EP4392477A1 - Flammgeschützte, teilaromatische polyamide - Google Patents

Flammgeschützte, teilaromatische polyamide

Info

Publication number
EP4392477A1
EP4392477A1 EP22768722.5A EP22768722A EP4392477A1 EP 4392477 A1 EP4392477 A1 EP 4392477A1 EP 22768722 A EP22768722 A EP 22768722A EP 4392477 A1 EP4392477 A1 EP 4392477A1
Authority
EP
European Patent Office
Prior art keywords
polyamide
acid
weight
units
mol
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
EP22768722.5A
Other languages
German (de)
English (en)
French (fr)
Inventor
Christian Schubert
Samuel Clark LIGON
Botho Hoffmann
Sabyasachi Gaan
Nikita DRIGO
Muhammad Rashid NAZIR
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.)
EMS Chemie AG
Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
Original Assignee
EMS Chemie AG
Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
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 EMS Chemie AG, Eidgenoessische Materialprufungs und Forschungsanstalt EMPA filed Critical EMS Chemie AG
Publication of EP4392477A1 publication Critical patent/EP4392477A1/de
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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

Definitions

  • the present invention relates to inherently flame-resistant, partially aromatic polyamides based on aliphatic diamines, aromatic dicarboxylic acids, partially containing phosphorus, and optionally other polyamide-forming components.
  • the invention also relates to flame-retardant molding compositions based on inherently flame-resistant, partially aromatic polyamides. Both the polyamides and the molding compositions produced from them have good flame retardancy and good mechanical properties. These molding compounds are suitable for the production of particularly thin-walled moldings for the electrical and electronics industry, such as housings, housing components or connectors.
  • the invention relates to the use of the polyamides and polyamide molding compounds according to the invention for the production of moldings, in particular components for the electrical and electronics industry and for the automobile industry.
  • plastics For some uses, high demands are placed on plastics with regard to their flame-retardant properties. Because of the risk of short circuits, it is essential that plastics are flame-retardant, particularly when used in electrical or electronic devices.
  • plastics with a reactive flame retardant are also used, i.e. the flame retardant is part of the plastic and was chemically bonded to it during polymerisation.
  • flame-retardant additives include nitrogen-based compounds such as melamine and urea, brominated polystyrenes, and organophosphorus compounds.
  • Another essential requirement for plastics are good mechanical properties, which can be further improved by fiber reinforcement, among other things.
  • the prior art contains a number of examples of glass-fiber-reinforced, flame-retardant molding compositions. Achieving fire protection class UL 94 V0 represents a particular challenge for glass fiber reinforced polyamide molding compounds.
  • EP 1 613 698 A1 relates to halogen-free, flame-retardant molding compositions based on partly aromatic, partly crystalline polyamides which contain salts of phosphinic acids as flame retardants. Because of their dimensional stability at high temperatures and the favorable fire these molding compounds are suitable for the production of thin-walled moldings for the electrical and electronics industry.
  • the particulate flame retardants used lead to a reduction in the mechanical properties, in particular with regard to the stress at break, the elongation at break, the impact and notched impact properties, a deterioration in the surface quality and corrosion of the plant parts used for production and processing.
  • CN 101 735 455 A describes a process for the preparation of aromatic polyoxadiazoles from terephthalic acid, hydrazine and modified isophthalic acid in a solvent and flame-resistant, high-temperature-resistant fibers wet-spun therefrom.
  • the modified isophthalic acid has chloro, bromo, or diphenylphosphine oxide or diphenylphosphine sulfide substituents.
  • US Pat. No. 4,837,394 relates to electrostatic toner particles based on a polyester resin which, as a monomer, contains, inter alia, a dimethyl isophthalate provided with a phosphonium substituent.
  • the quaternary phosphonium groups act as charge carriers in the toner particles. Due to the homogeneous distribution of the charge carriers, a very low content of quaternary phosphonium groups in the range from 10' 9 to 10' 4 mol/g is already sufficient to implement an electrostatographic imaging process. However, this does not achieve adequate flame protection.
  • US Pat. No. 3,108,991 discloses linear polyamides based on bis(aminoalkyl)alkylphosphines and aliphatic or aromatic dicarboxylic acids and aliphatic diamines and bis(carboxyalkyl)alkylphosphine oxides.
  • the polyamides described are soluble in cold or warm water and have low softening points.
  • US 2,646,420 relates to oriented fibers based on linear condensation polymers containing phosphorus in the polymer chain.
  • the fibers also have good mechanical properties, in particular high green strength and good resilience.
  • the phosphorus-containing monomer used is bis(carboxyphenyl)methylphosphine oxide, which is condensed with various glycols or decanediamine.
  • WO 2018 071790 A1 discloses flame-retardant polyamides that contain phosphorus in the polymer chain.
  • the bis(4-methoxy- carbonylphenoxy)phenylphosphine oxide is produced from methylparaben and phenylphosphonic acid dichloride.
  • the reaction of this phosphorus-containing dicarboxylic acid with m-xylylenediamine (MXDA) is described.
  • MXDA m-xylylenediamine
  • JP11286545A describes phosphorus-containing copolyamides with a high glass transition temperature, which can be prepared by polycondensation in an inert solvent at temperatures of 50 to 200.degree.
  • 2,5-Dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphinic acid and derivatives thereof are mentioned as the phosphorus-carrying monomer.
  • the copolyamides based on the dicarboxyphenylphosphinic acids mentioned and the diamine 4,4'-oxydianiline and isophthalic acid as a further dicarboxylic acid have glass transition temperatures in the range from 240 to 276.degree. Therefore, these polyamides cannot be polycondensed in the melt.
  • the polyamides and polyamide molding compounds according to the invention should preferably have a fire protection classification V0 according to UL94 for specimens with a thickness of 0.35 to 3.2 mm, in particular 0.5 mm.
  • Formula 1 Formula 2 Formula 3 where the substituents R1, R2 are each independently C1 - C8-alkyl or aryl and the substituents R3, R4, R5 are each independently H, alkyl, aryl, F, CI, Br or P(R1)( R2) are O;
  • semi-crystalline polyamides In addition to a glass transition temperature, semi-crystalline polyamides have a pronounced melting point and show in dynamic differential calorimetry (DSC) according to ISO 11357 (2013) at a heating rate of 20 K/min provides a heat of fusion of at least 15 J/g, more preferably at least 20 J/g, most preferably in the range of 25 to 80 J/g.
  • DSC dynamic differential calorimetry
  • F a,w-aminocarboxylic acids, lactams. It is preferred if the total diamines used and the total dicarboxylic acids used in the polyamide X in a molar ratio of 1.06:1 to 1:1.06, particularly preferably from 1.03:1 to 1:1.03 and particularly preferably in a molar ratio of 1.01:1 :1.01 are present in the polyamide X.
  • a further preferred embodiment of the present invention provides that the diamines D are selected from the group consisting of m-xylylenediamine (MXDA), p- xylylenediamine (PXDA) and mixtures thereof.
  • Diamine D is particularly preferably selected as m-xylylenediamine.
  • a further preferred embodiment of the present invention provides that the aliphatic dicarboxylic acids E are selected from the group consisting of cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, adipic acid, 1,7-heptanedioic acid, 1,8- Octanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid, 1,15-pentadecanedioic acid, 1,16- hexadecanedioic acid, 1,17-heptadecanedioic acid, 1,18-octadecanedioic acid, and mixtures thereof.
  • the aliphatic dicarboxylic acids E are particularly preferably selected from the group consisting of dicarboxylic acids having 6 to 18 carbon atoms, in particular adipic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid, cyclohexane-1 ,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid and mixtures thereof.
  • dicarboxylic acids having 6 to 18 carbon atoms in particular adipic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid, cyclohexane-1 ,3-dicarboxylic acid, cyclohexane-1,4-dicarbox
  • the polyamides X can contain at least one monofunctional carboxylic acid G1 or monofunctional amine G2 as monofunctional regulator G in copolymerized form.
  • the monofunctional regulators G are used for the end-capping of the polyamides produced according to the invention.
  • all monocarboxylic acids G1 which are capable of reacting with at least some of the available amino groups under the reaction conditions of the polyamide condensation are suitable.
  • Suitable monocarboxylic acids G1 are aliphatic monocarboxylic acids, alicyclic monocarboxylic acids and aromatic monocarboxylic acids.
  • the aliphatic diamines are selected from the group consisting of 1,6-hexanediamine, 2-methyl-1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,3-bis(aminomethyl)cyclohexane (BAC);
  • the diamines containing aromatic moieties are selected from the group consisting of m-xylylenediamine, p-xylylenediamine, and mixtures thereof;
  • the polyamide X is a polyamide in which the at least one further polyamide unit is selected from the group AB, AE and F, the content of the polyamide unit AC being 1 to 99 mol %, preferably 10 to 90 mol%, particularly preferably 10 to 60 mol% and the sum of the contents of the polyamide units AB, AE, and F being 1 to 99 mol%, preferably 10 to 90 mol%, particularly preferably 40 to 90 mol% , in each case based on the sum of the polyamide units AB, AC, AE and F.
  • a polyamide X which comprises at least the polyamide units AB, AC and AE and where the content of the polyamide unit AC is 1 to 99 mol%, preferably 10 to 90 mol%, particularly preferably 10 to 60 mol% and where the Content of the polyamide units AB or AB and AE is 1 to 99 mol%, preferably 10 to 90 mol%, particularly preferably 40 to 90 mol%, based in each case on the sum of the polyamide units AB, AC and AE.
  • the polyamide X is a polyamide which comprises at least the polyamide units AB and AC, and the monomer units A, B and C are preferably derived from the following molecules, which are amidically bound in the polyamide X:
  • A Acyclic aliphatic diamine selected from the group consisting of 1,6-hexanediamine, 1,10-decanediamine, 1,3-bis(aminomethyl)cyclohexane (BAC);
  • Aromatic non-phosphorus dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, and mixtures thereof;
  • aromatic dicarboxylic acid selected from the group consisting of 3,5-dicarboxyphenyldiphenylphosphine oxide, 3,5-dicarboxyphenyldimethylphosphine oxide, 3,5-dicarboxyphenyldiethylphosphine oxide, 2,4-dicarboxyphenyldiphenylphosphine oxide, 2,4-dicarboxyphenyldimethylphosphine oxide, 2,4-dicarboxyphenyldiethylphosphine oxide.
  • the aromatic dicarboxylic acids B are selected from the group consisting of terephthalic acid or a mixture of terephthalic acid and isophthalic acid.
  • a polyamide X is preferred which comprises at least the polyamide units AB and AC and where the polyamide units AB consist of
  • polyamide units AB which are derived from terephthalic acid in combination with hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane and/or or derive 1.10-decanediamine,
  • polyamide units AB which are derived from isophthalic acid in combination with hexamethylenediamine, 1,3-bis-(aminomethyl)cyclohexane and /or derive 1.10-decanediamine, where the parts by weight of components (a1) and (a2) together add up to 100 parts by weight, based on the polyamide units AB.
  • the polyamide X consists exclusively of the polyamide units AC and AB and/or AE.
  • the polyamide X is therefore the systems AB/AC, AC/AE or AB/AC/AE, which can also contain monofunctional regulators G as further components.
  • the content of polyamide units AC is preferably 1 to 99 mol %, particularly preferably 10 to 90 mol % and particularly preferably 10 to 60 mol %, and the content of polyamide units AB and/or AE is preferably 1 to 99 mol %. , particularly preferably 10 to 90 mol% and particularly preferably 10 to 40 mol%, based in each case on the sum of the polyamide units AB, AC and AE.
  • the polyamides X are preferably partially crystalline polyamides which have an enthalpy of fusion of at least 15 J/g, particularly preferably at least 20 J/g.
  • the polyamide X in high molecular weight or post-condensed form preferably has a solution viscosity r
  • the polyamides X preferably have a phosphorus content of at least 1.0% by weight, particularly preferably a phosphorus content in the range from 1.5 to 7% by weight and particularly preferably in the range from 1.7 to 4.0% by weight.
  • polyamide X preferably comprises a polycondensation reaction between at least one aromatic phosphorus-free dicarboxylic acid B and/or an aliphatic dicarboxylic acid E, at least one phosphorus-containing aromatic dicarboxylic acid C according to formula 1, 2 and/or 3, where the substituents R1, R2 are each independently C1 - C8-alkyl or aryl and the substituents R3, R4, R5 are each independently H, alkyl, aryl, F, CI, Br or P(R1)(R2)O, and at least one aliphatic diamine A and optionally further monomers D and F, if appropriate in the presence of monofunctional regulators G and/or process auxiliaries.
  • Preferred process auxiliaries are inorganic and organic stabilizers, catalysts and defoamers.
  • Preferred catalysts are phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acid, phenylphosphinic acid and/or their salts with monovalent to trivalent cations such as Na, K, Mg, Ca, Zn or Al and/or their esters, such as B. triphenyl phosphate, triphenyl phosphite or tris (nonylphenyl) phosphite. Hypophosphorous acid and its salts, such as sodium hypophosphite, are particularly preferred as catalysts.
  • the polyamide X starting from the monomers A to F in a pressure vessel to form a high molecular weight polymer with a preferred number-average molar mass (Mn) of greater than 3000 g/mol, particularly preferably in the range from 4000 to 20,000 g/mol, or polycondensed to give what is known as a precondensate, which has a lower number-average molar mass (Mn), preferably below 3000 g/mol, particularly preferably in the range from 800 to 2500 g/mol.
  • Mn number-average molar mass
  • the pre-condensate can be converted into a high-molecular polymer by solid-phase and/or melt post-condensation, with a preferred number-average molar mass (Mn) of greater than 3000 g/mol, particularly preferably greater than 4000 g/mol, in particular in the range of 4000 up to 20,000 g/mol.
  • Mn number-average molar mass
  • the precondensates can be post-condensed in the solid phase at temperatures in the range from 150 to 300 °C.
  • the melt post-condensation preferably takes place at temperatures of 300 to 400° C. in an extruder.
  • Mixtures of two or more different precondensates can preferably also be converted into a high molecular weight polyamide by post-condensation.
  • a polyamide X precondensate according to the invention can also be post-condensed together with another precondensate which does not contain the polyamide units AC to give a high molecular weight polyamide X.
  • the invention also includes the provision of a polyamide molding compound FM containing the polyamide X, and at least one filler and/or at least one additive and/or at least one polyamide Y different from polyamide X.
  • Polyamide Y is preferably selected from the group consisting of: Polyamide 6, Polyamide 66, Polyamide 610, Polyamide 612, Polyamide 614, Polyamide 616, Polyamide 1010, Polyamide 1012, Polyamide 1014, Polyamide 1016, Polyamide 11, Polyamide 12, Polyamide 6 /12, polyamide 6I, polyamide 9T, polyamide 10T, polyamide 6T/6I, polyamide 6T/66, polyamide 6T/10T or mixtures thereof.
  • Polyamides 6T/6I, 6T/66, 6T/10T and mixtures thereof are very particularly preferred as polyamide Y.
  • the polyamide molding composition FM contains the following components or preferably consists of the following components:
  • At least one additive S different from X and T 0.01 to 50% by weight of at least one additive S different from X and T; where components S, T and X together add up to 100% by weight.
  • the polyamide molding compound FM contains the following components or preferably consists of the following components:
  • the polyamide Y is selected from the group consisting of polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 616, polyamide 1010, polyamide 1012, polyamide 1014, polyamide 1016, polyamide 11, polyamide 12, polyamide 6/12, polyamide 6I, polyamide 9T, polyamide 10T, polyamide 6T/6I, polyamide 6T/66, polyamide 6T/10T or mixtures thereof.
  • component T is contained in the polyamide molding composition FM at 10 to 60% by weight, more preferably at 20 to 55% by weight and particularly preferably at 25 to 50% by weight, with these amounts relate to the total of components X, T, S or the total of components P, T, S or the total weight of the polyamide molding composition FM.
  • the glass fibers used have a cross-sectional area that is either circular (or synonymously round) or non-circular (or synonymously flat), in the latter case the measurement ratio of the major cross-sectional axis to the minor cross-sectional axis is at least 2, preferably in the range of 2 to 6.
  • Glass fibers can be reinforced with short fibers (e.g. cut glass with a length of 2 to 50 mm) or continuous fibers (long glass or rovings).
  • the glass fibers used according to the invention are short glass fibers with a diameter in the range from 6 to 20 ⁇ m and preferably from 9 to 12 ⁇ m.
  • the glass fibers are in the form of chopped glass with a length of 2 to 50 mm.
  • E and/or S glass fibers are used according to the invention.
  • all other types of glass fiber such as e.g. B. A, C, D, M, R glass fibers or any mixtures thereof or mixtures with E and / or S glass fibers can be used.
  • the sizings customary for polyamide, such as e.g. B. various aminosilane sizings are used, with high-temperature-stable sizings being preferred.
  • Glass fibers with a circular and non-circular cross-section can also be used to reinforce the molding compositions according to the invention, the proportion of flat glass fibers preferably predominating, i.e. making up more than 50% by weight of the total mass of the fibers.
  • the glass fibers can be provided with a size suitable for thermoplastics, in particular for polyamide, containing an adhesion promoter based on an amino or epoxy silane compound.
  • component T is a high-strength glass fiber or so-called S-glass fiber.
  • This is preferably based on the ternary system silica-alumina-magnesia or on the quaternary system silica-alumina-magnesia-calcia, with a composition of 58 to 70% by weight silica (SiO 2 ), 15 to 30% by weight alumina (AI2O3), 5 to 15% by weight magnesium oxide (MgO), 0 to 10% by weight calcium oxide (CaO) and 0 to 2% by weight other oxides such as zirconium dioxide (ZrO 2 ), boron oxide (B 2 O 3 ), titanium dioxide (TiO 2 ), iron oxide (Fe 2 O 3 ), sodium oxide, potassium oxide or lithium oxide (Li 2 O) is preferred.
  • component S is selected from the group consisting of lubricants, heat stabilizers, processing stabilizers, processing aids, viscosity modifiers, antioxidants, agents against heat decomposition and decomposition by ultraviolet light, UV blockers, lubricants and mold release agents, colorants, in particular dyes, inorganic pigments , organic pigments, plasticizers, flame retardants, impact modifiers and mixtures thereof.
  • the polyamide molding compositions FM can also contain flame retardants as additives, the flame retardant additives preferably being halogen-free.
  • Preferred flame retardant additives are phosphinic acid salts and/or diphosphinic acid salts, which are preferably used together with a synergist, in particular a nitrogen-containing synergist and/or a nitrogen- and phosphorus-containing flame retardant, preferably melamine or condensation products of melamine, such as particularly preferably selected from the group: Meiern, melam, melon , reaction products of melamine with polyphosphoric acid, such as melamine polyphosphate, reaction products of condensation products of melamine with polyphosphoric acid, or mixtures thereof.
  • the phosphinic acid salts particular preference is given to the aluminum, calcium or zinc salts of alkyl or dialkylphosphinic acids, in particular aluminum diethylphosphinate.
  • Compounds of monovalent or bivalent copper e.g. salts of monovalent or bivalent copper with inorganic or organic acids or monovalent or bivalent phenols, oxides of monovalent or bivalent copper, or complex compounds of copper salts with ammonia, amines, amides, Lactams, cyanides or phosphines, preferably Cu(I) or Cu(II) salts of hydrohalic acids, hydrocyanic acids or the copper salts of aliphatic carboxylic acids.
  • Lanthanide compounds selected from the group consisting of acetates, fluorides, chlorides, bromides, iodides, oxyhalides, sulfates, nitrates, phosphates, chromates, perchlorates, oxalates, the monochalcogenides of sulfur, selenium and tellurium, carbonates, hydroxides, oxides, trifluoromethanesulfonates , acetylacetonates, alcoholates, 2-ethylhexanoates of the lanthanides lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium and - hydrates of the salts mentioned and - mixtures of the said Links.
  • a preferred embodiment of the heat stabilizer consists of the combination of organic heat stabilizers (especially Irgafos 168 and Irganox 1010), a bisphenol A based epoxy (especially Epikote 1001) and a copper stabilization based on Cul and Kl.
  • organic heat stabilizers especially Irgafos 168 and Irganox 1010
  • a bisphenol A based epoxy especially Epikote 1001
  • a copper stabilization based on Cul and Kl is, for example, Irgatec NC66 or Recylobyk 4371. Heat stabilization based exclusively on Cul and Kl is particularly preferred.
  • Component S can also include impact modifiers, preferably these are selected from the group consisting of polyolefins, polyolefin copolymers, styrene copolymers, styrene block copolymers, ionic ethylene copolymers, which can be partially neutralized by metal ions, and mixtures thereof.
  • the impact modifiers are preferably functionalized.
  • the polyamide molding compositions FM preferably contain 0 to 35% by weight, particularly preferably 5 to 20% by weight, of impact modifiers.
  • the impact modifiers of component S are functionalized by copolymerization and/or by grafting.
  • a compound selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid derivatives and mixtures thereof and/or unsaturated glycidyl compounds is particularly preferably used for this purpose.
  • the proportion by weight of each individual compound used for the functionalization is preferred in the range from 3 to 25% by weight, particularly preferably from 4 to 20% by weight and particularly preferably from 4.5 to 15% by weight, based in each case on the total weight of the functionalized impact modifiers S.
  • 0.2 to 1.0 g of the sample to be determined is dissolved in benzyl alcohol or a mixture of o-cresol and benzyl alcohol at 100 °C and, after adding benzoic acid, with a 0.1 molar tetra-n-butylammonium hydroxide solution titrated.
  • the flammability was tested by vertical burning tests according to UL-94 VB according to IEC 60695-11-10 on specimens measuring 127 x 12.7 x 0.5 mm.
  • the specimens were produced using the compression molding process (Lindenberg hot press, 320 - 330 °C). Before the combustion tests, the test specimens were conditioned for 48 hours in a standard climate at 23 °C and a relative humidity of 50%.
  • the pre-condensates were post-condensed in a Binder VDL53 vacuum oven at 200 °C and 30 mbar in the solid phase for a period of 24 to 120 hours before they were then mixed in a second stage in a microcompounder (Xplore MC 15HT) at 300 to 300 mbar 330 °C were further polycondensed.
  • the microextruder is equipped with two valves and a heated channel that allows material to be recycled into the top of the microextruder. Despite the short length of the screw, residence times of several minutes can be achieved thanks to this closed-loop operation.

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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)
  • Polyamides (AREA)
EP22768722.5A 2021-08-27 2022-08-23 Flammgeschützte, teilaromatische polyamide Pending EP4392477A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH70213/21A CH718926A1 (de) 2021-08-27 2021-08-27 Flammgeschützte, teilaromatische Polyamide.
PCT/EP2022/073369 WO2023025741A1 (de) 2021-08-27 2022-08-23 Flammgeschützte, teilaromatische polyamide

Publications (1)

Publication Number Publication Date
EP4392477A1 true EP4392477A1 (de) 2024-07-03

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EP22768722.5A Pending EP4392477A1 (de) 2021-08-27 2022-08-23 Flammgeschützte, teilaromatische polyamide

Country Status (7)

Country Link
EP (1) EP4392477A1 (ko)
KR (1) KR20240050404A (ko)
CN (1) CN118159586A (ko)
CA (1) CA3229749A1 (ko)
CH (1) CH718926A1 (ko)
MX (1) MX2024002301A (ko)
WO (1) WO2023025741A1 (ko)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3108991A (en) * 1961-08-07 1963-10-29 American Cyanamid Co Water-soluble linear polyamides and compositions containing the same
US4032517A (en) 1975-07-22 1977-06-28 Monsanto Company Phosphorus-containing copolyamides and fibers thereof
JP4092516B2 (ja) 1998-04-01 2008-05-28 日産化学工業株式会社 耐熱性含リンポリアミド共重合体
DE10316873A1 (de) 2003-04-11 2004-11-11 Ems-Chemie Ag Flammgeschützte Polyamidformmassen
TWI413644B (zh) * 2008-01-15 2013-11-01 Nat Univ Chung Hsing 磷系雙胺及其衍生物之製造方法
CN101735455B (zh) 2008-11-14 2012-07-11 无锡华东创新材料研究院 一种专用的芳香族聚噁二唑及其阻燃耐高温聚噁二唑纤维的制备方法
CN106589353A (zh) * 2015-10-14 2017-04-26 上海杰事杰新材料(集团)股份有限公司 阻燃耐高温尼龙共聚物及其制备方法
CA3039054A1 (en) 2016-10-14 2018-04-19 Rhodia Operations Phosphorus based co-monomer for polyamides

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CN118159586A (zh) 2024-06-07
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KR20240050404A (ko) 2024-04-18
CH718926A1 (de) 2023-02-28

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