EP3997176A1 - Mélange de polymères ternaire, en particulier pour l'extrusion de tuyaux, tuyau en matière plastique thermoplastique fabriqué à partir d'un tel mélange et son utilisation - Google Patents

Mélange de polymères ternaire, en particulier pour l'extrusion de tuyaux, tuyau en matière plastique thermoplastique fabriqué à partir d'un tel mélange et son utilisation

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Publication number
EP3997176A1
EP3997176A1 EP20734687.5A EP20734687A EP3997176A1 EP 3997176 A1 EP3997176 A1 EP 3997176A1 EP 20734687 A EP20734687 A EP 20734687A EP 3997176 A1 EP3997176 A1 EP 3997176A1
Authority
EP
European Patent Office
Prior art keywords
polyamide
polypropylene
range
polyolefin
thermoplastic elastomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20734687.5A
Other languages
German (de)
English (en)
Inventor
Heinz Spelthann
Daniel DE BEER
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.)
Voss Automotive GmbH
Original Assignee
Voss Automotive GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Voss Automotive GmbH filed Critical Voss Automotive GmbH
Publication of EP3997176A1 publication Critical patent/EP3997176A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2021/00—Use of unspecified rubbers as moulding material
    • B29K2021/003—Thermoplastic elastomers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0088—Blends of polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes

Definitions

  • the present invention relates to a thermoplastic polyamide-polyolefin blend, in particular for the production of fluid-carrying pipes by extrusion, at least containing a polyolefin, a polyamide and a compatibilizer.
  • the invention also relates to a plastic pipe made from such a blend and its use.
  • Fluid-carrying line systems which are used in particular in motor vehicles as
  • Line sections pipes - or hoses in flexible training - aulweise which via line connectors, such as. B. mandrels, interconnectable or connected, are subject to a variety of requirements.
  • Such line systems can in particular means for generating pressure, such. B. pumps or compressors, by means of which the fluid is conveyed through the system. This results in requirements with regard to pressure resistance.
  • means for generating or dissipating heat By using means for generating or dissipating heat, heating or cooling can be provided. From this and by changing the
  • Wall must be present.
  • the wall of the pipe must have a certain resetting behavior - from the expanded state that occurs during the expanding process - so that, in particular without the use of further fastening means, such as. B. by hose clamps, a tight fit on the mandrel.
  • further fastening means such as. B. by hose clamps
  • pure polyolefin pipes do not meet this requirement because they have too high a tendency to creep, which is unsuitable for mandrel connections.
  • the pipe must also be resistant to media. So z. B a certain zinc chloride resistance must be guaranteed, especially in cooling water applications. This is determined according to the standard SAE J 2240-2008. PA 6 and PA 66 as well as their blends with polyolefins do not meet this media resistance. These materials are also resistant to hydrolysis at cooling water temperatures>
  • a wall made of PA12 With regard to the use of material in the pipe wall, at least three options for setting an optimal balance between the requirement profile and manufacturing costs can be differentiated.
  • German utility model of the applicant DE 20 2011 110 917 U1 describes a heatable fluid line that has at least two length sections that are different in terms of their material properties and / or their structural shape, on the one hand at least a first length section consisting of consists of a first material containing a first polymer, and on the other hand a second
  • Length section which consists of a second material which contains a second polymer, the material of the second length section being more flexible and / or having a higher strength than the material of the first length section.
  • the material of the first length section can in particular contain a polymer that is an engineering plastic, while the material of the second length section can in particular contain a polymer that is a high-performance plastic.
  • the continuous use temperature can be determined in various ways. In the method according to UL 746 B a so-called temperature index is given, ie the temperature is determined at which the polymer material still has half its tensile strength after 60,000 or 100,000 hours
  • polyethylene PE
  • polypropylene PP
  • polyvinyl chloride PVC
  • PMMA polymethacrylic acid methyl ester
  • ABS acrylonitrile-butadiene-styrene
  • PS polystyrene
  • Engineering plastics include polyamide (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonate (PC) and polyoxymethylene (POM).
  • PA polyamide
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PC polycarbonate
  • POM polyoxymethylene
  • the high-performance plastics include polytetrafluoroethylene (PTFE),
  • PVDF Polyvinylidene fluoride
  • PSU polysulphones
  • PAEK polyaryl ether ketones
  • PPS polyphenylene sulphides
  • PI polyimides
  • a polyamide in particular PA 6, PA 66, PA 11 or PA 12, can advantageously be selected as the polymer material of the first length section, which results in a low-cost production of the Fluid line according to the invention can be guaranteed.
  • Polyamides are generally classified as engineering plastics, but they can also be given by a special design of their formulation, e.g. B. by copolymerization, the properties of high-performance plastics are given.
  • the first length section can be designed, for example, as a plastic molded tube, with filled engineering plastics such. B. fiber-reinforced plastics can be used.
  • the polymer of the second length section can advantageously be an elastomer, for example hydrogenated acrylonitrile butadiene rubber (HNBR), ethylene-propylene-diene rubber (EPDM) for a temperature load of up to 170 ° C, an ethylene-propylene - Rubber (EPM) for temperatures above 200 ° C or a thermoplastic elastomer (TPE).
  • HNBR hydrogenated acrylonitrile butadiene rubber
  • EPDM ethylene-propylene-diene rubber
  • EPM ethylene-propylene - Rubber
  • TPE thermoplastic elastomer
  • PA 12 elastomers appear particularly suitable. These are block copolymers made from PA 12 and from polyether segments (polyether block amides PEBA). They show the essential properties of PA12, whereby the elastomeric character becomes more and more pronounced with increasing polyether content. The polymers become elastically more flexible and tougher at low temperatures.
  • the utility model DE 20 2011 110 917 U1 also describes a preferred embodiment of a first length section of a fluid line with a second option for achieving an optimal balance between the requirement profile and manufacturing effort .
  • the Pipe wall constructed in two layers. It comprises an outer wall, preferably made of an engineering plastic such as PA 12, and an inner wall, preferably made of a fluoropolymer such as PTFE.
  • Inner wall can preferably be comparatively thin in the sense of only a superficial coating of the outer wall, i. H. approximately with a maximum wall thickness of 300 ⁇ m, the comparatively thicker outer wall ensuring the required mechanical stability.
  • Material-economical production method - mainly from the engineering plastic - the length section has a load-appropriate heat and cold resistance and, in particular due to the fluorine-containing polymer of the inner wall, an increased resistance to the fluid flowing in it, for example increased chemical resistance, especially with regard to water absorption and / or hydrolysis.
  • the compounding thus firmly bonds at least two substances with one another.
  • the aim of compounding is to
  • Twin-screw extruders in which the starting materials, which are usually in granular form, are melted and intimately mixed. If two polymers are compounded, this creates a so-called one
  • polyblend Such a polyblend - also known as a polymer alloy (English: “alloy”) - is a special compound, but a compound is not always a blend. Specific types of blends are mixtures of polyolefins, such as polyethylene (PE) and / or polypropylene (PP), which due to the above. Criteria under which mass plastics are to be classified, with polyamides as representatives of the higher-quality technical or even - as mentioned above - possibly the
  • polyethylene with the aid of a process for compatibilization, such as the use of peroxides, block copolymers or specially selected compatibilizers.
  • These blends are characterized e.g. B. by increased impact strength and reduced water absorption.
  • high-impact polyamides by compounding polyamide is known exclusively with modified polyolefins, especially with acid- or anhydride-functional polyethylenes.
  • the production of such polyamide blends is e.g. B. described in: Kunststoffe 65 (1975), p. 139 ff, Kunststoffe 80 (1991), p 838 ff, EP 0 469 693 A2 and in the literature cited therein - z. B.
  • a special challenge is that - since one polymer acts as a "high molecular weight" solvent for the other in a mixture of two different polymers - the possibilities for arranging the polymer segments are often drastically reduced, so that a strongly restricted or a non- The result is miscibility of the polymers, which is shown thermodynamically, for example, in the enthalpy of mixing of different homopolymers which deviates from zero. The entropy of mixing is also used as a measure.
  • Polyolefins depend on the chemical structure of the polymer chain, such as from
  • miscibility doors spoken in the phase diagram. Often there is only a miscibility in a certain proportion of the constituents of the mixture. The percentage of different types of polymer in a blend is therefore very important. However, the miscibility, which according to thermodynamics is understood to be complete single-phase, must be distinguished from a general compatibility of the different polymers. Polymers are compatible when the corresponding blends show the desired properties without having to be completely homogeneously miscible. They can therefore also be designed in two or more phases, with one of the polymers being able to form a matrix for the other polymer and any other ingredients that may be present. A prerequisite for this, however, is the provision of a suitable compatibilizer tailored to the constituents of the mixture. However, it can also be assumed that the quantitative proportions of the constituents are highly significant.
  • a polyamide-polyolefin blend similar to the type mentioned above is known from DE 603 02 719 T2. It describes flame-retardant compositions which - based on the weight, the total amount being 100 parts - contain the following components: 50 to 75 parts of the mixture of polyamide and polyolefin and 25 to 50 parts of the mixture containing: 0.1 to 48.8 parts of a flame retardant, 0.1 to 30 parts of a phosphorus
  • Plasticizer 0.1 to 10 parts of a zeolite, the total of these three products being between 25 and 50 parts.
  • functionalization of the polymers through the use of copolymers is apparently intended - although not expressly emphasized.
  • These compositions are said to be suitable for protecting electrical cables and optical fibers and for molding electrical housings and preventers and therefore have an insulating effect.
  • a polyamide-polyolefin blend of the type mentioned at the beginning is known from DE 60 2004 001 610 T2. Therein the use of constructions with at least one layer of a mixture of polyamide and containing nanofillers Described polyolefin, wherein the polyamide forms the matrix, and where at least one layer of another material is optionally present to achieve a barrier effect.
  • the mixture is thermoplastic and can be used to make bottles, tanks, containers, pipes and vessels of all kinds.
  • An ethylene-butyl acrylate-maleic anhydride copolymer and a polypropylene are described as compatibilizers
  • the present invention is based on the object of providing a polyamide-polyolefin blend, in particular for the production of fluid-carrying pipes, of the generic type mentioned at the outset, and one produced therefrom, preferably as
  • Zinc chloride solutions and the blend is easy to process
  • Pipe connector elements should be guaranteed.
  • a similar expansion and creep behavior as that of PA 12 should be guaranteed.
  • Compatibilizer is contained in a range from 7.5 to 50 parts by weight based on 100 parts of the mixture of the polypropylene and the polyamide and contains a partially neutralized ionomer, which is a copolymer containing ethylene and acrylic acid monomer units.
  • Polypropylene-based thermoplastic elastomers are among the
  • thermoplastic elastomers TPE-O
  • TPE-O thermoplastic elastomers
  • They combine the properties of a semi-crystalline polyolefin and an amorphous elastomer component. It can in particular be a polymer blend with an uncrosslinked phase from the polymer which is dispersed in a polypropylene-containing matrix
  • EPDM Ethylene Propylene Diene Rubber
  • thermoplastic elastomer also contain an ethylene-propylene copolymer (abbreviation E / P) as the second phase.
  • E / P ethylene-propylene copolymer
  • thermoplastic elastomer the polyamide-polyolefin blend according to the invention is not just a binary but a ternary polymer alloy, that is to say a polyblend whose three constituents advantageously each have their own way
  • the compatibilizer which contains as at least one first component a partially neutralized ionomer, which is a copolymer that contains ethylene and acrylic acid monomer units
  • a partially neutralized ionomer which is a copolymer that contains ethylene and acrylic acid monomer units
  • three different types of crosslinking are known for copolymers that contain ethylene and acrylic acid monomer units: physical, ionic and covalent.
  • the radical copolymerization of ethylene and acrylic acid results in highly branched polymers.
  • the carboxy groups cause very good adhesion to polar materials, while the polyethylene matrix adheres well to non-polar carrier materials. They can act to promote adhesion between the polypropylene of the TPE-O and the polyamide. Hydrogen bridges also form between the carboxy groups, which ensure good internal cohesion through physical cross-linking.
  • ethylene-acrylic acid copolymers - as provided according to the invention - are then neutralized with metal ions, such as Na + , K + , Ca 2+ , Mg 2+ or Zn 2+ , for crosslinking in the context of the second type of crosslinking, these groups accumulate ion clusters together, and ionic networks are formed.
  • metal ions such as Na + , K + , Ca 2+ , Mg 2+ or Zn 2+
  • Blends in which mixed forms of the three types of crosslinking mentioned can be present are also advantageous according to the invention.
  • Ionomers are obtained by copolymerization of a non-polar with a polar monomer, as in the case according to the invention from ethylene and acrylic acid monomer units (English abbreviation: EAA - Ethylene Acrylate Acid).
  • EAA - Ethylene Acrylate Acid ethylene and acrylic acid monomer units
  • the polar bonds push back the crystallization and lead to the aforementioned "ionic crosslinking”.
  • ionomers Compared to conventional thermoplastics, ionomers have the advantage that both secondary valence forces and ionic bonds are effective in them. These ion bonds are particularly strong and give the substance its characteristic properties. In addition, unlike most other plastics, they can also serve as electrolytes.
  • Polyblend according to the invention behaves like a thermoplastic elastomer, so that it is very suitable for pipe extrusion. This applies optimally when it is in the stated proportions in the range from 7.5 to 50 parts by weight based on 100 parts of the mixture of the polypropylene-based
  • thermoplastic elastomer and the polyamide is contained in the blend according to the invention.
  • the compatibilizer can advantageously be used as a second additional optional component, a terpolymer of ethylene, alkyl acrylate and glycidyl methacrylate, e.g. B. ethylene methacrylic glycidyl methacrylate (EnMaGma).
  • the mass ratio of the first component of the compatibilizer to the second component of the compatibilizer can - if present - be in the range from 0.05 to 2.0, preferably in the range from 0.2 to 1.0.
  • crosslinking behavior achieved in this way preserves the positive properties of the ionomer, but advantageously lowers the high melting temperature occurring in the case of the ionomers mentioned, which - considered as a pure material for the ionomer - would be in the range of 290 ° C to 330 ° C, in the sense of a improved extrudability at lower processing temperatures.
  • Polyamides are an extremely large class of polymers, the individual representatives of which can be produced in different ways.
  • the presence of functional amide groups —CO — NH— or also —CO — NR— in the macromolecule is characteristic, where R describes an organic, in particular aliphatic or also aromatic radical.
  • polyamides which are derived from an aminocarboxylic acid of the type H2N- (CH2) x-COOH or the corresponding
  • PA 6 for a polymer made from e-caprolactam or w-aminocaproic acid [NH- (CH2) 5-CO] n, with n as the degree of polymerization.
  • PA 11 is made from 11-aminoundecanoic acid and PA 12 from laurolactam or w-aminodecanoic acid.
  • PA 11 and PA 12 are cold-resistant down to at least -50 ° C and continuously heat-resistant up to +80 ° C. By adding stabilizers and plasticizers However, the resistance to cold or heat can be reduced to values of -60 ° C or
  • Notched impact strength In addition, it has good to very good chemical resistance to grease, oils, fuels, hydraulic fluids, many solvents, salt solutions and other chemicals.
  • PA 66 for the polymer of hexamethylenediamine (HMDA, 1, 6-diaminohexane) and adipic acid [NH- (CH2) 6-NH-CO- (CH2) 4-CO] n.
  • PA 6 10 stands for the polymer made from HMDA and sebacic acid (decanedioic acid, 1,8-octanedicarboxylic acid, HOOC- (CH2) 8-COOH).
  • Particularly suitable polyamides for the blend according to the invention are long-chain polyamides in the mono- or dimer, such as PA 11, PA 12, PA 6 10, PA 6 12, PA 6 14, in which Z 3 11 or Z2 3 10 ( at Z1 3 6).
  • a content of additives such as fillers, heat stabilizers, antioxidants, anti-aging agents, plasticizers or plasticizers, lubricants,
  • Lubricants and / or flow aids can be provided, the additives in a range of 0.5 to 25 parts by weight, preferably 4 to 15 parts by weight, based on 100 parts of the mixture of the polypropylene-based thermoplastic elastomer and the polyamide.
  • the blend according to the invention is in a tube, in particular in a
  • polypropylene-based thermoplastic elastomer as a blend component with a reduced material wall compared to the use of pure PA12
  • a pipe according to the invention is characterized in that its wall is made using the thermoplastic polyamide-polyolefin blend according to the invention, in which the polyolefin is a polypropylene-based thermoplastic elastomer, which in a mass ratio in the range from 0.06 to 4.8 to the polyamide
  • the compatibilizer is contained in a range from 7.5 to 50 parts by weight based on 100 parts of the mixture of the polypropylene and the polyamide and contains a partially neutralized ionomer which is a copolymer which contains ethylene and acrylic acid monomer units.
  • the pipe can advantageously be produced in particular by extrusion, but the polyblend according to the invention is also suitable for the production of other extrusion goods, such as corrugated pipes and profiles, etc.
  • the pipe wall can advantageously be designed in particular in one layer, but the production of a multi-layer pipe by, for example, coextrusion of one or more further layers lying radially inside and / or outside the layer consisting of the blend according to the invention is not excluded.
  • each individual partial feature of the exemplary embodiment can also have an inventive significance in isolation from all other partial features described in connection therewith, either by itself or in combination with only a few other partial features. So can
  • the branded products listed in Table 2 below can be replaced with alternative materials with the same or at least largely similar chemical structure with no or only marginal change in the minimum and maximum values of the percentages.
  • the comparison pipes were made from VESTAMID® X7393. It is a standardized molding compound according to ISO 1874-PA12-HIP, EHL, 22-005, which is used as type PA 12-PHLY according to DIN 73 378 and DIN 74 324 for flexible pipes and hoses for the automotive industry. According to the above-mentioned ISO standard (including the measuring methods prescribed therein), the polymer has the properties listed in Table 1.
  • the polymer is supplied as granules and is one when processed
  • plasticized, highly viscous PA 12 molding compound with optimized low-temperature impact strength after solidification. It is especially for an extrusion of semi-hard Suitable for pipes with high burst pressure resistance.
  • the recommended melt temperature for profile extrusion is 220 ° C to 250 ° C.
  • Grilamid 2S which can be obtained from EMS-Grivory, is PA 6 10 and, as already mentioned, is produced by the polycondensation of hexamethylenediamine and sebacic acid. Hexamethylenediamine is extracted from petroleum while
  • Sebacic acid is obtained from the organic raw material castor oil through a multi-stage chemical process.
  • Polyamide 6 10 therefore advantageously consists of 62 percent renewable raw materials.
  • Other special features of Grilamid 2S (PA 6 10) are its low water absorption and good properties
  • Vistamaxx TM 6202 is offered as granules by Exxon Mobil and is a polypropylene-based thermoplastic elastomer with isotactic propylene Repeating units and statistical distribution of ethylene groups in the polyolefin copolymer.
  • the ethylene content is 15 to 16% by mass.
  • polypropylene-based thermoplastic elastomer an ethylene content of less than 40 mass% is considered optimal, in particular an ethylene content in the range of only 7 mass% to 25 mass%, preferably in the range of 12 mass% to 19 mass%. -%. Accordingly, the propylene content is higher than that of the known polypropylene-based thermoplastic elastomers described above.
  • Vistamaxx TM 6202 does not use the classic Ziegler-Natta catalysts, which have the disadvantage that they usually have to be used as heterogeneous catalysts on a carrier material because they are not soluble in organic solvents but is made with metallocene catalysts.
  • Metallocenes are a group of organometallic compounds in which a central metal atom is sandwiched between two cyclopentadienyl ligands (C5H5, abbreviation: Cp). The metallocene catalyst is the
  • the viscoelastic properties can advantageously be influenced in the sense of a reduced tendency to creep.
  • Vistamaxx TM 6202 has the properties listed in Table 3.
  • Table 3 Properties of Vistamaxx TM 6202
  • Lotader® AX 8900 Typical properties of Lotader® AX 8900 are shown in Table 4 below.
  • Lotader® AX 8900 is a terpolymer with statistical distribution of its
  • Glycidyl methacrylate (8 mass%). It is produced in high pressure autoclaves and sold by Arkema.
  • the glycidyl methacrylate causes a reactivity towards OH, COOH and NH2 groups, which during the mixing process in the melt with the polymers for which it is used as a compatibilizer, an optimally homogeneous
  • Lotader® AX 8900 is not only compatible with LDPE, but advantageously also with ethylene-containing copolymers, such as the ethylene-containing TPE-O described above.
  • the use of Aclyn® 295 in the polyblend according to the invention has a positive effect on a high level of corrosion resistance, in particular to zinc chloride solutions.
  • Bruggoien® H333 is a heat stabilizing additive from the Brüggemann group of companies. Those sold under the brand name Bruggoien®
  • Heat stabilizers are used to prevent the phenomenon that occurs with many polymer materials, due to the influence of heat, light and
  • Atmospheric oxygen the physical properties and the appearance of the respective plastic can be changed considerably.
  • processing stabilizers which primarily counteract polymer degradation in the melt phase - i.e. during compounding, injection molding or extrusion - and long-term stabilizers that are used during the use of the finished part
  • high ambient temperatures 60 ° - 130 ° C
  • UV stabilizers for effective protection of the finished parts against polymer degradation by UV radiation.
  • Combinations of various heat-stabilizing additives can result in additional synergy effects.
  • the Bruggolens® H333 additive used is the active ingredient copper iodide, which stabilizes polyamides at temperatures of up to 180 ° C.
  • Irganox® 1098 is the trade name for benzene propanamide, N, N'-1, 6-hexanediyl- bis [3,5-bis (1, 1-dimethylethyl) -4-hydroxy. It is a sterically hindered phenolic compound. It is what is called a primary antioxidant
  • Antioxidant I is manufactured by the company BASF in order to achieve increased thermal stability in polymers, in particular in polyamides, with its addition in particular causing discoloration of the polymer
  • the polysiloxane product Dow-Corning® is shown in Table 2 as a further additive
  • Ultra high molecular weight (UH MW) means that the mean molecular weight of the siloxane is above 300,000 g / mol and that the polysiloxane has a kinematic viscosity of above 5,000,000 - determined according to DIN 51562 (01/1999) at 40 ° C.
  • Blend according to the invention it improves the flowability and reduces the
  • the LDPE owns
  • Compatibility Maker - a high level of compatibility with the
  • polypropylene-based thermoplastic elastomer of the formulation polypropylene-based thermoplastic elastomer of the formulation.
  • Table 2 lists Proviplast® 024 from the company as the last ingredient in the formulation
  • Proviron It is a plasticizer that in particular
  • PA 6 10, PA 6 12, PA 10 10, PA 11 and PA 12 are equally good for PA 6 10, PA 6 12, PA 10 10, PA 11 and PA 12 as
  • Proviplast® 024 is by its chemical nature a sulphonamide, namely N-butylbenzenesulphonamide.
  • the polypropylene-based thermoplastic elastomer in the preferred blend composition is in a mass ratio of 0.154 (10/65) to the polyamide. It is therefore in a preferred range from 0.1 to 3.0. According to the invention this should
  • Mass ratio at least in the range of 0.05 to 5.0.
  • the compatibility maker (sum of the first component and the second
  • the Compatibility agents should according to the invention at least in a range of 12 to 30 parts by weight, based on 100 parts of the mixture of the
  • polypropylene-based thermoplastic elastomer and the polyamide.
  • Compatibility maker for the terpolymer made from ethylene, alkyl acrylate and
  • Glycidyl methacrylate as the second compatibilizer component is 0.187 (3/16). It is therefore in a preferred range from 0.2 to 1.0.
  • the mass ratio should be at least in the range from 0.05 to 2.0.
  • the compound was produced in a twin screw extruder with a screw diameter of 25 mm.
  • the constituents introduced in the solid state were melted and in one
  • the pipes were produced in an extruder with a screw diameter of 45 mm.
  • a barrier screw with a ratio of length L to diameter D of 25 was used. Characteristic of a
  • the barrier screw is that in the plasticizing zone an additionally inserted web, the so-called barrier web, separates the solids from the melt.
  • the freshly melted material can be transferred from the solids channel via the barrier web into the Melt channel flow while the barrier gap is dimensioned so that the solid is retained. This ensures a well-digested melt and prevents unmelted solid particles from escaping from the plasticizing zone.
  • the temperatures in the extruder were as follows: feed zone - 240 ° C, compression zone - 245 ° C, discharge zone - 250 ° C, extrusion head - 250 ° C.
  • Pipes according to the invention could equally be described by the specification 4.05 ⁇ 1 mm.
  • Tables 5 and 6 contain representations of the tensile tests on the pipes using the ZWICK ROELL Z020 in accordance with the DIN EN ISO 527-2: 2012-06 standard
  • the tube according to the invention contains fewer volatile components than the comparison tube, as can be seen from the weight loss during heat aging, which indicates that the low tensile modulus in
  • Comparative material is achieved via plasticizers. Overall, due to the increase in tensile strength and the decrease in elongation at break after
  • the blend according to the invention has good processability by extrusion, with the ability to assemble pipes according to the invention on mandrels as pipe connector elements is ensured. In making more durable
  • the polymer blend according to the invention advantageously has an optimal combination of the material properties of long-chain polyamides as technical ones
  • Plastics in particular with similar creep resistance, media resistance and flexibility as PA 12, with a high media resistance and low-cost (inexpensive) production as well as the easy availability of polyolefins as mass-produced plastics.
  • Thermoplastic plastic pipes according to the invention have in particular an excellent ability for crack-free and creep-free assembly on one

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

La présente invention concerne un mélange de polyamide-polyoléfine thermoplastique, en particulier pour l'extrusion de tuyaux destinés au transport de fluides, contenant au moins une polyoléfine, un polyamide et un agent compatibilisant. Afin d'obtenir une haute résistance aux produits chimiques, en particulier à l'eau de refroidissement et aux solutions aqueuses de chlorure de zinc, ainsi qu'une bonne ouvrabilité du mélange par extrusion et une aptitude à l'assemblage d'une matière plastique produite à partir du mélange à l'état brut sur des mandrins comme éléments de raccordement de tuyaux, en optimisant le rapport entre le profil d'exigences et l'effort de fabrication, la présente invention concerne le fait que la polyoléfine soit un élastomère thermoplastique à base de polypropylène qui se trouve dans un rapport pondéral compris entre 0,05 et 5,0 par rapport au polyamide, l'agent compatibilisant étant contenu dans une plage de 7,5 à 50 parties en masse, sur la base de 100 parties du mélange d'élastomère thermoplastique à base de polypropylène et de polyamide, et l'agent compatibilisant contenant comme au moins premier composant un ionomère partiellement neutralisé qui est un copolymère contenant des motifs monomères d'éthylène et d'acide acrylique.
EP20734687.5A 2019-07-11 2020-06-22 Mélange de polymères ternaire, en particulier pour l'extrusion de tuyaux, tuyau en matière plastique thermoplastique fabriqué à partir d'un tel mélange et son utilisation Pending EP3997176A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019118856.3A DE102019118856A1 (de) 2019-07-11 2019-07-11 Ternäres Polymerblend, insbesondere zur Rohrextrusion, thermoplastisches Kunststoffrohr aus einem derartigen Blend sowie dessen Verwendung
PCT/EP2020/067275 WO2021004764A1 (fr) 2019-07-11 2020-06-22 Mélange de polymères ternaire, en particulier pour l'extrusion de tuyaux, tuyau en matière plastique thermoplastique fabriqué à partir d'un tel mélange et son utilisation

Publications (1)

Publication Number Publication Date
EP3997176A1 true EP3997176A1 (fr) 2022-05-18

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Country Status (4)

Country Link
EP (1) EP3997176A1 (fr)
CN (1) CN114040944B (fr)
DE (1) DE102019118856A1 (fr)
WO (1) WO2021004764A1 (fr)

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CN114040944A (zh) 2022-02-11
WO2021004764A1 (fr) 2021-01-14
DE102019118856A1 (de) 2021-01-14
CN114040944B (zh) 2024-04-05

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