EP4087896A1 - Matériaux polyamides ayant des caractéristiques de performance à long terme améliorées - Google Patents

Matériaux polyamides ayant des caractéristiques de performance à long terme améliorées

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Publication number
EP4087896A1
EP4087896A1 EP21700691.5A EP21700691A EP4087896A1 EP 4087896 A1 EP4087896 A1 EP 4087896A1 EP 21700691 A EP21700691 A EP 21700691A EP 4087896 A1 EP4087896 A1 EP 4087896A1
Authority
EP
European Patent Office
Prior art keywords
copper
polyamide
halogen
polyamides
use according
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
EP21700691.5A
Other languages
German (de)
English (en)
Inventor
Klaus Bergmann
Kristina Frädrich
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.)
L Brueggemann GmbH and Co KG
Original Assignee
L Brueggemann GmbH and Co KG
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 L Brueggemann GmbH and Co KG filed Critical L Brueggemann GmbH and Co KG
Publication of EP4087896A1 publication Critical patent/EP4087896A1/fr
Pending legal-status Critical Current

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    • C08K5/053—Polyhydroxylic alcohols
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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    • 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
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    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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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    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
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    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the present invention relates to polyamide materials with improved long-term use properties, processes for long-term stabilization of polyamides and the use of specific additive compositions for long-term stabilization of polyamides.
  • thermo-oxidative or photo-oxidative reactions take place at temperatures above 70 ° C or by high-energy radiation on the polyamide surface.
  • the surface yellows and becomes increasingly matt and cracked. This leads to the embrittlement of the material and thus to the impairment of the mechanical properties of the molded part.
  • suitable stabilizers By adding suitable stabilizers, the oxidative damage to the polyamide can be delayed, so that the time until the polyamide parts become brittle can be delayed.
  • stabilizers for different temperature ranges.
  • Typical classes of stabilizers for polyamides are copper-based stabilizers, secondary aromatic amines and stabilizers based on sterically hindered phenols.
  • Sterically hindered phenols are mostly used in combination with secondary antioxidants, especially phosphites or phosphonates. These blends of sterically hindered phenols with phosphites or phosphonates are referred to below as phenolic stabilizers or as phenolic antioxidants.
  • the copper-based stabilizers typically comprise at least one copper compound and at least one further halogen-containing component, which is referred to as a synergist.
  • the combination of copper compounds with halogen-containing synergists is referred to below as a copper stabilizer.
  • housings for controls, connectors and sensors are usually made of polyamide materials, since polyamides can withstand the boundary conditions required there particularly well.
  • the high ambient temperatures to which the assemblies are exposed play an important role.
  • the increasing miniaturization and the ever closer packing of components contribute in this context to a progressive increase in temperature requirements.
  • manufacturers have increasingly been confronted with corrosion problems, especially electrical corrosion, which resulted in corresponding failures.
  • Analytical investigations on corroded contacts showed that iodides and bromides, which were identified as components of the copper-based stabilizers in the polyamide materials used, were significantly involved in the corrosion process.
  • thermoplastics such as polyphenylene sulfide and partially aromatic polyamides and are therefore looking for new solutions for essentially aliphatic polyamide materials for electrical applications that have increased performance at high temperatures and do not require the addition of copper and halogen compounds for stabilization .
  • these stabilizers do not act like classic antioxidants in polyamides, but that they form a protective layer at elevated temperatures in the presence of oxygen, which as a barrier ("patina”) is not or very little permeable to oxygen and thus a more extensive one Prevents oxidation of the polyamide areas below.
  • a sealing step (annealing step) is at high
  • polyamide components are used that are based on polyamide compositions that contain “barrier-forming” additives. These are, for example, charge air cooler end caps, resonators and charge air lines.
  • partially aromatic polyamide compositions containing glass fibers and polyols which have a significantly improved long-term stability at very high temperatures.
  • WO2010 / 014785 A1 discloses partially aromatic polyamides reinforced with glass fibers for the high temperature range, which additionally contain polyols and secondary aromatic amines or sterically hindered amines (or combinations of these two substance classes).
  • a solution for unreinforced polyamide compositions in the low temperature range has not yet been presented.
  • a thermal stabilizer such as a copper salt-based additive can be used Significantly extend retention times in the high temperature range.
  • a high-temperature treatment for producing a surface barrier layer is regarded as essential.
  • EP 1 780241 A1 proposes the use of nanoscale fillers.
  • EP3115407A1 relates to thermally stabilized polyamide-based compositions based on iron oxalate and dipentaerythritol in combination with one another for the temperature range above 180 ° C.
  • EP 3059283 discloses a large number of polyamide compositions with improved heat resistance for electrical applications, in which a substance with a polyol structure is contained which has at least one epoxy group or one carbodiimide group. This enables a coupling reaction with the polyamide, which is essential for the technology disclosed in EP 3059283.
  • the tendency of polyols to migrate in polyamide is minimized by the reactive coupling to the polyamide matrix.
  • Polyol components chemically directly coupled to the polyamide matrix are also disclosed in EP 2 829 576 A1.
  • EP 2881439 describes a polyamide composition reinforced with glass fibers with improved heat resistance at high temperatures, which contains both a polyol and a copolymer, defined via the MFI, of olefin with at least one methacrylic acid ester or acrylic acid ester.
  • the polyamide material is aged at 200 ° C.
  • Similar compositions are also disclosed in EP 2 878 630 A1.
  • it is considered essential that the polyamide composition necessarily contains partially aromatic polyamides or polyamide 4/6.
  • a reference to stabilization within the meaning of the invention described below by iron compounds or reinforcing materials, such as glass fibers, is not to be found in this document.
  • EP 3093312A1 discloses polyamide compositions with improved heat resistance at high temperatures above 180 ° C. which, in addition to polyamide, contain a citric acid salt, dipentaerythritol and at least one filler or reinforcing material.
  • CN 108070253 A discloses polyamide compositions. It is based on a
  • compositions must therefore contain nanoparticles with a specified particle size.
  • halogen-containing and / or copper-containing stabilizers are used.
  • Another type of polyamide compositions in which stabilization at elevated temperatures poses a particular challenge are the impact-modified polyamides. Due to the presence of both a polyamide component and a rubber-elastic polymer component, the particular challenge in these is to achieve temperature stabilization despite the chemically very different essential polymer components. This problem is particularly pronounced at temperatures above 140 ° C.
  • the present invention has the object of specifying a way with which the desired stabilization can be achieved at the specified long-term use temperatures, so in particular to enable polyamide compositions that have an improved long-term stabilization against heat over a wide range (even at high temperatures above 150 ° C and up to 170 ° C and in special cases also above 170 ° C), and at the same time also efficiently stabilized at temperatures below 150 ° C with regard to a significant extension of the possible service life, preferably with regard to at least one option of a) to c), in particular both a) and b), as well as c), optionally c) and b): a) with simultaneous suitability for electrical applications (low content of ionic components); b) and with regard to suitability for both reinforced and unreinforced polyamides; c) as well as impact modified polyamides.
  • the present invention surprisingly enables the desired stabilization of polyamides through the use of components which are already known, but which were previously known in the prior art in other contexts or for other processes. Nevertheless, a significantly improved stabilization can be achieved at long-term use temperatures of 100 ° C. to 170 ° C., in particular 150 ° C., with simultaneous suitability for electrical applications.
  • the stabilizers to be used according to the invention are readily dispersible in polyamides, so that they are easy to handle.
  • the stabilizers according to the invention can be incorporated into polyamides by conventional methods and distributed there; in addition, the stabilizer components can be easily compounded for use, for example by compounding with a matrix of conventional materials such as waxes or polymers.
  • the present invention thus enables the following advantages to be realized:
  • the stabilized polyamides can be used in particular in electrical applications in which high requirements are made with regard to the absence of ionic components (such as copper salts, halogen-containing alkali metal salts, etc.).
  • the amount of stabilizer or type of stabilizer mixture used can be adapted to the desired stabilization time (service life of the product) and to the specific requirements with regard to the presence or absence of ionic components. Due to the very good stabilization by the components essential according to the invention, it may be possible, for example, to use small amounts of copper stabilizers in order to achieve a further improvement in stabilization without the electrical properties (creepage resistance) suffering too much as a result of the very small addition of these components. This can be achieved in particular when using copper complexes.
  • components may be thinner, since a material thickness previously considered necessary (due to a desired redundancy or a corresponding safety factor) can be reduced (since the polyamides stabilized according to the invention can withstand longer loads even with lower material thicknesses).
  • improved stabilization can be achieved when using a polyol compound or an iron compound without the need to use the activation by high-temperature treatment described as necessary in the prior art to produce a barrier layer.
  • This is particularly advantageous because it is also possible to produce very thin components in which the creation of a barrier layer (carbonization of the surface) is not possible, since otherwise there would be an unacceptable impairment of the mechanical characteristics.
  • a polyol component preferably a polyol with 2 or more hydroxyl groups, preferably a polyol with 2 to 12 hydroxyl groups and a molecular weight of 64 to 2000 g / mol, particularly preferably pentaerythritol, dipentaerythritol and tripentaerythritol (and mixtures thereof ), especially dipentaerythritol.
  • the polyol is a dendritic polymer with terminal OH groups. The molecular weight of such a dendritic polymer is preferably in the range from 1000 to 2000 g / mol.
  • the number of hydroxyl groups in this case is preferably in a range from 6 to 60 hydroxyl groups.
  • One example are hydroxy-functional dendritic polyesters, which are formed by polymerizing a polyalcohol core with 2,2-dimethylol propionic acid and which have good thermal stability.
  • alditols and cyclitols can also be used as polyol compounds, with mannitol, erythritol and myo-inositol being preferred.
  • the second alternative according to the invention is the use of an iron compound, preferably an iron (II) compound, in particular iron oxalate.
  • an iron compound preferably an iron (II) compound, in particular iron oxalate.
  • these components are used either with a reinforcing agent described here or, in the case of using a polyol compound, with a copper- and halogen-free antioxidant or with a reinforcing agent described here and additionally with a copper- and halogen-free antioxidant.
  • the amount of polyol component used is usually in the range from 0.1 to 7% by weight (all data, also below, for example for the iron compound, based on the total compound), preferably 0.5 to 5% by weight, particularly preferred 1 to 4% by weight, in particular 1 to 3% by weight.
  • the amount of iron compound used is usually in the range from 0.1 to 1% by weight, in particular 0.2 to 0.6% by weight
  • the use of a polyol component is preferred.
  • the copper- and halogen-free antioxidant is preferably a secondary aromatic amine or a sterically hindered phenol, which is usually used in combination with phosphites (such a combination is also referred to below as a phenolic antioxidant, or such combinations are mentioned when one hindered phenol as an antioxidant). Combinations of copper and halogen-free antioxidants are also possible. However, it is preferred to use either a secondary aromatic amine or a sterically hindered phenol (typically in combination with a secondary antioxidant such as phosphites) alone, without further copper- and halogen-free stabilizers.
  • Secondary aromatic amines which can be used in the present invention can be both monomeric and polymeric secondary aromatic amines. Prefers the molecular weight of these components is 260 g / mol or more, more preferably 350 g / mol or more. Secondary aromatic amines are compounds in which the amine nitrogen atom is bonded to two organic substituents, at least one of which, preferably both, are aromatic.
  • Suitable examples are 4,4'-di (a, a-dimethylbenzyl) diphenylamine (commercially available for example under the name Naugard 445), para- (paratoluenesulfonylamido) diphenylamine (commercially available for example under the name Naugard SA), the reaction product of diphenylamine with Acetone (commercially available, for example, under the name Aminox), N, N'-di- (2-naphthyl) -p-phenylenediamine, 4,4'-bis (a-methylbenzyhydryl) diphenylamine and other compounds known to those skilled in the art, for example disclosed in EP 0 509282 B1.
  • aminic stabilizers in which both an aromatic and an aliphatic substituent are present, for example alkyl-aryl-substituted amines or alkyl-aryl-substituted phenylenediamines, are also suitable.
  • p-phenylenediamines such as N- (1,3-dimethylbutyl) -N‘-phenyl-p-phenylenediamine, or N-phenyl-N‘-isopropyl-p-phenylenediamine.
  • systems based on 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) can also be used, preferably polymerized TMQ.
  • Condensation products of diphenylamines such as alkylated diphenylamines or arylated diphenylamines with ketones and / or aldehydes, are also possible.
  • Condensation products which can also be oligomeric or polymeric, e.g. from diphenylamines with acetone or from diphenylamines with acetone and formaldehyde, are preferred.
  • the amount of secondary aromatic amine used is usually in the range from 0.05 to 3% by weight (all data based on the amount of polyamide used), preferably 0.1 to 2% by weight, particularly preferably 0.25 to 1, 5% by weight, in particular 0.5 to 1.25% by weight.
  • Suitable sterically hindered phenols are compounds in which space-filling substituents are present adjacent to the phenolic OH group, for example tert-butyl groups.
  • a particularly suitable example of such stabilizers is 2,6-di-tert-butyl-methylphenol.
  • stabilizers of this type can also be used, including also dimeric structures, that is to say two phenolic groups linked by a suitable organic unit, such as 2,2'-methylene-bis (6-t-butyl-4-methyl-phenol) etc., and also bifunctional phenols, thio-bis-phenols, such as 4,4'thio-bis-6 (t-butyl-metacresol), multifunctional phenols, polyphenols, such as, for example, reaction products of butylated p-cresol with dicyclobutadiene.
  • the amount of phenol component used is usually in the range from 0.01 to 3% by weight (all data based on the amount of polyamide used), preferably 0.1 to 2% by weight, particularly preferably 0.25 to 1.5% by weight .-%, in particular 0.5 to 1.25% by weight.
  • the fillers and reinforcing materials to be used according to the invention can be in the form of fibers or particles (or any transition forms).
  • Organic and inorganic fillers and reinforcing materials can be used.
  • Preferred examples are glass fibers, carbon fibers, glass spheres, ground glass, kieselguhr, wollastonite, talc, kaolin, phyllosilicates, CaF2, CaC0 3 and aluminum oxides. It is also possible to use nanoscale materials, in particular those in which the D50 value is less than 900 nm for one dimension.
  • Suitable nanoscale fillers are those substances which can be added at any stage of production and can be finely distributed in the nanometer range.
  • the nanoscale fillers that can be replaced according to the invention can be surface-treated. However, it is also possible to use untreated fillers or mixtures of untreated and treated fillers.
  • the nanoscale fillers preferably have a particle size of less than 500 nm in at least one dimension.
  • the fillers are preferably minerals that already have a layer structure, such as layered silicates and double hydroxides.
  • the nanoscale fillers used according to the invention are preferably selected from the group of oxides, oxide hydrates of metals or semimetals.
  • the nanoscale fillers are selected from the group of oxides and oxide hydrates of an element, selected from the group consisting of boron, aluminum, calcium, gallium, indium, silicon, germanium, tin, titanium, zirconium, zinc, ytrium or iron.
  • the nanoscale fillers are either silicon dioxide or silicon dioxide hydrates.
  • the nano-scale fillers are present in the polyamide molding compound as a uniformly dispersed, layered material. Before being incorporated into the matrix, they have a layer thickness of 0.7 to 1.2 nm and an interlayer distance between the mineral layers of up to 5 nm.
  • Minerals preferred according to the invention which already have a layer structure, are natural and synthetic phyllosilicates and double hydroxides such as hydrotalcite.
  • nanofillers based on silicones, silica or silsesquioxanes are also suitable.
  • Layered silicates in the context of the invention are understood to mean 1: 1 and 2: 1 layered silicates.
  • layers of Si0 4 tetrahedra are linked to one another in a regular manner with those of M (0.0H) 6 octahedra.
  • M stands for metal ions such as Al, Mg, Fe.
  • a tetrahedral and an octahedron layer are connected to one another. Examples of this are kaolin and serpentine minerals.
  • Examples of 2: 1 layered silicates are talc, vermiculite, lllite and smectite, whereby the smectites, which also include montmorillonite, can be easily swelled with water because of their layered charge. Furthermore, the cations are easily accessible for exchange processes.
  • the nanoscale fillers are preferably selected from the group of natural and synthetic sheet silicates, in particular from the group of bentonite, smectite, montmorillonite, saponite, beidellite, nontronite, hectorite, stevensite, vermiculite, lllite, pyrosite, the group of kaolin and serpentine minerals, double hydroxides, or such fillers based on silicones, silica or silsesquioxanes, with montmorillonite being particularly preferred.
  • the fillers and reinforcing materials can also be surface-treated. Surface modifications based on aminoalkylsilanes or aminoalkylsiloxanes or aminoalkyltrialkoxysilanes are particularly preferred.
  • fibrous reinforcing materials in particular glass fibers (particularly preferably made of E-glass) and carbon fibers, and on the other hand to use glass spheres as non-fibrous reinforcing materials.
  • glass fibers and glass spheres are due to their good availability and cheap Price base and especially preferred in the context of the present invention because of their exceptionally good effectiveness.
  • Glass spheres and glass fibers can also be used in combination.
  • the glass fibers are used in particular in the form of short glass fibers for the production of polyamide materials for injection molding and / or extrusion.
  • the glass fibers are preferably used as continuous fibers and / or as long glass fibers.
  • the production of preconcentrates with the reinforcing material (long glass or endless glass fibers) described below is of course not possible.
  • other preconcentrates in the production of such composites, also with other reinforcing materials, such as short glass fibers, glass spheres or other particle-shaped reinforcing materials.
  • fibrous materials can also be used in combination.
  • glass spheres hollow or filled glass spheres can be used.
  • solid glass spheres so-called “microspheres” made of borosilicate glass or silicate glass with diameters in the range from 5 to 250 ⁇ m are used.
  • compositions and molded polyamide parts made therefrom which contain, inter alia, polyol compounds, but nevertheless tend to form surface deposits to a significantly reduced extent with heat aging at ⁇ 170 ° C.
  • this problem could be solved by adding a high concentration of glass beads and / or fiber-like reinforcing materials, preferably carbon or glass fibers, particularly preferably glass fibers, to the polyamide in addition to the polyol compound (which leads to fiber-reinforced polyamide compositions ), or that the polyol compound is first incorporated into a carrier, preferably polymeric carrier, together with either glass spheres or fiber-like reinforcing materials, preferably carbon and / and glass fibers, particularly preferably glass fibers.
  • glass spheres and glass fibers can also be incorporated into the pre-concentrate at the same time.
  • This pre-concentrate is produced in a first step with a carrier, preferably a polymeric carrier, in a manner known to the person skilled in the art.
  • a carrier preferably a polymeric carrier
  • the polyol compound, a non-copper antioxidant and the glass fibers are introduced into the melt and evenly distributed in the polymeric carrier.
  • This additive is then mixed with the polyamide to be modified in the melt. This can also take place in the production of a high-modulus composite described above with long glass fibers or continuous fibers.
  • the content of glass fibers (or carbon fibers or glass spheres) can be kept very low in this way and an additional dosage of glass fibers or glass spheres (to prevent the polyol compound from blooming) during compounding of the polyamide is no longer necessary .
  • This variant leads to polyamide compositions which have such a low proportion of fibers or glass spheres that they can be regarded as unreinforced polyamide compositions.
  • the addition of the fibers or balls to the pre-concentrate (polyol masterbatch) serves only to prevent migration of the polyol compound to the surface of a molded part under conditions of use that include elevated temperatures.
  • polyamide and stabilizer components are either melted and mixed with one another, or compounded by suitable processes (in particular when using glass fibers or glass spheres).
  • the polyamide is first melted and then the stabilizer components are mixed in, for example in the form of a blend.
  • the stabilizer components are added to the molten polyamide in the form of a premix (concentrate or masterbatch).
  • this preconcentrate can be produced in batch mixers which allow very good, homogeneous distribution, for example in a Buss kneader.
  • continuous mixers such as preferably twin-screw extruders or ZSK- Extruder.
  • the same polyamide that is then mixed with the pre-concentrate can be used as the matrix material. But it is also possible to choose a different polyamide or a different polymer or a non-polymeric material. Optionally, further additives can be added during the masterbatch production.
  • the additive according to the invention further contains at least one additive selected from the group consisting of antioxidants, nucleating agents, stabilizers, lubricants, mold release agents,
  • the additive particularly preferably additionally contains nucleating agents and / or lubricants.
  • the pre-concentrate is provided in the form of a mixture of the additive (s) with a carrier.
  • the carrier is preferably a polymeric carrier that can be easily incorporated into the polyamide to be modified and is easy to disperse or dissolve therein.
  • the polymeric carrier is preferably thermally stable at the processing temperatures typical for polyamides, and contains or forms as few volatile constituents as possible and does not discolour during processing.
  • the polymeric carrier is preferably selected from a polymer or copolymer from the monomers ethylene, propylene or other olefins, methacrylic acid, vinyl acetate, acrylic acid, acrylic acid ester, or methacrylic acid ester.
  • the polymeric carrier is particularly preferably an ethylene-vinyl acetate copolymer (EVA) or an olefin-acrylic acid ester copolymer or an olefin-methacrylic acid ester copolymer, in particular an ethylene-methyl acrylate copolymer (EMA), an ethylene-ethyl acrylate copolymer (EEA) or an ethylene-butyl acrylate copolymer (EBA).
  • EBA ethylene-methyl acrylate copolymer
  • EMA ethylene-methyl acrylate copolymer
  • EVA ethylene-vinyl acetate copolymer
  • EBA ethylene-butyl acrylate copolymer
  • the use of a copolymer described here as a carrier for the pre-concentrate can markedly reduce the tendency of the polyol component to migrate. This effect is particularly pronounced and therefore preferred in the context of the present invention when the copolymers described here are used as a carrier component for a pre-concentrate containing polyol.
  • the carrier is a polyamide, all common polyamides being possible, preferably PA6 or PA6.6.
  • polymeric carrier materials with reactive groups can also be used, such as, for example, maleic anhydride or glicydyl methacrylate-containing copolymers with olefins.
  • examples are ethylene-ethyl acrylate-glycidyl methacrylate terpolymer (E-EA-GMA), ethylene-butyl acrylate-glycidyl methacrylate terpolymer (E-BA-GMA), ethylene-vinyl acetate copolymer functionalized with maleic anhydride (E-VA-MA), styrene-ethylene Butylene-styrene copolymer functionalized with maleic anhydride (SEBS-MA).
  • E-EA-GMA ethylene-ethyl acrylate-glycidyl methacrylate terpolymer
  • E-BA-GMA ethylene-butyl acrylate-glycidyl methacrylate terpolymer
  • SEBS-MA
  • non-polymeric supports can also be used.
  • lubricants such as primary and secondary fatty acid amide waxes, for example ethylene-bis-stearamide (EBS), erucamide and stearamide, metal soaps for example metal stearates, paraffin waxes, polyolefin waxes, Fischer-Tropsch waxes, fatty acid esters of pentaerythritol, polar synthetic waxes (for example oxidized polyolefin waxes or grafted polyolefin waxes) or other waxes, as well as other substances that are also known as additives for polyamides.
  • EBS, erucamide, long-chain esters of pentaerythritol and oxidized polyolefin waxes are preferred.
  • the carrier preferably polymeric carrier, ideally has a melting point which is lower than the melting point of the polyamide to be processed. This enables, on the one hand, the gentle and energy-saving introduction of the additives into the carrier during the production of the pre-concentrate and, furthermore, it also simplifies the introduction into the polyamide.
  • the stabilizing components during the production of the polyamide, ie the monomer mixture. This enables very good mixing without an additional mixing process, which reduces manufacturing costs and times.
  • the additives and / or aggregates mentioned can, however, also be used separately in the process according to the invention, for example by a separate metering in during the production of polyamides stabilized according to the invention.
  • polyamides are polymers with recurring carbonamide groups -CO-NH- in the main chain. You educate yourself
  • Polyamides are available in a wide variety by varying the monomer components. The most important representatives are aliphatic polyamides, for example polyamide 6 from e-caprolactam, polyamide 6.6 from hexamethylenediamine and adipic acid, polyamide 6.10 and 6.12, polyamide 10.10, polyamide 12.12, polyamide 11, polyamide 12, PACM-12 and polyamide 6-3-T, PA4.6 and partially aromatic polyamides (polyphthalamides PPA), such as PA6T, PA6T / 6I or PA6T / 6.6.
  • impact-modified polyamides can also be used, this encompassing both grafted polyamides and mixtures of polyamides with modifying components (such as rubber-elastic polymers).
  • Impact modified polyamides to be used in the context of the present invention are, in particular, polyamides compounded with impact modifiers, elastomers and / or rubbers.
  • impact modifiers examples include EPM or EPDM rubbers, elastomeric copolymers of ethylene and acrylic monomers, ABS, ASA, NR, SES, SEBS or SIS elastomers, butadiene-based elastomers, isoprene-based elastomers, silicone rubbers and mixtures thereof.
  • elastomeric impact modifiers are present in the mixing ratios with the polyamide known to the person skilled in the art.
  • polyamides can also be stabilized, for example further copolyamides or copolymers of polyamides with other segments, for example with polyesters. It is also possible to stabilize blends of different polyamides and blends of polyamides with other polymers. Polyamide 6, polyamide 6.6 and copolyamides made from polyamide 6 and polyamide 6.6 are particularly preferred.
  • the present invention provides a system that can safely stabilize polyamides over a wide temperature range, this temperature range including temperatures below 150 ° C and also temperatures of 150 ° C or more. The temperature range of 150 ° C or higher extends in particular over temperatures of 160 ° C or higher, including 170 ° C.
  • the present invention thus makes it possible to achieve stabilization over the desired temperature range (100 ° C. to 170 ° C.), copper compounds and halogen compounds being dispensed with, while at the same time the high-temperature treatment described in the prior art for creating a barrier layer is omitted can.
  • Stabilized polyamide compositions of this aspect of the present invention therefore preferably comprise, as stabilizers, exclusively the copper and halogen-free systems for temperature stabilization described here. Nevertheless, even within the scope of the present invention, in areas of application that allow this, the use of such components is not excluded. So, as shown in particular by the following experimental data, an overall improved system is made available, so that significant extensions of the stabilization periods can also be realized.
  • the polyalcohols can also be combined with copper stabilizers, preferably based on copper complexes (particularly preferably based on copper complexes in combination with nonionic halogen-containing synergists).
  • copper stabilizers preferably based on copper complexes (particularly preferably based on copper complexes in combination with nonionic halogen-containing synergists).
  • This also allows improved long-term stabilization even at temperatures of over 160 ° C. In this case, too, an upstream sealing process for forming a protective layer is not required.
  • this combination allows formulations to be designed with low copper and halogen contents in the material, so that the electrical properties of the corresponding materials are only slightly or not negatively influenced at all. This is especially true when copper complexes and organic halogen compounds are used, since these have the least (disadvantageous) effect on the electrical properties.
  • the copper stabilizers to be used optionally according to the invention can be chosen freely. Typical examples include two essential components, namely a mixture of copper compounds and special halogen-containing compounds (also referred to here as synergists).
  • the copper compound used can be any copper salt (Cul, CuBr, copper acetate, CuCN, copper stearate, ...) or any other copper compound such as CuO, CU2O, copper carbonate or any complex of copper.
  • the synergist to be used according to the invention is a halogen-containing component, such as a halogenated polymer, an alkali or alkaline earth salt (such as Kl, KBr, etc.), or an organic compound with halogen substituents, such as halogen-containing aromatic or aliphatic phosphates.
  • a halogen-containing component such as a halogenated polymer, an alkali or alkaline earth salt (such as Kl, KBr, etc.), or an organic compound with halogen substituents, such as halogen-containing aromatic or aliphatic phosphates.
  • the amounts of copper and halogen in the polyamide are selected depending on the desired use of the polyamide and the desired additional stabilization.
  • the amount of copper used is not limited as long as the mechanical properties of the polyamide are not adversely affected.
  • additional copper stabilizers are only optionally used in small amounts in order to achieve particularly good stabilization.
  • amounts of copper ranging from 1 to 1000 ppm Cu, preferably 3 to 200 ppm Cu, more preferably 5 to 150 ppm Cu are used.
  • the amounts of copper used will normally be in the lower ranges, that is to say preferably 200 ppm or less, in particular 150 ppm or less less, more preferably 100 ppm, 75 ppm, or 50 or less.
  • the amounts of synergist used (in each case based on ppm halogen) thus result from the ratios disclosed above.
  • the amount added for the synergist is not subject to any particular restriction. However, additions of more than 1% generally do not lead to any improvement in the stabilizer effect.
  • the amounts used are typically in the range from 10 to 10,000 ppm. Preferred amounts are in the range of 30 to 2000 ppm, more preferably 50 to 1500 ppm.
  • Optional copper complexes to be used according to the invention are complexes of copper with ligands such as triphenylphosphines, mercaptobenzimidazoles, glycine, oxalates and pyridines.
  • ligands such as triphenylphosphines, mercaptobenzimidazoles, glycine, oxalates and pyridines.
  • Chelating ligands such as ethylenediaminetetraacetates, acetylacetonates, ethylenediamines, diethylenetriamines, triethylenetetra-amines, triethylenetetra-amines, can also be used.
  • Examples of the preferred phosphine chelate ligands are 1,2-bis
  • these ligands can be used individually or in combination for complex formation.
  • the syntheses required for this are known to the person skilled in the art or are described in the specialist literature on complex chemistry.
  • these complexes can contain typical inorganic ligands, such as water, chloride, cyano ligands, etc. in addition to the ligands mentioned above.
  • Copper complexes with the complex ligands triphenylphosphines, mercaptobenzimidazoles, acetylacetonates and oxalates are preferred. Triphenylphosphines and mercaptobenzimidazoles are particularly preferred.
  • Preferred complexes of copper used according to the invention are usually formed by reaction of copper (I) ions with the phosphine or mercaptobenzimidazole compounds.
  • these complexes can be obtained by reacting triphenylphosphine with a copper (I) halide suspended in chloroform (G. Kosta, E. Reisenhofer and L. Stafani, J. Inorg. Nukl. Chem. 27 (1965) 2581).
  • it is also possible to reductively react copper (II) compounds with triphenylphosphine in order to obtain the copper (I) addition compounds F.U. Jardine, L. Rule,
  • the complexes optionally used according to the invention can, however, also be prepared by any other suitable method.
  • Suitable copper compounds for preparing these complexes are the copper (I) or copper (II) salts of hydrohalic acids, of hydrocyanic acid or the copper salts of aliphatic carboxylic acids.
  • suitable copper salts are copper (l) chloride, copper (l) bromide, copper (l) iodide, copper (l) cyanide, copper (II) chloride, copper (II) acetate or copper (II) stearate.
  • alkyl or aryl phosphines are suitable.
  • phosphines which can be used according to the invention are triphenylphosphine (TPP), substituted triphenylphosphines, trialkylphosphines and diarylphosphines.
  • TPP triphenylphosphine
  • An example of a suitable trialkyl phosphine is tris (n-butyl) phosphine.
  • the triphenylphosphine complexes are more stable than the trialkylphosphine complexes.
  • Triphenylphosphine is also preferred from an economic point of view because of its commercial availability.
  • Suitable complexes can be represented by the following formulas: [Cu (PPh3) 3X], [Cu2X2 (PPh 3 ) 3 ], [Cu (PPh3) X] 4 and [Cu (PPh3) 2X], where X is selected from CI, Br, I, CN, SCN or 2-MBI.
  • Complexes which can optionally be replaced according to the invention can, however, also contain further complex ligands.
  • Examples are bipyridyl (e.g. CuX (PPh3) (bipy), where X is CI, Br or I), biquinoline (e.g. CuX (PPhb) (biquin), where X is CI, Br or I) and 1,10-phenanthroline, o-phenylenebis (dimethylarsine), 1,2-bis (diphenylphosphino) ethane and terpyridyl.
  • the copper salt optionally to be used according to the invention can be any desired copper salt.
  • Salts of monovalent or divalent copper with inorganic or organic acids are preferred.
  • suitable copper salts are the copper (I) salts such as Cul, CuBr, CuCl or CuCN, copper (II) salts such as CuCh, CuBr2, Cuh, copper acetate, copper sulfate, copper stearate, copper propionate, copper butyrate, copper lactate, copper benzoate or copper nitrate, as well the ammonium complexes of the salts mentioned above.
  • copper (I) salts such as Cul, CuBr, CuCl or CuCN
  • copper (II) salts such as CuCh, CuBr2, Cuh, copper acetate, copper sulfate, copper stearate, copper propionate, copper butyrate, copper lactate, copper benzoate or copper nitrate, as well the ammonium complexes of the salts mentioned above.
  • compounds such as copper acetylacetonate or copper EDTA can also be used. It is also possible to use mixtures of different copper salts. If necessary, copper powder can also
  • the synergist optionally to be used according to the invention for the copper components is not restricted, as described above; in addition to alkali halides, in particular Kl and KBr, halogenated polymers, organic compounds with halogens as substituents, such as aromatic halogen-containing compounds, such as brominated polystyrenes or poly (pentabromobenzyl) are preferred ) acrylates and also halogen-containing aromatic and aliphatic phosphates or phosphonate esters, such as tris (haloaromatic) phosphates or phosphonate esters, e.g. tris (2,4-dibromophenyl) phosphate, tris (2,4-dichlorophenyl) phosphate and T ris (2,4,6 -tribromophenyl) phosphate.
  • alkali halides in particular Kl and KBr
  • halogenated polymers organic compounds with halogens as substituents, such as aromatic
  • halogen-containing aliphatic phosphates are tris (halohydrocarbyl) phosphates or phosphonate esters. Tris (bromohydrocarbyl) phosphates (brominated aliphatic phosphates) are preferred. In particular, in these compounds no hydrogen atoms are bonded to an alkyl carbon atom which is in the alpha position to a carbon atom connected to a halogen. This means that no dehydrohalogenation reactions can occur.
  • Example compounds are Tris (3-bromo-2,2 bis (bromomethyl) propyl) phosphate, T ris (dibromoneopentyl) phosphate, T ris (trichloroneopentyl) phosphate,
  • T ris chlorodibromoneopentyl phosphate and T ris (bromodichloroneopentyl) phosphate.
  • Tris dibromoneopentyl phosphate and tris (tribromoneopentyl) phosphate are preferred.
  • halogenated, in particular brominated, polystyrenes which are substituted by bromine on the aromatic nucleus are particularly preferred here.
  • the present invention achieves the desired stabilization, however, through the use of the essential components defined in the claims and above, so that the present invention in particular also enables work without copper-containing and without halogen-containing components.
  • the polyamide compositions stabilized by the present invention are therefore free from copper-containing components / compounds; or free from halogen-containing compounds, in particular free from halides of alkali and / or alkaline earth elements; or free from copper-containing components / compounds and free from halogen-containing compounds, in particular free from halides of alkali and / or alkaline earth elements.
  • halogens especially bromine and chlorine, but also iodine, considered to be harmful to electrical components due to the interactions of the halide anions with intermetallic phases. Therefore, a requirement to reduce the halogen content has become widespread in the electrical and electronics industry.
  • the present invention uses halogen-free stabilizers, so that there are no problems here.
  • halogen-containing stabilizers are used in the context of the present invention (as additional stabilizers, for example to produce specific property profiles), the amounts used are so small that no problems with regard to electrocorrosion are to be feared in these embodiments either, because the good Effectiveness can be dosed low, so that appropriate limit values can be met.
  • polyamide was compounded in a conventional manner with the stabilizers mentioned, either directly or as a pre-concentrate in a carrier, and the mechanical and other properties to be tested were evaluated on test specimens. The aging conditions are given in each case.
  • a polyamide 6.6 from BASF was used (Ultramid A27 E).
  • the compounding took place with a twin screw extruder from Leistritz ZSE27MAXX - 48D.
  • the additives were metered in gravimetrically during compounding.
  • the compound was produced on a “Demag Ergotech 60 / 370-120 concept” injection molding machine to determine the mechanical parameters (ISO 527) and impact strength (ISO 179/1 part).
  • test rods were stored at the temperatures mentioned in the examples in hot air ovens.
  • the E-modulus [MPa], tensile strength [MPa] (elongation [%]) and breaking stress [MPa] (elongation [%]) were measured in a tensile test according to ISO 527 using a static Zwick Z010 materials testing machine.
  • Irganox 1098 N, N'-hexane-1,6-diylbis (3- (3,5-di-tert-butyl-4 hydroxyphenylpropionamide))
  • Irgaphos 168 Tris- (2,4-di-tert-butylphenyl) phosphite
  • Naugard 445 4,4'-bis (a, a-dimethylbenzyl) diphenylamine
  • Iron oxalate was used in the form of a 5% masterbatch of iron (II) oxalate dihydrate in polyamide 6.
  • Copolymer A ethylene-methyl acrylate copolymer
  • Copolymer B ethylene-butyl acrylate copolymer
  • Copolymer C ethylene-vinyl acetate copolymer
  • Copolymer D ethylene-acrylic acid copolymer
  • Filler A calcined silica.
  • Filler B montmorillonite.
  • Filler C boehmite
  • Filler D glass spheres with a particle size in the range 35 ⁇ m
  • Table 1 Stabilization of polyamide 6.6. unreinforced, heat aging at 150 ° C
  • the pre-concentrates were each produced on a Leistritz ZSE 27 MAXX 48D twin-screw extruder at 100 ° C. to 180 ° C. (in a corresponding temperature profile) with a throughput of 10 kg / h.
  • Table 2a Evaluation of the formation of deposits in polyamide 6.6 after aging at 150 ° C. when using various stabilizers according to the invention and in comparative examples:
  • polyols tend to migrate and bloom during heat storage. This effect was observed when using secondary aromatic amines alone or when using Copper complex-based stabilizers alone not observed. Although the combination of polyols and secondary aromatic amines according to the invention leads to a significantly increased tendency to migrate and to significantly stronger formation of deposits on the finished part (index in Table 2a increases from rating 3 to rating 7), the stabilizing effect is very good. The same was observed analogously with the combination of polyols with copper-based stabilizers.
  • the example according to the invention obtained by direct addition of dipentaerythritol and Naugard 445 shows increased deposit formation (rating 7), but is excellent with regard to heat stabilization.
  • the present invention aims to solve this problem. It is therefore a further decisive additional object of the invention to significantly reduce this increased tendency to migrate, since the practicality would otherwise be severely restricted. It was found that the use of a suitable polymeric preconcentrate can significantly reduce the tendency of additives according to the invention to migrate in unreinforced polyamides during hot storage. As the results in Table 2a show using a pre-concentrate without filler, the selection of the polymeric carrier is very important for success in terms of reducing the tendency to migrate.
  • the flow properties can be designed in such a way that, for example, injection molding is very good and with excellent flow properties.
  • a kit is made available that enables different requirements to be addressed in a targeted manner.
  • Both the selection of the polymeric carrier material, the selection of the filler / reinforcing material and the concentration of the components in the pre-concentrate are important influencing factors with regard to the results to be achieved, as the results shown show.
  • Table 2b Stabilization of polyamide 6.6 unreinforced, especially with additives according to the invention in the form of preconcentrates; Heat aging at 150 ° C
  • the flowability of the variants was determined using HKR (high pressure capillary viscometer).
  • the results show that the apparent viscosity relevant for the injection molding process (at a shear rate of 1000s -1 ) and thus the flowability of the resulting polyamide materials even through the addition of fibers or other fillers in the pre-concentrate (VK9 contains 30% glass fibers) remains at the same level and not is deteriorated in comparison to variants without the addition of fillers.
  • the pre-concentrates with reinforcing materials such as glass fibers or carbon fibers can also be used for processing the resulting polyamide materials in injection molding and extrusion.
  • Example 3 The additives listed in Table 3 were compounded with PA 6.6 and the time was determined until the tensile strength fell to 90% of the initial value.
  • the use of the polyol component improves the flow properties, even when using glass fibers or glass spheres in the pre-concentrate (to prevent migration in the finished workpiece), so that also with regard to processing / shaping due to the use of fibers or balls in the pre-concentrate (which leads to a certain proportion of fibers or balls in the compound) no disadvantages can be observed.
  • Example 4 The additives listed in Table 4 were compounded with PA 6.6 and the time was determined until the tensile strength after heat aging drops to 90% of the initial value.
  • the desired long-term stability of the polyamide materials is achieved even at higher temperatures in the range from 100 to 170 ° C if, instead of a higher aging temperature (to form the protective layer), a method is used in which the compound is produced at the same time glass fibers and / or fillers are added to the polyol in the melt (see Table 4).
  • glass fibers or other fillers alone have a positive effect on the long-term stability of the materials, but this is comparatively low and is usually not sufficient on its own to meet the high requirements with regard to metal replacement in practice, especially in the automotive sector.
  • Table 5 shows that even when using a filler in particle form (that is, no fiber form), a significant improvement in heat stability can be obtained, since the polyol component again shows an unexpected synergistic effect with the reinforcing component. However, this synergistic effect is clearly more pronounced when glass fibers are used and is even more evident with longer storage times. It is particularly important here that, according to the invention, the tensile strength values are applied at a high level over a long period of time, while a significant reduction occurs only with filler but also only with glass fibers, in particular with very long heat aging times (which are more representative of the actual requirements during use ).
  • Example 6 The additives listed in Table 6 were compounded with PA 6.6 and the time determined for the tensile strength to drop to 90% of the initial value.
  • the stabilizers typical for polyamides have no effect. Even with copper-based antioxidants, the effect is only very slight at temperatures of 200 ° C and above. In the case of polyamide compositions with simultaneous use of a polyalcohol, it becomes clear at these very high temperatures that the polyalcohol is decisive for the effect. Additions of further stabilizers do not lead to an extension of the stabilization times.
  • Table 7 Stabilization of polyamide 6.6 reinforced with glass fibers; Heat aging at 150 ° C
  • Test plaques 3 ⁇ 5 cm and 3 mm thick were produced on the injection molding machine from the compositions described in Table 8, and the CTI values particularly relevant for electrical applications were measured in accordance with the IEC-60112 standard.

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

Abstract

La présente invention concerne un procédé de stabilisation à long terme de polyamides et l'utilisation d'une composition d'additif spécifique pour la stabilisation à long terme de polyamides.
EP21700691.5A 2020-01-09 2021-01-11 Matériaux polyamides ayant des caractéristiques de performance à long terme améliorées Pending EP4087896A1 (fr)

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DE4112324A1 (de) 1991-04-16 1992-10-22 Basf Ag Stabilisierte thermoplastische teilaromatische polyamidformmassen
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EP3093312A1 (fr) 2015-05-12 2016-11-16 LANXESS Deutschland GmbH Masses de formage thermoplastiques
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JP7478243B2 (ja) 2024-05-02
US20230120837A1 (en) 2023-04-20

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