 U1 DE202008014218 U1 DE 202008014218U1 DE 200820014218 DE200820014218 DE 200820014218 DE 202008014218 U DE202008014218 U DE 202008014218U DE 202008014218 U1 DE202008014218 U1 DE 202008014218U1
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thermoplastic elastomers
elastomers according
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polystyrene
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Rehau Automotive SE and Co KG
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    • 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
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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    • C08J3/00—Processes of treating or compounding macromolecular substances
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    • 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
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    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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
    • C08L53/02—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 of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—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 of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers

Abstract

Thermoplastische Elastomere mit verbesserten elastischen Eigenschaften, die für die Extrusionsverarbeitung geeignet sind, erhältlich durch dynamische Vulkanisation einer Zusammensetzung mindestens folgender Komponenten:
– EPDM
– Styrolblockcopolymer (SEES)
– Polypropylen-Copolymer
– Olefinblockcopolymer OBC
– Füllstoff
– Paraffinisches Extenderöl
– Alkylphenolharz
– Zinnchlorid.Thermoplastic elastomers having improved elastic properties suitable for extrusion processing obtainable by dynamic vulcanization of a composition of at least the following components:
- EPDM
Styrene block copolymer (SEES)
- Polypropylene copolymer
- Olefin block copolymer OBC
- filler
- Paraffinic extender oil
- Alkylphenol resin
- tin chloride.

Figure 00000001
Figure 00000001

Description

Die Erfindung betrifft thermoplastische Elastomere mit verbessertem Rückstellverhalten.The This invention relates to thermoplastic elastomers having improved Recovery behavior.

Thermoplastische Elastomere (TPE) sind dem Fachmann seit Jahren bekannt. In den letzten Jahren gewinnen sie immer mehr an Bedeutung, nicht zuletzt in der Automobilindustrie, aber auch im Bauwesen.thermoplastic Elastomers (TPE) have been known to the skilled person for years. In the last Years they gain more and more importance, not least in the Automotive industry, but also in construction.

Dieses mengenmäßige Wachstum ist zurückzuführen auf die interessante Kombination einer Thermoplast-Verarbeitung mit dem Erzielen von elastischen Materialeigenschaften des Kautschuks.This quantitative growth is due on the interesting combination of a thermoplastic processing with the achievement of elastic material properties of the rubber.

Man unterscheidet, je nach chemischen Aufbau, einerseits zwischen Blockcopolymeren aus einem Makromolekül basierend auf Styrolpolymeren (TPE-S), Polyetheramiden (TPE-A), Polyetherester (TPE-E), thermoplastische Polyurethane (TPE-U)) und – andererseits – Elastomerblends, die nebeneinander aus einer thermoplastischen, unvernetzten und einer teil- und/oder vollvernetzten Phase bestehen.you differs, depending on the chemical structure, on the one hand between block copolymers from a macromolecule based on styrene polymers (TPE-S), Polyetheramides (TPE-A), Polyetherester (TPE-E), thermoplastic Polyurethanes (TPE-U)) and - on the other hand - elastomer blends, The side by side of a thermoplastic, uncrosslinked and a partially and / or fully networked phase.

Die Vernetzung der Elastomerblends erfolgt mittels einer sogenannten dynamischen Vulkanisation, also während der Aufbereitung.The Crosslinking of the elastomer blends takes place by means of a so-called dynamic vulcanization, ie during the treatment.

Die Gruppe der thermoplastischen Elastomere auf Basis von Polyolefinblends (TPE-V) ist am weitesten verbreitet. Für die Weichphase werden in der Regel hochmolekulare EPDM Co- und Terpolymere eingesetzt. Die Vernetzung während der Aufbereitung erfolgt durch Phenolharze [ US 41041210 ], durch Schwefel oder Peroxide [ US 4267080 , US 3806558 , US 4732940 , US 4785045 ]. Auch bekannt ist die Vernetzung durch Platin-katalysierte Hydrosilylierungsreaktionen [ EP 0855426 A1 , US 5597867 , US 5672660 ] oder durch Silankondensationsreaktionen [ DE-OS 1413063 A1 , DE 4402943 ].The group of thermoplastic elastomers based on polyolefin blends (TPE-V) is the most widely used. For the soft phase usually high molecular weight EPDM copolymers and terpolymers are used. The crosslinking during the treatment takes place by means of phenolic resins [ US 41041210 ], by sulfur or peroxides [ US 4267080 . US 3806558 . US 4732940 . US 4785045 ]. Also known is crosslinking by platinum-catalyzed hydrosilylation reactions [ EP 0855426 A1 . US 5597867 . US 5672660 ] or by silane condensation reactions [ DE-OS 1413063 A1 . DE 4402943 ].

Durch die Vernetzung der Weichphase, ob physikalisch reversibel oder chemisch irreversibel, erhalten die thermoplastischen Elastomere gummiartige Eigenschaften, wie z. B. ein hohe Flexibilität auch im Bereich tiefer Temperaturen und eine hohe Elastizität (Rückstellvermögen).By the crosslinking of the soft phase, whether physically reversible or chemical irreversibly, the thermoplastic elastomers get rubbery Properties, such. B. a high flexibility in the Low temperature range and high elasticity (resilience).

Einsatz finden thermoplastische Elastomere in erster Linie bei den verschiedensten Dichtungsanwendungen. Hier wird, je nach Belastungssituation, zwischen statischen, semidynamischen oder dynamischen Dichtungen unterschieden.commitment find thermoplastic elastomers primarily in the most diverse Sealing applications. Here, depending on the load situation, between static, semi-dynamic or dynamic seals.

Für Dichtungsanwendungen ist ein sehr gutes Rückstellvermögen des Materials notwendig, welches durch eine höchstmögliche Elastizität gewährleistet wird. Üblicherweise erfolgt dies durch vollvernetzte Vulkanisate verschiedener Kautschuke (z. B. EPDM, SBR, NBR). Nachteilig ist jedoch, dass das Material nach der Vulkanisation nicht mehr thermoplastisch ist.For Sealing applications is a very good recovery of the material necessary, which by a highest possible Elasticity is ensured. Usually this is done by fully cured vulcanizates of various rubbers (eg EPDM, SBR, NBR). The disadvantage, however, is that the material after vulcanization is no longer thermoplastic.

Aufgrund des Einsatzes eines unvernetzten thermoplastischen Anteils werden die elastischen Eigenschaften eines TPE-V's im Vergleich zum vollvernetzten Kautschuk eingeschränkt.by virtue of the use of an uncrosslinked thermoplastic moiety the elastic properties of a TPE-V compared to fully crosslinked Restricted rubber.

Es stellte sich daher die Aufgabe, thermoplastische Elastomere bereitzustellen, die ein sehr gutes Rückstellvermögen aufweisen.It It was therefore the object to provide thermoplastic elastomers, which have a very good resilience.

Überraschenderweise konnte die Aufgabe dadurch gelöst werden, dass neben dem EPDM-Kautschuk zusätzlich ein Polymer auf Basis Styrol-Blockcopolymer, insbesondere ein Polystyrol-b-poly(ethylen/buten)-b-polystyrol bzw. Polystyrol-b-poly(ethylen/ethylen/propylen)-b-polystyrol, als thermoplastischer Kautschuk und/oder neben dem PP der Thermoplastphase zusätzlich ein Olefin-Blockcopolymer (OBC) eingesetzt wird.Surprisingly the task could be solved by the fact that beside the EPDM rubber additionally a polymer based on styrene block copolymer, in particular a polystyrene-b-poly (ethylene / butene) -b-polystyrene or Polystyrene-b-poly (ethylene / ethylene / propylene) -b-polystyrene, as a thermoplastic Rubber and / or in addition to the PP of the thermoplastic phase in addition an olefin block copolymer (OBC) is used.

Die erfindungsgemäße Zusammensetzung ist vorzugsweise für die Extrusionsverarbeitung geeignet und umfasst folgende Komponenten:

  • – 20 bis 60 Gew.-% EPDM Mooney M + L bei 125°C = 42, 100% ölverstreckt, wobei das EDPM ein Terpolymer aus Ethylen-Propylen-Kautschuk mit 1,4-Hexadien und/oder Dicyclopentadien und/oder Ethylidennorbornen ist,
  • – 2 bis 30 Gew.-% Styrolblockcopolymer (SEES) ausgewählt aus Polystyrol-b-poly(ethylen/buten)-b-polystyrol und/oder Polystyrol-b-poly(ethylen/ethylen/propylen)-b-polystyrol (30 m% Styrol),
  • – 10 bis 50 Gew.-% Polypropylen-Copolymer wobei das Polypropylen-Copolmer isotaktisch oder ataktisch ist, oder ein Random-Copolymer, MFI (2,16 kg/230°C) = 1 g/10 min,
  • – 5 bis 50 Gew.-% Olefinblockcoplymer OBC MFI (2,16 kg/190°C) ≤ 5 g/10 min,
  • – 5 bis 30 Gew.-% anorganischer Füllstoff wie z. B. Kreide und/oder Talkum und/oder Kaolin,
  • – 10 bis 60 Gew.-% paraffinisches Extenderöl υ (20°C) = 450 mPas,
  • – 0,5 bis 5 Gew.-% Alkylphenolharz Erweichungspunkt (R&B) = 60°C,
  • – 0,1 bis 1 Gew.-% Zinnchlorid (SnCl2) Gehalt SnCl2 > 98%,
  • – 0,5 bis 10 Gew.-% Stabilisatoren (z. B. Verarbeitungsstabilisatoren, UV-Stabilisatoren, usw.).
The composition according to the invention is preferably suitable for extrusion processing and comprises the following components:
  • 20 to 60% by weight EPDM Mooney M + L at 125 ° C = 42, 100% oil drawn, wherein the EDPM is a terpolymer of ethylene-propylene rubber with 1,4-hexadiene and / or dicyclopentadiene and / or ethylidenenorbornene .
  • 2 to 30% by weight of styrene block copolymer (SEBS) selected from polystyrene-b-poly (ethylene / butene) -b-polystyrene and / or polystyrene-b-poly (ethylene / ethylene / propylene) -b-polystyrene (30 m % Styrene),
  • 10 to 50% by weight of polypropylene copolymer wherein the polypropylene copolymer is isotactic or atactic, or a random copolymer, MFI (2.16 kg / 230 ° C) = 1 g / 10 min,
  • 5 to 50% by weight of olefin block copolymer OBC MFI (2.16 kg / 190 ° C.) ≦ 5 g / 10 min,
  • - 5 to 30 wt .-% of inorganic filler such. As chalk and / or talc and / or kaolin,
  • 10 to 60% by weight of paraffinic extender oil υ (20 ° C.) = 450 mPas,
  • 0.5 to 5% by weight of alkylphenol resin softening point (R & B) = 60 ° C.,
  • 0.1 to 1% by weight tin chloride (SnCl 2 ) content SnCl 2 > 98%,
  • 0.5 to 10% by weight of stabilizers (eg processing stabilizers, UV stabilizers, etc.).

In einem gleichläufigen Zweischneckenkneter werden diese Komponenten bei Zylindertemperaturen von (aufsteigend) 180 bis 220°C compoundiert und gleichzeitig dynamisch vulkanisiert.In a co-rotating twin-screw kneader become these components at cylinder temperatures of (ascending) 180 to 220 ° C compounded and vulcanized dynamically at the same time.

Je nach Drehzahleinstellung beträgt die mittlere Verweilzeit im Compounder erfindungsgemäß 1,5 bis 3 min, bevorzugt sind 2 min.ever after speed setting is the mean residence time in the compounder according to the invention 1.5 to 3 minutes, preferably are 2 min.

Der Massedruck liegt erfindungsgemäß bei 20 bis 30 bar, bevorzugt bei 25 bar, die Massetemperatur zwischen 225 und 240°C, bevorzugt bei 225°C.Of the Melt pressure according to the invention is 20 to 30 bar, preferably at 25 bar, the melt temperature between 225 and 240 ° C, preferably at 225 ° C.

Erfindungsgemäß geschieht die Verarbeitung in der Extrusion bei Temperaturen von 180 bis 240°C, die Verarbeitung kann aber auch im Spritzgussverfahren bei 190 bis 240°C erfolgen.According to the invention happens the processing in the extrusion at temperatures of 180 to 240 ° C, the Processing can also be done by injection molding at 190 to 240 ° C respectively.

Ausführungsbeispieleembodiments

Die Erfindung soll nachfolgend an 5 Ausführungsbeispielen (Bsp. 1 bis Bsp. 5) gemäß Tabelle 1 näher erläutert werden. Vergleichsbeispiel Bsp. 1 Bsp. 2 Bsp. 3 Bsp. 4 Bsp. 5 EPDM 100 100 80 80 80 100 PP 39 6 38 5 30 5 SEES 20 20 20 10 OBC 33 33 8 25 Füllstoff 10 10 9 9 9 9 Öl/Vernetzer 35 35 46 46 46 43 Additiv 9 9 12 12 10 10 Tabelle 1 The invention will be explained in more detail below with reference to 5 exemplary embodiments (Ex. 1 to Ex. 5) according to Table 1. Comparative example Example 1 Ex. 2 Example 3 Example 4 Example 5 EPDM 100 100 80 80 80 100 PP 39 6 38 5 30 5 SEES 20 20 20 10 OBC 33 33 8th 25 filler 10 10 9 9 9 9 Oil / crosslinker 35 35 46 46 46 43 additive 9 9 12 12 10 10 Table 1

Als Vergleichsbeispiel wird eine Zusammensetzung gemäß Tab. 1 gewählt (Angaben in Teilen).When Comparative example is a composition according to Tab. 1 selected (in parts).

Der Anteil des Vernetzers im Öl-Vernetzer-Gemisch beträgt 10 bis 15%.Of the Proportion of the crosslinker in the oil-crosslinker mixture is 10 to 15%.

In einem gleichläufigen Zweischneckencompounder ZE 25-48d werden folgende Komponenten in den angegebenen Anteilen gemischt und dabei die dynamische Vulkanisation durchgeführt:

  • – EPDM EPDM-Terpolymer mit 1,4-Hexadien als Terkomponente, Mooney M + L bei 125°C = 42, 100% ölverstreckt
  • – PP Polypropylen-Copolymer, MFI (2,16 kg/230°C) = 1 g/10 min
  • – SEBS Styrolblockcopolymer, (Polystyrol-b-poly(ethylen/buten)-b-polystyrol), 30 m% Styrol
  • – OBC Olefinblockcopolymere, MFI (2,16 kg/190°C) ≤ 5 g/10 min
  • – Füllstoff Talkum, Dichte = 2,75 g/cm3
  • – Öl Paraffinisches Extenderöl, υ (20°C) = 450 mPas
  • – Vernetzer Alkylphenolharz, Erweichungspunkt (R&B) = 60°C
  • – SnCl2 Gehalt SnCl2 > 98%
  • – Additive Stabilisatoren (z. B. Verarbeitungsstabilisatoren, UV-Stabilisatoren, usw.).
In a co-rotating twin-screw compounder ZE 25-48d, the following components are mixed in the stated proportions and the dynamic vulcanization is carried out:
  • EPDM EPDM terpolymer with 1,4-hexadiene as the ter component, Mooney M + L at 125 ° C = 42, 100% oil drawn
  • - PP polypropylene copolymer, MFI (2.16 kg / 230 ° C) = 1 g / 10 min
  • - SEBS styrene block copolymer, (polystyrene-b-poly (ethylene / butene) -b-polystyrene), 30% styrene
  • OBC olefin block copolymers, MFI (2.16 kg / 190 ° C) ≤ 5 g / 10 min
  • - filler talc, density = 2.75 g / cm 3
  • - Oil Paraffinic extender oil, υ (20 ° C) = 450 mPas
  • - Crosslinker alkylphenol resin, softening point (R & B) = 60 ° C
  • SnCl 2 content SnCl 2 > 98%
  • - Additive stabilizers (eg processing stabilizers, UV stabilizers, etc.).

Erfindungsgemäß ist es wesentlich, Olefinblockcopolymere (OBC) für die Herstellung der thermoplastischen Elastomere einzusetzen.According to the invention It is essential to use olefin block copolymers (OBC) for the preparation to use the thermoplastic elastomers.

OBC sind Olefin-Blockcopolymere auf Basis Ethylen-Octen.OBC are olefin block copolymers based on ethylene-octene.

Diese liegen als Compound aus Polyethylen (PE) mit Ethylen-Octen-Blöcken vor.These lie as a compound of polyethylene (PE) with ethylene-octene blocks in front.

Die Ethylen- und Octen-Blöcke umfassen jeweils mehrere Monomereinheiten.The Ethylene and octene blocks each comprise multiple monomer units.

OBC sind nicht zu verwechseln mit sogenanntem „Engage”, das ein Random-Ethylen-Octen-Copolymer darstellt.OBC are not to be confused with so-called "Engage", which is a random ethylene-octene copolymer.

Die eingesetzten OBC's sind wie folgt charakterisiert: Schmelzpunkt 105–135°C Schmelzenthalpie 32–45 J/g Kristallinität DSC Smp. bei 124,4°C und Kristallisation bei 96,6°C Dichte 0,84–0,90 g/cm3 Shore-Härte A 60–A 90 MFI 0,5–15 g/10 min bei 2,16 kg und 190°C. The OBC's used are characterized as follows: melting point 105-135 ° C melting enthalpy 32-45 y / g crystallinity DSC mp at 124.4 ° C and crystallization at 96.6 ° C. density 0.84-0.90 g / cm 3 Shore hardness A 60-A 90 MFI 0.5-15 g / 10 min at 2.16 kg and 190 ° C.

OBC's zeichnen sich aus durch hohe Flexibilität, gute Wärmeformbeständigkeit und niedrigen Druckverformungsrest.OBC's are characterized by high flexibility, good heat resistance and low compression set.

Die Rohstoffe werden über gravimetrische Dosierorgane an zwei verschiedenen Dosieröffnungen kontinuierlich zugegeben und dabei die Polymerschmelze über eine Vakuumpumpe entgast. Die bevorzugte Zylindertemperatur liegt (aufsteigend) zwischen 180 und 220°C.The Raw materials are fed via gravimetric dosing to two continuously added to different dosing openings while degassing the polymer melt via a vacuum pump. The preferred cylinder temperature is (rising) between 180 and 220 ° C.

Die Parameter wurden so gewählt, dass sich eine mittlere Verweilzeit von zwei Minuten ergibt. Bevorzugt ist eine Schneckendrehzahl von 250 min–1. Dabei stellt sich ein Massedruck von 25 bar, bei einer Massetemperatur von 225°C, ein.The parameters were chosen to give a mean residence time of two minutes. Preferred is a screw speed of 250 min -1 . This results in a melt pressure of 25 bar, at a melt temperature of 225 ° C, a.

Die resultierenden thermoplastischen Elastomere weisen die in der Tabelle 2 aufgeführten Eigenschaften auf. Vergleichsbeispiel Bsp. 1 Bsp. 2 Bsp. 3 Bsp. 4 Bsp. 5 Shore A (15 sec) ISO 868 72 41 64 32 51 24 DVR (70°C/24 h) in % ISO 815, PK B 43 35 40 31 40 35 Reißfestigkeit in N/mm2 DIN 53504 8 4 9 5 7 4 Reißdehnung in % DIN 53504 480 390 490 560 520 450 Weiterreißf. in N/mm DIN 53507 14 6 11 6 8 3 Tabelle 2 The resulting thermoplastic elastomers have the properties listed in Table 2. Comparative example Example 1 Ex. 2 Example 3 Example 4 Example 5 Shore A (15 sec) ISO 868 72 41 64 32 51 24 DVR (70 ° C / 24 h) in% ISO 815, PK B 43 35 40 31 40 35 Tear strength in N / mm 2 DIN 53504 8th 4 9 5 7 4 Elongation at break in% DIN 53504 480 390 490 560 520 450 Weiterreißf. in N / mm DIN 53507 14 6 11 6 8th 3 Table 2

Die Verarbeitung der thermoplastischen Elastomere im Spritzgussverfahren zur Herstellung der zu den Prüfungen notwendigen Probekörper erfolgte bei 230°C.The Processing of thermoplastic elastomers by injection molding for the preparation of the test specimens necessary for the tests took place at 230 ° C.

Charakterisierung des Rückstellverhaltens („Schnappigkeit”)Characterization of the return behavior ( "Snappiness")

Um das elastische Rückstellverhalten genauer charakterisieren zu können, wurden Hystereseversuche (10% bzw. 50% Dehnung, Haltezeit 5 s, 10 mm/min, 10 Zyklen) an Zugprüfkörpern aus „Vergleichsbeispiel” (2) und „Bsp. 1” (1) durchgeführt.In order to be able to characterize the elastic recovery behavior more accurately, hysteresis tests (10% or 50% elongation, holding time 5 s, 10 mm / min, 10 cycles) on tensile test specimens from "Comparative Example" (US Pat. 2 ) and "Ex. 1" ( 1 ) carried out.

Die Ergebnisse sind in den 1 und 2 wiedergegeben.The results are in the 1 and 2 played.

Die Dehnung ist in % angegeben, die Spannung in N/mm2.The elongation is given in%, the stress in N / mm 2 .

In 1 beträgt die Dehnung 10%, entsprechend in 2 50%.In 1 the elongation is 10%, corresponding to 2 50%.

Die Relaxationen während der Haltezeit im Hystereseversuch beträgt im „Vergleichsbeispiel” (2) 0,08–0,11 N/mm2 und im „Bsp. 1” (1) 0,01–0,02 N/mm2 (s. 1).The relaxation during the hold time in the hysteresis test is in the "Comparative Example" ( 2 ) 0.08-0.11 N / mm 2 and in the "Ex. 1" ( 1 ) 0.01-0.02 N / mm 2 (s. 1 ).

Die geringere Relaxation bzw. die Abnahme des Spannungsabfalls zeigt ein elastischeres Verhalten des Beispiels 1 (1). Ebenfalls bestätigen die kleineren bleibenden Dehnungen die höhere Reversibilität/Elastizität des Beispiels 1 (1).The lower relaxation or the decrease in the voltage drop shows a more elastic behavior of Example 1 (1). Also, the smaller residual strains confirm the higher reversibility / elasticity of Example 1 ( 1 ).

So zeigt die Prüfung bei 50% Dehnung (s. 2) für das Vergleichsbeispiel (2) eine bleibende Dehnung (= Dehnung bei Spannung 0 N/mm2) während der Entlastung > 20% im Vergleich zum Bsp. 1 (1) von ca. 10%. Auch bei der Belastung lässt sich ab dem 2. Zyklus eine deutlich geringere bleibende Dehnung des Bsp. 1 (1) gegenüber dem Vergleichsbeispiel (2) nachweisen.Thus, the test at 50% elongation (s. 2 ) for the comparative example ( 2 ) a permanent elongation (= strain at stress 0 N / mm 2 ) during the discharge> 20% compared to Ex. 1 ( 1 ) of about 10%. Even with the load, a significantly lower permanent elongation of Ex. 1 (from the 2nd cycle) can be 1 ) compared to the comparative example ( 2 ).

Es gelingt damit, erfindungsgemäß thermoplastische Elastomere bereitzustellen, die – neben der hervorragenden thermoplastischen Verarbeitbarkeit insbesondere im Extrusionsverfahren – eine außergewöhnlich hohe Elastizität bei gleichzeitig hoher Reversibilität aufweisen und für Dichtungen, die dauerhaft dynamischen Belastungen ausgesetzt sind, sich als hervorragend geeignet erweisen.It thus succeeds according to the invention thermoplastic Elastomers provide, in addition to the excellent thermoplastic processability, especially in the extrusion process - a exceptionally high elasticity have high reversibility at the same time and for Seals that are permanently exposed to dynamic loads, prove to be excellent.

ZITATE ENTHALTEN IN DER BESCHREIBUNGQUOTES INCLUDE IN THE DESCRIPTION

Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Zitierte PatentliteraturCited patent literature

  • - US 41041210 [0006] - US 41041210 [0006]
  • - US 4267080 [0006] - US 4267080 [0006]
  • - US 3806558 [0006] US 3806558 [0006]
  • - US 4732940 [0006] US 4732940 [0006]
  • - US 4785045 [0006] US 4785045 [0006]
  • - EP 0855426 A1 [0006] EP 0855426 A1 [0006]
  • - US 5597867 [0006] US 5597867 [0006]
  • - US 5672660 [0006] US 5672660 [0006]
  • - DE 1413063 A1 [0006] - DE 1413063 A1 [0006]
  • - DE 4402943 [0006] - DE 4402943 [0006]

Zitierte Nicht-PatentliteraturCited non-patent literature

  • - ISO 868 [0031] - ISO 868 [0031]
  • - ISO 815, PK B [0031] - ISO 815, PK B [0031]
  • - DIN 53504 [0031] - DIN 53504 [0031]
  • - DIN 53504 [0031] - DIN 53504 [0031]
  • - DIN 53507 [0031] - DIN 53507 [0031]

Claims (9)

Thermoplastische Elastomere mit verbesserten elastischen Eigenschaften, die für die Extrusionsverarbeitung geeignet sind, erhältlich durch dynamische Vulkanisation einer Zusammensetzung mindestens folgender Komponenten: – EPDM – Styrolblockcopolymer (SEES) – Polypropylen-Copolymer – Olefinblockcopolymer OBC – Füllstoff – Paraffinisches Extenderöl – Alkylphenolharz – Zinnchlorid.Thermoplastic elastomers with improved elastic properties necessary for extrusion processing suitable, obtainable by dynamic vulcanization a composition of at least the following components: - EPDM - styrene block copolymer (SEBS) - Polypropylene copolymer - Olefin block copolymer OBC - filler - Paraffinic extender - Alkylphenol resin - tin chloride. Thermoplastische Elastomere nach Anspruch 1, dadurch gekennzeichnet, dass die Komponenten zu folgenden Anteilen in der Zusammensetzung enthalten sind: – 20 bis 60 Gew.-% EPDM, Mooney M + L bei 125°C = 42, 100% ölverstreckt, wobei das EPDM ein Ethylen-Propylen Terpolymer ist und die Terkomponente aus 1,4-Hexadien und/oder Dicyclopentadien und/oder Ethylidennorbornen besteht, – 2 bis 30 Gew.-% Styrolblockcopolymer (SEES), ausgewählt aus (Polystyrol-b-poly(ethylen/buten)-b-polystyrol) und/oder Polystyrol-b-poly(ethylen/ethylen/propylen)-b-polystyrol (30 m% Styrol), – 10 bis 50 Gew.-% Isotaktisches Polypropylen-Copolymer, MFI (2,16 kg/230°C) 1 g/10 min, – 5 bis 50 Gew.-% Olefinblockcoplymer OBC, MFI (2,16 kg / 190°C) ≤ 5 g/10 min, – 5 bis 30 Gew.-% anorganischer Füllstoff, ausgewählt aus Talkum und/oder Kreide und/oder Kaolin, – 10 bis 60 Gew.-% Paraffinisches Extenderöl, υ (20°C) = 450 mPas, – 0,5 bis 5 Gew.-% Alkylphenolharz, Erweichungspunkt (R&B) = 60°C, – 0,1 bis 1 Gew.-% Zinnchlorid (SnCl2), Gehalt SnCl2 > 98%, – 0,5 bis 10 Gew.-% Stabilisatoren (z. B. Verarbeitungsstabilisatoren, UV-Stabilisatoren, usw.).Thermoplastic elastomers according to claim 1, characterized in that the components are present in the composition in the following proportions: 20 to 60 wt.% EPDM, Mooney M + L at 125 ° C = 42, 100% oil drawn, the EPDM being a Ethylene-propylene terpolymer and the terpolymer consists of 1,4-hexadiene and / or dicyclopentadiene and / or ethylidenenorbornene, - 2 to 30% by weight of styrene block copolymer (SEES) selected from (polystyrene-b-poly (ethylene / butene) -b-polystyrene) and / or polystyrene-b-poly (ethylene / ethylene / propylene) -b-polystyrene (30 m% styrene), - 10 to 50 wt% isotactic polypropylene copolymer, MFI (2.16 kg / 230 ° C) 1 g / 10 min, - 5 to 50 wt% olefin block copolymer OBC, MFI (2.16 kg / 190 ° C) ≤ 5 g / 10 min, - 5 to 30 wt% inorganic filler selected from talcum and / or chalk and / or kaolin, - 10 to 60% by weight paraffinic extender oil, υ (20 ° C) = 450 mPas, - 0.5 to 5% by weight alkylphenol resin, softening point (R & B) = 60 ° C, - 0.1 to 1 wt .-% tin chloride (SnCl 2 ), content SnCl 2 > 98%, - 0.5 to 10 wt .-% stabilizers (eg. Processing stabilizers, UV stabilizers, etc.). Thermoplastische Elastomere nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das OBC einen Schmelzpunkt von 105 bis 135°C aufweist.Thermoplastic elastomers according to claim 1 or 2, characterized in that the OBC has a melting point of 105 up to 135 ° C has. Thermoplastische Elastomere nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das OBC eine Dichte von 0,84 bis 0,90 g/cm3 aufweist.Thermoplastic elastomers according to one of the preceding claims, characterized in that the OBC has a density of 0.84 to 0.90 g / cm 3 . Thermoplastische Elastomere nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die dynamische Vulkanisation bei Zylindertemperaturen von (aufsteigend) 180 bis 220°C erfolgt.Thermoplastic elastomers according to one of the preceding Claims, characterized in that the dynamic Curing at cylinder temperatures from (rising) 180 to 220 ° C takes place. Thermoplastische Elastomere nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Massetemperatur an der Düse zwischen 225 und 240°C, bevorzugt 225°C, beträgt.Thermoplastic elastomers according to one of the preceding Claims, characterized in that the melt temperature at the nozzle between 225 and 240 ° C, preferably 225 ° C, is. Thermoplastische Elastomere nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Verweilzeit im Compounder 1,5 bis 3 Minuten, bevorzugt 2 Minuten, beträgt.Thermoplastic elastomers according to one of the preceding Claims, characterized in that the residence time in the compounder 1.5 to 3 minutes, preferably 2 minutes. Thermoplastische Elastomere nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass der Massedruck 20 bis 30 bar, bevorzugt 25 bar, beträgt.Thermoplastic elastomers according to one of the preceding Claims, characterized in that the mass pressure 20 to 30 bar, preferably 25 bar. Thermoplastische Elastomere nach einem der Ansprüche 1 bis 8 zur Verwendung als Gummiersatz, insbesondere für den Automobilbau und den Hochbau.Thermoplastic elastomers according to one of the claims 1 to 8 for use as a rubber substitute, in particular for the automotive industry and building construction.
DE200820014218 2008-10-24 2008-10-24 Thermoplastic elastomers Expired - Lifetime DE202008014218U1 (en)

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US8686087B2 (en) 2009-10-02 2014-04-01 Dow Global Technologies Llc Block composites in soft compounds
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WO2011041698A1 (en) * 2009-10-02 2011-04-07 Dow Global Technologies Inc. Block copolymers in soft compounds
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