WO2019122184A1 - Matière à mouler conductrice à base de polyamide et utilisations de celle-ci - Google Patents

Matière à mouler conductrice à base de polyamide et utilisations de celle-ci Download PDF

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Publication number
WO2019122184A1
WO2019122184A1 PCT/EP2018/086291 EP2018086291W WO2019122184A1 WO 2019122184 A1 WO2019122184 A1 WO 2019122184A1 EP 2018086291 W EP2018086291 W EP 2018086291W WO 2019122184 A1 WO2019122184 A1 WO 2019122184A1
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Prior art keywords
polyamide
range
weight percent
layer
weight
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German (de)
English (en)
Inventor
Georg Stöppelmann
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EMS Patent AG
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EMS Patent AG
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Priority to CH00741/20A priority Critical patent/CH715732B1/de
Publication of WO2019122184A1 publication Critical patent/WO2019122184A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/04—4 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes

Definitions

  • the present invention relates to a thermoplastic polyamide molding composition having preferably particularly good electrical conductivity properties and good resistance to washing out against fuels, in particular suitable as a material for lines for fuels in the automotive sector, and uses of such polyamide molding compositions.
  • Fuel lines for the vehicle sector are known from US-A-2014/2461 11, which comprise at least five layers and comprise barrier layers, adhesion promoter layers and further functional layers.
  • a layer of fluoropolymer is provided on the inside and a layer of EVOH (ethylene-vinyl alcohol copolymer) as the barrier layer.
  • EVOH ethylene-vinyl alcohol copolymer
  • EP-A-1 645 412 describes lines for fuel cells made of thermoplastic materials.
  • As the inner layer a layer of a polyamide molding composition is proposed, and as possible subsequent layers various proposals are made, including EVOH layers. Concrete examples of Layer structures are not given, and to ensure a connection between an optional EVOH layer and the polyamide inner layer, it is expressly pointed out the need for a coupling agent in the form of a separate additional layer.
  • US-A-2009/269532 describes a conduit of at least two layers, both of polyamide, which is a core element, to provide the inner layer with only an organic stabilizer and expressly not with a copper stabilizer.
  • polyamide which is a core element
  • such structures are improved over aging, especially in contact with hot air, compared to the prior art and are more resistant in contact with corrosive liquids.
  • three-layer structures with a central EVOH layer are disclosed, they always have organic stabilization on the inside and copper stabilization on the outside.
  • US-A-2015/353792 describes primer materials for use, for example, in multi-layer fuel lines.
  • Complex copolyamides of the general structure A / B / C for example of the type 6/612/12, are proposed, and it is shown that such adhesion between two different polyamide layers can be ensured.
  • EP-A-0 445 706 proposes layered structures as fuel lines which have at least 3 layers of at least 2 different polyamides.
  • a layer structure with an inner layer of impact-modified polyamide 6, an intermediate layer of EVOH and an outer layer of impact-modified polyamide 6 is worked and shown that such a structure is not sufficiently resistant to cold impact.
  • GB 2390658 discloses, inter alia, a fuel line with a barrier layer of EVOH with an inner layer of polyamide 6 and an outer layer of polyamide 612, or also with inner layer and outer layer of polyamide 612.
  • the inner layer can be conductively equipped or it can be on the inside give another conductive layer. Elongation at break of 150% is achieved.
  • the inner layer is preferably made of polyamide 612 or 610, and directly adjoins the layer of EVOH.
  • Specifically disclosed are in particular structures in which only three layers are present and in which the outer layers consist exclusively of polyamide 610, or polyamide 612 or polyamide 6.
  • Another fuel line according to the prior art can be found in EP-Al 452 307 described.
  • a barrier layer is provided on the basis of EVOH, and to ensure adhesion to the barrier layer and a good resistance to peroxide, it is specifically proposed not to form the inner layer based on a polyamide 6 homopolymer, but on the basis of a mixture of polyamide homopolymers containing a compatibilizer.
  • different polyamide homopolymers are given, but usually without making specific statements about which polyamide homopolymers have a particularly good adhesion to the barrier layer and a resistance to specific chemicals.
  • thermoplastic multilayer composites are likewise described which have a layer of EVOH as the barrier layer. Adjacent to this layer is described in EP-A-1 162 061 a layer of a molding composition based on polyamide, wherein a plurality of possible polyamides is given in a general manner. Specifically, in the examples, however, only an inner layer of polyamide 6 is disclosed. In EP-A-0 036 968 it is specifically aimed that copolyamides have improved adhesion to barrier layers of EVOH. As inner layers always layers of mixtures of polyamide and polyolefin, or polyamide layers are given.
  • US-A-2005/0263202 describes a fuel system component based on polyamide 610 or polyamide 612 with carbon nanotubes or steel fibers and an impact modifier and a low proportion of plasticizer. Examples are not worked on and properties of such components are not specified. It is about providing a molding compound with good zinc chloride resistance, since this parameter is essential for the life of the pipe.
  • WO-A-2006/037615 proposes a composition of an outer layer of a fuel line.
  • the addition of a conductivity additive is generally discussed, and for the inner layers based on polyamide 6 also worked, for the outer layer based on polyamide 612, polyamide 610 or polyamide 1010, however, not.
  • US-A-2011/0027512 uses carbon nanotubes as an additive to carbon black in the context of conductively-equipped fuel pipelines, with carbon black accounting for the majority and only very low levels of nanotubes being used. Since a carbon black concentration of up to> 20% by weight may be necessary, this application addresses the combination with a compelling olefinic thermoplastic, e.g. LLDPE, as a matrix component in addition to polyamide.
  • LLDPE olefin
  • the polyamide used in the matrix is polyamide 11 only and only properties of lines given on this basis.
  • WO-A-2010/128013 also uses carbon nanotubes or carbon fibers in the case of polyamide molding compounds. Here, however, the water absorption of short-chain polyamides is combated, by means of a polypropylene and a coupling agent. Only polyamide 6 and polyamide 66 are used as the polyamide matrix.
  • US-A-2014065338 discloses a monolayer tube comprising a melt blended thermoplastic composition consisting essentially of a polyamide resin selected from the group consisting of PA 614, PA 616, PA 618 and mixtures thereof; and optionally: one or more polymeric toughening agents; one or more plasticizers; and one or more functional additives.
  • Conductivity is neither addressed nor does it convey the attached carbon black conductivity, as it is formulated as a pure dye and is not able to be present in too low an amount of less than 1%.
  • thermoplastic multilayer composite in the form of a hollow body, comprising at least one inner layer based on polyamides, at least one barrier layer and at least one thermoplastic outer layer. It is proposed to form the inner layer based on polyamide 69, polyamide 610, polyamide 61 1, polyamide 612, polyamide 613, polyamide 614, polyamide 618 or mixtures thereof and the barrier layer based on ethylene / vinyl alcohol copolymers (EVOH) or on Basis of fluoropolymers, and the outer layer of a mixture based on different polyamide homopolymers with a compatibilizer.
  • EVOH ethylene / vinyl alcohol copolymers
  • polyamide 610 or Polyamide 612 as the basis for such a layer structure for a fuel line for liquid fuels such as gasoline or diesel described and uses of such a thermoplastic multilayer composite as a fuel line or as a fuel tank.
  • Polyamide 616 is not mentioned.
  • the polyamide molding composition according to the invention has a very good washout resistance to, in particular, at least partially alcohol-containing fuels. This is reflected in the very good mechanical properties even after prolonged contact with the fuel.
  • the molding compound is particularly suitable as an inner layer (with contact to the fuel) of a gasoline line.
  • the present invention accordingly proposes a polyamide molding composition having preferably good electrical conductivity or deep surface resistance and / or surface resistivity, respectively, consisting of the following components:
  • polyamide selected from the group consisting of: polyamide 616, polyamide 516, polyamide 1016, or mixtures thereof;
  • the component (A2) other than (Al) is thus expressly not selected as polyamide 616, polyamide 516, polyamide 1016, or mixtures thereof.
  • components (B) and (C) are different from (Al) and / or (A2). It is found that such a polyamide molding composition is capable of unexpectedly achieving the above object, as shown in the experimental evidence set forth below.
  • volume resistivity volume resistivity according to DIN EN 62631-3-2 (2016) in the range of 1 * 10 2 to 1 * 10 6 ohm * m or at most 5 * 10 3 ohm * m, preferably in the range of 1 * 10 3 to 5 * 10 3 ohm * m.
  • Such a polyamide molding composition may preferably be characterized in that the proportion of polyamide (Al) in the range of 50-75 weight percent, preferably in the range of 60-70 weight percent.
  • the polyamide (Al) is preferably selected as polyamide 616.
  • the polyamide (Al) preferably has a relative solution viscosity, measured in m-cresol according to ISO 307 (2007) at a temperature of 20 ° C in the range of 2.0-2.4, preferably from 2.05 to 2.35.
  • the at least one polyamide (Al) has a melting point in the range of 175-240 ° C or 190-240 ° C, preferably 177-220 ° C.
  • the level of plasticizer (B) is preferably in the range of 5-20% by weight, preferably in the range of 5-15 or 10-15% by weight.
  • the at least one plasticizer (B) is selected as Hydroxybenzoeklareester- (such as 2-hexyldecyl-4-hydroxybenzoate, HDPB) or sulfonamide-based plasticizer, preferably the class of N-substituted Sulfonamide plasticizer, especially preferred as BBSA (N-butylbenzenesulfonamide).
  • suitable hydroxybenzoic acid ester-based plasticizers are systems such as: 2-hexyldecyl-4-hydroxybenzoate, hexyloxyethoxyethyl p-hydroxybenzoate;
  • the proportion of impact modifier (C) is preferably in the range of 5-20 weight percent, in particular in the range of 10-16 weight percent.
  • the at least one impact modifier is preferably selected as an ethylene- ⁇ -olefin copolymer modified with an acid, more preferably as an ethylene / ⁇ -olefin copolymer grafted with an acid anhydride, especially maleic anhydride, especially such modified or grafted ethylene / butylene , Ethylene / propylene, or ethylene-propylene / ethylene-butylene copolymer.
  • the proportion of partially crystalline polyamide (A2) is preferably in the range of 1-25% by weight, preferably in the range of 5-15% by weight.
  • the partially crystalline polyamide (A2) is preferably selected from the group consisting of: polyamide 6, polyamide 66, polyamide 11, polyamide 12.
  • the proportion of partially crystalline polyamide (A2) and / or parts of polyamide (A1) can be used as matrix for a masterbatch for at least one of components (D) and / or (E).
  • the proportion of conductivity additive (D) is preferably in the range from 1 to 15, preferably 2 to 10 percent by weight, in particular in the range from 3 to 8 percent by weight.
  • the conductivity additive (D) is preferably carbon nanotubes, preferably single-walled, double-walled or multi-walled carbon nanotubes.
  • carbon black, graphene or graphene derivatives, or a combination of carbon nanotubes, carbon black and / or graphene or graphene derivatives Preferably, the conductivity additive (D) and / or the entire molding composition is free of carbon fibers.
  • the carbon nanotubes preferably have the following properties, cumulatively or individually considered: a length to outside diameter ratio in the range of 5-5000, preferably in the range of 100-2000, more preferably in the range of 500-1500,
  • the proportion of additives (E) is preferably in the range of 0.01-3% by weight, preferably in the range of 0.5-1% by weight.
  • the additives (E) are furthermore preferably selected from at least one additive of the following group: antioxidant; non-conductive pigments; UV absorber; UV stabilizers; Heat and heat stabilizers; Hydrolysis stabilizers, flame retardants; Adhesion promoters; Compatibility agent; Lubricant; Antiblocking agent, nucleating agent, crystallization accelerator,
  • Crystallization retarders chain-extending additives, or mixtures of these systems.
  • the present invention relates to a plastic conduit having at least one layer of a polyamide molding composition as set forth above, wherein this plastic conduit is preferably characterized in that it is formed as a multi-layer composite in the form of a hollow body enclosing an interior, and the layer of a polyamide molding composition as set forth above the inner layer forms the multilayer composite inwardly.
  • Such a plastic conduit may be formed to consist of at least three layers, the inner layer adjacent to the inner space, in the case of exactly three layers of a middle layer adjacent to the inner layer and an outer layer adjacent to the middle layer.
  • the outer layer is preferably formed on the basis of polyamide 612, polyamide 616, polyamide 1012, polyamide 1016, polyamide 12, polyamide 11, and is the middle layer adjacent to the inventive layer preferably formed on the basis of EVOH or fluoropolymers.
  • Such a plastic conduit may also be formed to consist of four layers, the inner layer adjacent to the interior of the above-described polyamide molding compound, an inner middle layer adjacent to the inner layer, a middle layer adjacent to the inner middle layer, and an outer layer adjacent to the middle layer , wherein also here the outer layer is preferably based on polyamide 612, polyamide 616, polyamide 12, polyamide 11, polyamide 1012, polyamide 1016, each alone or in a mixture of two or more of these polyamides, is formed or substantially consists thereof, and wherein here too the middle layer can be formed on the basis of EVOH or fluoropolymers.
  • Such a plastic line is further preferably characterized in that the inner layer has a copper stabilization, preferably based on Cul, particularly preferably as Cul / KI, for example in a weight ratio of 1: 4 - 1: 8, wherein the copper stabilizer in a proportion in the range 0.01-0.10 weight percent, or in an amount of 0.03-0.07 weight percent, wherein the weight percent is based on 100 weight percent of the material for forming the inner layer.
  • the copper stabilizer therefore, e.g. Cul / KI (weight ratio preferably in the range of 1: 6) are used, for example in a proportion of about 0.05 percent by weight based on the total mass of the inner layer.
  • the outer layer of such a plastic line may contain an impact modifier, preferably in an amount in the range of 10-25% by weight or in a range of 10-20% by weight, wherein the impact modifier is preferably an acid-modified ethylene- ⁇ -olefin polymer.
  • Copolymer is, in particular preferably one with an acid anhydride, especially with maleic anhydride, grafted ethylene / a-olefin copolymer, in particular so modified or grafted ethylene / butylene, ethylene / propylene, or ethylene propylene / ethylene butylene copolymer, wherein the weight percent are based on 100 weight percent of the material for making the outer layer.
  • the outer layer preferably consists of:
  • A_I Polyamide 612, polyamide 616, polyamide 1012, polyamide 1016, polyamide 11 or polyamide 12 (alone or as a mixture), preferably with a relative solution viscosity, measured in sulfuric acid according to ISO 307 (2007) at a temperature of 20 ° C in Range of 2.1 - 2.4, preferably 2.15 - 2.30; (B_I) 5-30% by weight impact modifier;
  • plasticizer preferably based on N-substituted benzenesulfonamides, and / or hydroxybenzoic acid esters
  • additives preferably selected from the group:
  • Crystallization accelerators pigments, dyes, UV absorbers, UV stabilizers, IR absorbers, processing aids, lubricants, stabilizers, heat stabilizers, and mixtures thereof
  • the plastic conduit may be characterized in that the middle layer is based on EVOH or consists of an EVOH, preferably an EVOH with an ethylene content in the range of 20-25% by weight, preferably in the range of 25-30% by weight.
  • the outer layer has a thickness in the range of 0.1 -0.6 mm, preferably in the range of 0.1 -0.2 mm or 0.4-0.5 mm.
  • the middle layer preferably has a thickness in the range of 0.05-0.2 mm, preferably in the range of 0.075-0.125 mm.
  • the inner middle layer has a thickness in the range of 0.1-0.6 mm, preferably in the range of 0.1-0.2 mm or 0.4-0.5 mm, and, if present, the middle layer over a thickness in the range of 0.05-0.2 mm , preferably in the range of 0.075-0.125 mm.
  • the total wall thickness of a multi-layer composite is then typically in the range of 0.5-2.5 mm, preferably in the range of 0.75-1.5 mm.
  • Such a plastic pipe is preferably characterized in that it is produced in an extrusion process, or in the case of a multilayer plastic pipe, in a coextrusion process, also a production of the pipes in a sheathing process in the tandem extrusion process or in the extrusion blow molding one or more layers possible.
  • the plastic line may be formed in the form of a line, which may be at least partially formed as a corrugated pipe, preferably as a conduit for Internal combustion engines, in particular in the automotive sector, in particular for fuel, urea or coolant.
  • the present invention relates to a method for producing a plastic conduit as set forth above, characterized in that the at least one, or in the case of a multilayer plastic conduit, the 2 or 3 or 4 layers, in a continuous and / or discontinuous process, preferably in an extrusion blow molding, a tandem extrusion, a jacketing process or a (co) extrusion process, to a hollow body, in particular preferably to a pipe or a pipe or a container are formed.
  • Fig. 1 is a three-layer fuel line in a sectional view perpendicular to
  • Fig. 2 shows a four-layer fuel line in a sectional view perpendicular to
  • Figure 1 shows an exemplary fuel line 1 using a conductive polyamide molding compound according to the invention in a section transverse to the main course direction.
  • the cross-sectional area can be constant over the main course direction, d. H.
  • the tube may have a substantially hollow cylindrical shape.
  • cross-sectional area can also vary over the main course direction, for example in the form of a corrugated tube.
  • An interior 2 is enclosed by the pipe wall. On the interior 2 follows first radially outwardly an inner layer 3, which borders with the inner surface 7 of the inner space 2 and limits this. This inner layer is formed on the basis of the novel polyamide molding compound.
  • a middle layer 4 in the sense of a barrier layer, this can, for example, on Be formed based on EVOH.
  • outer layer 5 Directly adjacent to the outside of this middle layer 4 and again without intervening adhesion promoter layer follows an outer layer 5.
  • the outer layer 5 may be formed, for example based on polyamide 612 or 616.
  • the outer surface 6 of the outer layer 5 limits the line to the outside.
  • FIG. 2 shows another exemplary fuel line 1 using a conductive polyamide molding compound according to the invention in a section transverse to the main course direction. This is also a construction as used in the examples below.
  • An interior 2 is enclosed by the pipe wall. On the interior 2 follows first radially outwardly an inner layer 3, which borders with the inner surface 7 of the inner space 2 and limits this. This inner layer is formed on the basis of the novel polyamide molding compound.
  • inner middle layer 8 Immediately adjacent to the inner layer 3 without intermediate adhesion promoter layer follows an inner middle layer 8, which can function functionally as a primer layer.
  • the inner middle layer then directly adjoins a further outer middle layer 4 in the sense of a barrier layer, which may be formed, for example, on the basis of EVOH.
  • outer layer 5 Directly adjacent to the outside of this middle layer 4 and again without intervening adhesion promoter layer follows an outer layer 5.
  • the outer layer 5 may be formed, for example based on polyamide 612 or 616.
  • the outer surface 6 of the outer layer 5 limits the line to the outside.
  • the carbon nanotubes are multiwall carbon nanotubes (MWCNTs) with the following specifications: Average Diameter: 9.5 l0 9 m; average length: 1.5 pm; Carbon purity: 90%; Transition metal content: ⁇ 1%, BET surface area: 250 m 2 / g; Volume resistance: 10-4 W. cm.
  • MWCNTs multiwall carbon nanotubes
  • Tafmer MC-201 is an impact modifier in the form of a mixture of ethylene-propylene and ethylene-butylene copolymers grafted with maleic anhydride, namely g-MAH (-0.6%) blend of 67% EP copolymer (20 mol% propylene) + 33% EB Copolymer (15 mol% 1-butene).
  • Tubes were coextruded at mass temperatures between 210 and 260 ° C under vacuum of -56 mbar and an extrusion rate of 32.8 m / min.
  • the test specimens used were tubes with an outside diameter of 8 mm and a wall thickness of 1 mm.
  • the outer layer used was polyamide 612 with a layer thickness of 0.35 mm.
  • the examples vary only with respect to the inner layer.
  • the inner layer consists of the molding compound Bl, B2 or VB1 as indicated in Table 1, each with a layer thickness of 0.15 mm.
  • the length of the pipe has been adjusted according to the test requirements.
  • Zinc chloride test Test on a specimen of length 30 cm, according to SAE J2260 (2004) paragraph 7.12.2, after 200 hours in 50% w / w ZnCl 2 (aq.). A test for zinc chloride resistance is considered to be passed as long as the tube does not show any cracks or crevices after storage.
  • Pipe tensile tests were carried out in accordance with ISO 527-2 (2012). For Experiments were used specimens of length 150 mm (tensile tests in the extrusion direction) or 10 mm (in tensile tests transverse to the extrusion direction). Test temperature is 23 ° C and the test speed 100 mm / min (for experiments in the extrusion direction) or 25 mm / min when transverse to the extrusion direction. Specifically, the following measurements were made according to ISO 527:
  • test temperature is 23 ° C, unless otherwise specified by the standard (that is, in cold weather, appearance, washout).
  • Bursting pressure The bursting pressure of the shaped bodies produced is measured on the basis of DIN 73378 (1996) on hollow bodies with dimensions length 15 cm, inner diameter 6 mm and outer diameter 8, or wall thickness 1 mm.
  • Charpy impact strength and notched impact strength Measured to ISO79 / keU or ISO79 / keA on the ISO test rod, standard ISO / CD 3167, type Bl, 80 x 10 x 4 mm at a temperature of 23 ° C.
  • Relative viscosity DIN EN ISO 307 (2007), in 0.5% strength by weight m-cresol solution or 1% strength by weight sulfuric acid solution (PA6) at a temperature of 20 ° C.
  • test specimens comply with the requirements of IEC 62631-3-2 (2016): 100 c 100 c 2 mm
  • the molding composition unexpectedly has a very good electrical conductivity in combination with an improvement in washout resistance.
  • the above-mentioned ESD layer has improving effects on the mechanical properties, e.g. a higher elongation.
  • the improved electrical conductivity of the lines according to the invention is shown by the surface and volume resistivity of the inventive molding compositions is significantly smaller than that of the non-inventive example.
  • a quantity of constituents that is impermissible according to industrial requirements can be washed out of the comparative example.

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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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

L'invention concerne une matière à mouler conductrice à base de polyamide, en particulier pour une couche intérieure d'une conduite de carburant, ladite matière à mouler étant constituée des composants suivants : (A1) 30 à 93,9 % en poids d'un polyamide choisi dans le groupe comprenant : le polyamide 616, le polyamide 516, le polyamide 1016 ou des mélanges de ceux-ci ; (A2) 0 à 40 % en poids d'un polyamide semi-cristallin différent de (A1) ; (B) 5 à 25 % en poids de plastifiant ; (C) 3 à 30 % en poids de modifiant choc ; (D) 1 à 20 % en poids d'additif de conductivité, (E) 0 à 5 % en poids d'additifs différents de (B) - (D), la somme des composants (A1)-(E) représentant 100 % en poids de la matière à mouler à base de polyamide.
PCT/EP2018/086291 2017-12-22 2018-12-20 Matière à mouler conductrice à base de polyamide et utilisations de celle-ci Ceased WO2019122184A1 (fr)

Priority Applications (1)

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CH00741/20A CH715732B1 (de) 2017-12-22 2018-12-20 Leitfähige Polyamidformmasse und Verwendungen dafür.

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EP17209977 2017-12-22
EP17209977.2 2017-12-22

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WO2019122184A1 true WO2019122184A1 (fr) 2019-06-27

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CN113603999A (zh) * 2021-07-29 2021-11-05 宝新高分子科技(广州)有限公司 防水耐热组合物、防水耐热绝缘结构、防水耐热电线及其应用
US20220018467A1 (en) * 2018-12-12 2022-01-20 Ems-Chemie Ag Multilayer fuel line
WO2024044734A1 (fr) * 2022-08-26 2024-02-29 Martinrea International US Inc. Tube de gestion thermique en plastique multicouche tel que pour application automobile
DE102023130025A1 (de) * 2023-10-30 2025-04-30 Voss Automotive Gmbh Mehrschichtrohrleitung zum Durchleiten dielektrischer Fluide, Immersionskühlungskreislauf sowie Elektrofahrzeug mit zumindest einer immersionsgekühlten Batterie

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EP1036968A1 (fr) 1999-03-16 2000-09-20 Atofina Tube multicouche à base de polyamides pour le transport d'essence
EP1162061A1 (fr) 2000-06-09 2001-12-12 EMS-Chemie AG Stratifiés thermoplastiques
GB2390658A (en) 2002-07-13 2004-01-14 Tfx Group Ltd Multilayer articles
EP1449885A1 (fr) 2003-02-18 2004-08-25 Atofina Mélanges de polyamide et de polyoléfine contenant des nanotubes de carbone
EP1452307A1 (fr) 2003-02-28 2004-09-01 EMS-Chemie AG Laminé thermoplastique et multi-couche sous forme de corps creux
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EP1645412A1 (fr) 2004-10-11 2006-04-12 Degussa GmbH Système de tuyauterie pour des liquides et des gaz dans une pile à combustible
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220018467A1 (en) * 2018-12-12 2022-01-20 Ems-Chemie Ag Multilayer fuel line
US12392426B2 (en) * 2018-12-12 2025-08-19 Ems-Chemie Ag Multilayer fuel line
CN113603999A (zh) * 2021-07-29 2021-11-05 宝新高分子科技(广州)有限公司 防水耐热组合物、防水耐热绝缘结构、防水耐热电线及其应用
WO2024044734A1 (fr) * 2022-08-26 2024-02-29 Martinrea International US Inc. Tube de gestion thermique en plastique multicouche tel que pour application automobile
DE102023130025A1 (de) * 2023-10-30 2025-04-30 Voss Automotive Gmbh Mehrschichtrohrleitung zum Durchleiten dielektrischer Fluide, Immersionskühlungskreislauf sowie Elektrofahrzeug mit zumindest einer immersionsgekühlten Batterie

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