EP3962978A1 - Polyamide ignifugé - Google Patents

Polyamide ignifugé

Info

Publication number
EP3962978A1
EP3962978A1 EP20721241.6A EP20721241A EP3962978A1 EP 3962978 A1 EP3962978 A1 EP 3962978A1 EP 20721241 A EP20721241 A EP 20721241A EP 3962978 A1 EP3962978 A1 EP 3962978A1
Authority
EP
European Patent Office
Prior art keywords
acid
composition
component
components
flame retardant
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
EP20721241.6A
Other languages
German (de)
English (en)
Inventor
Oliver Steffen Henze
Birte NITZ
Tanja LANGE
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP3962978A1 publication Critical patent/EP3962978A1/fr
Pending legal-status Critical Current

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    • 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
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, 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
    • C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • 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
    • C08L77/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/329—Phosphorus containing acids

Definitions

  • the present invention relates to a composition containing at least one
  • the present invention further relates to a method for the production of such compositions and the use of a composition according to the invention for the production of moldings.
  • Polyamides have a high melt strength and very broad processing ranges. Polyamides are of particular importance industrially because they are distinguished by very good mechanical properties, in particular they have high strength and toughness, good
  • Chemical resistance and high abrasion resistance are used, for example, for setting fishing lines, climbing ropes and carpeting.
  • polyamides are used for the production of packaging films and packaging sleeves.
  • Copolyamides which combine the positive properties of different polyamides, are often used for packaging films and packaging sleeves. Various copolyamides are described in the prior art.
  • EP 0 352 562 describes films made from copolyamides, the copolyamides being produced from e-caprolactam and preferably from 1 to 10 parts by weight of a dimer acid and a diamine.
  • DE 28 46 596 describes moldings made from a copolyamide made from caprolactam, fatty acid dimers and flexamethylenediamine.
  • Polyamide 6 and 6,6 are of particular technical interest because of their excellent properties and can be used in many areas. However, polyamide 6 and 6,6 have very high melting temperatures.
  • WO 2018/050487 A1 describes copolyamides, the copolyamide being produced by polymerizing at least one lactam (A) and one
  • Monomer mixture (M) is. Furthermore, the production of a polymer film (P) containing such copolyamides is described.
  • Polyamide 6 and 6,6 are of particular technical interest because of their excellent properties and can be used in many areas. However, polyamide 6 and 6,6 have very high melting temperatures, which are above the decomposition temperatures of many flame retardants. Flame-retardant also in the setting and processing
  • Polyamides 6 and 6,6 require high temperatures.
  • Other polyamides such as polyamide 12 melt at lower temperatures, but are only available to a limited extent on the market. Accordingly, there is a need to produce flame-retardant polyamides which can be processed at low temperatures and have excellent flame retardancy.
  • one object was to provide materials which have an improved melt strength and thus a broad processing range, especially in the hardness range from 40 to 90D.
  • Another object was to provide materials that have an improved melt strength and thus a broad
  • composition (Z-2) containing at least
  • (B2) contains at least one C4-C12 diamine
  • composition (Z-2) according to the invention contains at least one copolyamide (PA-1).
  • the proportion of the copolyamide (PA-1) in the composition can vary within wide ranges and is, for example, in the range from 5% by weight to 95% by weight, based on the total composition, in particular in the range of 20% by weight 80% by weight, based on the total composition, preferably in the range from 25% by weight to 75% by weight, each based on the sum of components (I) and (II).
  • the present invention also relates to a composition as described above, the proportion of the copolyamide (PA-1) in the composition in the range from 5 to 95% by weight, based on the sum of the
  • At least one copolyamide is understood to mean both precisely one copolyamide and a mixture of two or more copolyamides.
  • the composition (Z2) can contain further polymers, for example further polyamides.
  • the composition (Z2) preferably contains no further polymers besides polyamides or copolyamides.
  • the copolyamide (PA-1) can be obtained according to the invention by polymerizing components (A) of at least one lactam, and (B) a monomer mixture (M) which contains components (B1) at least one C32-C40 dimer acid and (B2) at least one Contains C4-C12 diamine.
  • the ratio of components (A) and (B) used can vary within wide ranges.
  • Suitable copolyamides are described, for example, in WO 2018/050487 A1.
  • the copolyamide (PA-1) can preferably be obtained by polymerizing the components
  • (B2) contains at least one C4-C12 diamine, the percentages by weight of components (A) and (B) each being based on the sum of the percentages by weight of components (A) and (B).
  • component (A) and “at least one lactam” are used synonymously in the context of the present invention and therefore have the same meaning.
  • component (B) and “a monomer mixture (M)”. These terms are also used synonymously in the context of the present invention and therefore have the same meaning.
  • At least one lactam means both exactly one lactam and a mixture of two or more lactams. Precisely one lactam is preferred.
  • the at least one copolyamide is preferably prepared by polymerizing 15 to 84% by weight of component (A) and 16 to 85% by weight of the Component (B), the copolyamide is preferably produced by polymerizing 40 to 83% by weight of component (A) and from 17 to 60% by weight of component (B); the at least one copolyamide is particularly preferably produced by polymerisation from 60 to 80% by weight of component (A) and 20 to 40% by weight of component (B), the
  • Percentages by weight of components (A) and (B) are each based on the sum of the percentages by weight of components (A) and (B).
  • the sum of the percentages by weight of components (A) and (B) is preferably 100% by weight.
  • (A) and (B) refer to the percentages by weight of components (A) and (B) before the polymerization, i.e. when components (A) and (B) have not yet reacted with one another.
  • the weight ratio of components (A) and (B) may change during the polymerization.
  • the copolyamide is produced by polymerizing components (A) and (B).
  • the polymerization of components (A) and (B) is known per se to the person skilled in the art.
  • the polymerization of components (A) with (B) is usually a condensation reaction. During the condensation reaction, the component (A) reacts with those in the component
  • (B) contained components (B1) and (B2) and optionally those below
  • Component (B3) which can also be contained in component (B). Amide bonds form between the individual components.
  • Component (A) is usually at least partially open-chain, that is to say as an amino acid, during the polymerization.
  • Suitable catalysts are all catalysts known to the person skilled in the art, which catalyze the polymerization of components (A) and (B). Such catalysts are known to the person skilled in the art.
  • Preferred catalysts are phosphorus compounds such as sodium hypophosphite, phosphorous acid, triphenylphosphine or triphenylphosphite.
  • the copolyamide is formed, which therefore contains structural units which are derived from component (A) and structural units which are derived from component (B).
  • Building units which are derived from component (B) contain building units which are derived from components (B1) and (B2) and optionally from component (B3).
  • the copolyamide is formed as
  • the copolymer can be a random copolymer, it is also possible that it is a block copolymer.
  • blocks of units which are derived from component (B) and blocks of units which are derived from component (A) are formed. These take turns.
  • structural units derived from component (A) alternate with structural units derived from component (B). This alternation takes place statistically, for example, two units derived from component (B) can be followed by a unit derived from component (A), which in turn is followed by a unit derived from component (B), which then follows a structural unit follows which contains three structural units derived from component (A).
  • the at least one copolyamide (PA-1) is preferably a random copolymer.
  • the present invention therefore also provides a polymer film in which the at least one copolyamide is a random copolymer.
  • the production of the at least one copolyamide preferably comprises the following steps: a) Polymerization of components (A) and (B) to obtain at least one first
  • Copolyamide b) granulating the at least one first copolyamide obtained in step a) to obtain at least one granulated copolyamide, c) extracting the at least one granulated copolyamide obtained in step b) with water to obtain at least one copolyamide extracted, d) drying the copolyamide obtained in step c) obtained at least one extracted copolyamide at a temperature (Tr) to obtain the at least one copolyamide.
  • Tr temperature
  • Suitable reaction conditions are described, for example, in WO 2018/050487 A1.
  • step a) can take place in all reactors known to the person skilled in the art. Stirred tank reactors are preferred. Aids known to the person skilled in the art can also be used to improve the conduct of the reaction, for example defoamers such as
  • PDMS Polydimethylsiloxane
  • step b) the at least one first copolyamide obtained in step a) can be granulated by all methods known to the person skilled in the art, for example by means of strand granulation or underwater granulation.
  • step c) can be carried out by any of the methods known to the person skilled in the art.
  • step c) by-products formed during the polymerization of components (A) and (B) in step a) are usually extracted from the at least one granulated copolyamide.
  • step d) the at least one extracted copolyamide obtained in step c) is dried. Drying methods are known to those skilled in the art. According to the invention, the at least one extracted copolyamide is dried at a temperature (Tr).
  • the temperature (Tr) is preferably above the glass transition temperature (TGc) of the at least one
  • Copolyamide and below the melting temperature (TMc) of the at least one copolyamide.
  • the drying in step d) usually takes place for a period in the range from 1 to 100 hours, preferably in the range from 2 to 50 hours and particularly preferably in the range from 3 to 40 hours.
  • the at least one copolyamide usually has a glass transition temperature (TGc).
  • the glass transition temperature (TGc) is, for example, in the range from 20 to 50 ° C., preferably in the range from 23 to 47 ° C. and particularly preferably in the range from 25 to 45 ° C., determined in accordance with ISO 11357-2: 2014.
  • component (A) is at least one lactam.
  • Lactams are known as such to the person skilled in the art. Lactams having 4 to 12 carbon atoms are preferred according to the invention.
  • lactams are understood to mean cyclic amides which preferably have 4 to 12, particularly preferably 5 to 8, carbon atoms in the ring.
  • Suitable lactams are, for example, selected from the group consisting of 3-aminopropanoic acid lactam (propio-3-lactam; ß-lactam; ß-propiolactam), 4-aminobutanoic acid lactam (butyro-4-lactam; g-lactam; y-butyrolactam), 5- Aminopentanoic acid lactam (2-piperidinone; d-lactam; d-valerolactam), 6-aminohexanoic acid lactam (hexano-6-lactam: e-lactam; e-caprolactam), 7-aminoheptanoic acid lactam (heptano-7-lactam; z-lactam; z- Heptanolactam
  • the lactams can be unsubstituted or at least monosubstituted.
  • they can carry one, two or more substituents on the nitrogen atom and / or on the carbon atoms of the ring, which are independently selected from the group consisting of C5- to C10-alkyl, C5 - to C6-cycloalkyl and C5- to C10-aryl.
  • C5 to C10-alkyl substituents examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.
  • a suitable C5 to C6 cycloalkyl substituent is for example cyclohexyl.
  • Preferred C5 to C10 aryl substituents are phenyl and
  • component (B) is a monomer mixture (M).
  • the monomer mixture (M) contains the components (B1), at least one C32-C40 dimer acid and (B2) at least one C4-C12-diamine.
  • a monomer mixture (M) is understood to mean a mixture of two or more monomers, at least components (B1) and (B2) being contained in the monomer mixture (M).
  • component (B1) and “at least one C32-C40 dimer acid” are used synonymously in the context of the present invention and therefore have the same meaning. The same applies to the terms “component (B2)” and “at least one C4-C12 diamine”.
  • the monomer mixture (M) contains, for example, in the range from 45 to 55 mol%
  • Component (B) preferably contains in the range from 47 to 53 mol% of component (B1) and in the range from 47 to 53 mol% of component (B2) in each case based on the sum of the mol percent of components (B1) and ( B2), preferably based on the total amount of the component (B).
  • Component (B) particularly preferably contains in the range from 49 to 51 mol% of
  • Component (B) can additionally contain a component (B3), at least one C4-C20 diacid.
  • component (B3) and “at least one C4-C20 diacid” are used synonymously in the context of the present invention and therefore have the same meaning.
  • component (B) additionally contains component (B3), it is preferred that component (B) is in the range from 25 to 54.9 mol% of component (B1), in the range from 45 to 55 mol% % of component (B2) and in the range from 0.1 to 25 mol% of component (B3), each based on the total amount of substance of component (B).
  • Component (B) then particularly preferably contains in the range from 13 to 52.9 mol% of component (B1), in the range from 47 to 53 mol% of component (B2) and in the range from 0.1 to 13 mol -% of component (B3), each based on the total amount of substance of component (B).
  • Component (B) then more preferably contains in the range from 7 to 50.9 mol% of component (B1), in the range from 49 to 51 mol% of component (B2) and in the range from 0.1 to 7 mol -% of component (B3), each based on the total amount of substance
  • component (B) also contains component (B3), they add up
  • the monomer mixture (M) can also contain water.
  • component (B1) and (B2) and, if appropriate, (B3) of component (B) can react with one another to give amides. This reaction is known as such to the person skilled in the art. Therefore, component (B) can include components (B1) and (B2) as well
  • Component (B) optionally contain (B3) in completely reacted form, in partially reacted form or in unreacted form.
  • Component (B) preferably contains components (B1) and (B2) and, if appropriate, (B3) in unreacted form.
  • component (B1) is present as the at least one C32-C40 dimer acid and component (B2) as the at least one C4-C12-diamine and, if appropriate, component ( B3) as the at least one C4-C20 diacid.
  • component (B1) is at least one C32-C40 dimer acid.
  • “At least one C32-C40 dimer acid” in the context of the present invention means exactly one C32-C40 dimer acid and a mixture of two or more C32-C40 Dimer acids.
  • Dimer acids are also known as dimer fatty acids.
  • C32-C40 dimer acids are known as such to the person skilled in the art and are usually prepared by dimerizing unsaturated fatty acids. This dimerization can be catalyzed, for example, by clays.
  • Suitable unsaturated fatty acids for producing the at least one C32-C40 dimer acid are known to the person skilled in the art and, for example, unsaturated C16 fatty acids, unsaturated C16 fatty acids and unsaturated C20 fatty acids.
  • Component (B1) is therefore preferably prepared starting from unsaturated
  • Fatty acids selected from the group consisting of unsaturated C16 fatty acids, unsaturated C18 fatty acids and unsaturated C20 fatty acids, the unsaturated C18 fatty acids being particularly preferred.
  • a suitable unsaturated C16 fatty acid is, for example, palmitoleic acid ((9Z) -Flexadeca-9-enoic acid).
  • Suitable unsaturated C18 fatty acids are selected, for example, from the group consisting of petroselinic acid ((6Z) -octadeca-6-enoic acid), oleic acid ((9Z) -octadeca-9-enoic acid), elaidic acid ((9E) -octadeca-9-enoic acid ), Vaccenic acid ((1 1 E) -Octadeca-1 1 - enoic acid), linoleic acid ((9Z, 12Z) -Octadeca-9,12-dienoic acid), alpha-linolenic acid ((9Z, 12Z, 15Z) - octadeca-9 , 12,15-trienoic acid), gamma-linolenic acid ((6Z, 9Z, 12Z) -octadeca-6,9,12-trienoic acid), calendulic acid ((8E, 10E
  • Alpha-eleostearic acid (9Z, 1 1 E, 13E) -octadeca-9,1 1, 13-trienoic acid) and beta-eleostearic acid ((9E, 1 1 E, 13E) -octadeca-9, 1 1, 13-trienoic acid ).
  • Unsaturated cis-fatty acids selected from the group consisting of petroselinic acid ((6Z) - octadeca-6-enoic acid), oleic acid ((9Z) -octadeca-9-enoic acid), elaidic acid ((9E) -octadeca-9-enoic acid) are particularly preferred ), Vaccenic acid ((1 1 E) -Octadeca-1 1 -enoic acid), linoleic acid ((9Z, 12Z) -Octadeca-9, 12-dienoic acid).
  • Suitable unsaturated C20 fatty acids are selected, for example, from the group consisting of gadoleic acid ((9Z) - Eicosa-9-enoic acid), icosenoic acid ((1 1 Z) -Eicosa-1 1-enoic acid), arachidonic acid ((5Z, 8Z, 1 1Z, 14Z) -Eicosa-5,8,1 1, 14-tetraenoic acid) and
  • Timnodonic acid ((5Z, 8Z, 1 1Z, 14Z, 17Z) -Eicosa-5,8,1 1, 14,17-pentaenoic acid).
  • the component (B1) is particularly preferably at least one C36 dimer acid.
  • the at least one C36 dimer acid is preferably produced starting from unsaturated cis-fatty acids.
  • the C36 dimer acid is particularly preferably prepared starting from cis fatty acids selected from the group consisting of petroselinic acid ((6Z) -octadeca-6-enoic acid), oleic acid ((9Z) -octadeca-9-enoic acid), elaidic acid ((9E ) -Octadeca-9-enoic acid), Vaccenic acid ((1 1 U) -Octadeca-11-enoic acid) and linoleic acid ((9Z, 12Z) -Octadeca-9,12- dienoic acid).
  • trimer acids can also form, and residues of unreacted unsaturated fatty acids can also remain.
  • trimer acids The formation of trimer acids is known to the person skilled in the art.
  • component (B1) preferably contains at most 0.5% by weight of unreacted unsaturated fatty acid and at most 0.5% by weight of trimer acid, particularly preferably at most 0.2% by weight of unreacted unsaturated fatty acid and at most 0.2 % By weight trimer acid, based in each case on the total weight of component (B1).
  • Dimer acids are generally, and in particular in the context of the present invention, mixtures which are produced by oligomerization of unsaturated fatty acids. They can be produced, for example, by catalytic dimerization of vegetable, unsaturated fatty acids, the starting materials used in particular being unsaturated C16 to C20 fatty acids.
  • the linkage proceeds primarily according to the Diels-Alder type and, depending on the number and position of the double bonds of the fatty acids used to prepare the dimer acids, the result is mixtures of primarily dimeric products, the cycloaliphatic, linear-aliphatic, branched aliphatic and also between the carboxyl groups Have C6 aromatic hydrocarbon groups. Depending on the mechanism and / or
  • the aliphatic radicals can be saturated or unsaturated and the proportion of aromatic groups can also vary.
  • the radicals between the carboxylic acid groups then contain, for example, 32 to 40 carbon atoms. Fatty acids with 18 carbon atoms are preferably used for the production, so that the dimeric product thus has 36 carbon atoms.
  • the radicals which connect the carboxyl groups of the dimer fatty acids preferably have no unsaturated bonds and no aromatic hydrocarbon radicals.
  • Cie fatty acids preference is given to using Cie fatty acids in the production. Linolenic, linoleic and / or oleic acid are particularly preferably used.
  • Oligomerization Mixtures which mainly contain dimeric, but also trimeric molecules, as well as monomeric molecules and other by-products. Purification is usually carried out by distillation.
  • Commercially available dimer acids generally contain at least 80% by weight of dimeric molecules, up to 19% by weight of trimeric molecules and a maximum of 1% by weight of monomeric molecules and other by-products. It is preferred to use dimer acids of which at least 90% by weight, preferably at least 95% by weight, very particularly preferably at least 98% by weight, consist of dimeric fatty acid molecules.
  • the proportions of monomeric, dimeric and trimeric molecules and other by-products in the dimer acids can be determined, for example, by means of gas chromatography (GC). Before the GC analysis, the dimer acids are converted into the corresponding methyl esters using the boron trifluoride method (compare DIN EN ISO 5509) and then analyzed by GC.
  • GC gas chromatography
  • the fundamental characteristic of "dimer acids” is that their position comprises the oligomerization of unsaturated fatty acids.
  • This oligomerization mainly produces, that is, preferably at least 80% by weight, particularly preferably at least 90% by weight. %, very particularly preferably to at least 95% by weight and in particular to at least 98% by weight of dimeric products. The fact that the oligomerization thus produces predominantly dimeric products, precisely two
  • the dimer acids to be used are available as Flandels products. Examples include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid 0975, Radiacid 0976 and Radiacid 0977 from Oleon, Pripol 1006, Pripol 1009, Pripol 1012, and Pripol 1013 from Croda, Empol 1008, Empol 1012, Empol 1061 and Empol 1062 from BASF SE and Unidyme 10 and Unidyme TI from Arizona Chemical.
  • Component (B1) has, for example, an acid number in the range from 190 to 200 mg KOFI / g.
  • component (B2) is at least one C4-C12-diamine.
  • At least one C4-C12-diamine means in the context of the present invention exactly one C4-C12-diamine as well as a mixture of two or more C4-C12- Diamines.
  • C4-C12 diamine is understood to mean aliphatic and / or aromatic compounds having four to twelve carbon atoms and two amino groups (—NH2 groups). The aliphatic and / or aromatic compounds can be unsubstituted or additionally at least monosubstituted.
  • the aliphatic and / or aromatic compounds are additionally at least monosubstituted, they can carry one, two or more substituents which do not take part in the polymerization of components (A) and (B).
  • substituents are, for example, alkyl or
  • Suitable components (B2) are selected, for example, from the group consisting of 1,4-diaminobutane (butane-1,4-diamine; tetramethylenediamine; putrescine), 1,5-diaminopentane (pentamethylenediamine; pentane-1,5-diamine; cadaverine) , 1, 6-diaminohexane
  • Component (B2) is preferably selected from the group consisting of
  • Tetramethylene diamine pentamethylene diamine, flexamethylene diamine, decamethylene diamine and dodecamethylene diamine.
  • component (B3) optionally contained in component (B) is, according to the invention, at least one C4-C20 diacid.
  • “At least one C4-C20 diacid” in the context of the present invention means both exactly one C4-C20 diacid and a mixture from two or more C4-C20 diacids.
  • C4-C20 diacid is understood to mean aliphatic and / or aromatic compounds having two to eighteen carbon atoms and two carboxy groups (—COOH groups).
  • the aliphatic and / or aromatic compounds can be unsubstituted or additionally at least monosubstituted In the event that the aliphatic and / or aromatic compounds are additionally at least monosubstituted, they can carry one, two or more substituents which are involved in the polymerization of the
  • Components (A) and (B) do not participate.
  • substituents are, for example, alkyl or cycloalkyl substituents. These are known to the person skilled in the art.
  • the at least one C4-C20 diacid is preferably unsubstituted.
  • Suitable components (B3) are, for example, selected from the group consisting of butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), flexanedioic acid (adipic acid), fleptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid
  • Tridecanedioic acid Tridecanedioic acid, tetradecanedioic acid and flexadecanedioic acid.
  • Component (B3) is preferably selected from the group consisting of pentanedioic acid (glutaric acid), flexanedioic acid (adipic acid), decanedioic acid (sebacic acid) and dodecanedioic acid.
  • the composition (Z2) can be prepared, for example, by mixing the individual components, for example the polyamide (PA1) and the flame retardant (F1), for example in a suitable device such as an extruder or a kneader.
  • the composition (Z2) can be positioned under known conditions.
  • further additives such as, for example, further flame retardants or fillers can also be used. Suitable fillers, plasticizers or other flame retardants are known per se to the person skilled in the art.
  • the present invention also relates to a
  • the composition (Z2) contains a flame retardant (F1) selected from the group consisting of melamine cyanurates, magnesium hydroxide and phosphorus-containing flame retardants.
  • F1 flame retardant selected from the group consisting of melamine cyanurates, magnesium hydroxide and phosphorus-containing flame retardants.
  • Mixtures of different flame retardants for example mixtures containing one or more phosphorus-containing flame retardants, are also suitable for the purposes of the present invention.
  • the present invention also relates to a composition as described above, the composition having at least one first phosphorus-containing flame retardant (F1) selected from the group consisting of derivatives of phosphoric acid and derivatives of phosphonic acid and at least one further
  • Phosphorus-containing flame retardant (F2) selected from the group consisting of derivatives of phosphinic acid.
  • Suitable flame retardants are also metal hydroxides, for example.
  • metal hydroxides In the event of a fire, metal hydroxides only release water and therefore do not form any toxic or corrosive smoke gas products.
  • these hydroxides are able to reduce the smoke density in the event of fire.
  • the disadvantage of these substances is that they may promote the hydrolysis of thermoplastic polyurethanes and also influence the oxidative aging of the polyurethanes.
  • the metal hydroxide is particularly preferably selected from the group consisting of
  • compositions according to the invention can also contain phosphorus
  • Phosphorus-containing flame retardants for thermoplastic polyurethanes are used.
  • derivatives of phosphoric acid, derivatives of phosphonic acid or derivatives of phosphinic acid or mixtures of two or more are preferred several of these derivatives are used.
  • the phosphorus-containing flame retardant is liquid at 21 ° C.
  • Organic esters are derivatives of phosphorus-containing acids in which at least one oxygen atom bonded directly to the phosphorus is esterified with an organic radical.
  • the organic ester is an alkyl ester, in another preferred embodiment it is an aryl ester. All hydroxyl groups of the corresponding phosphorus-containing acid are particularly preferably esterified.
  • Suitable organic phosphate esters are, for example, the triesters of phosphoric acid, such as trialkyl phosphates and, in particular, triaryl phosphates, such as, for example, resorcinol bis
  • salts of the respective derivatives are particularly suitable
  • Phosphoric acid phosphonic acid or phosphinic acid, more preferably phosphinate salts.
  • Melamine polyphosphate or diethyl aluminum phosphinate, for example, are suitable for the purposes of the present invention.
  • Flame retardants are used. According to the invention, in principle all known nitrogen-containing flame retardants can be used for thermoplastic polyurethanes.
  • Suitable flame retardants in the context of the present invention are, for example, also melamine derivatives such as, in particular, melamine polyphosphate or melamine cyanurate.
  • the composition in the context of the present invention, it is also possible for the composition to contain mixtures of different flame retardants in addition to the thermoplastic polyurethane, for example a melamine derivative and a derivative of phosphoric acid, or a melamine derivative and a derivative of phosphinic acid or a melamine derivative, a derivative of phosphoric acid and a derivative of phosphinic acid.
  • a melamine derivative and a derivative of phosphoric acid for example a melamine derivative and a derivative of phosphoric acid, or a melamine derivative and a derivative of phosphinic acid or a melamine derivative, a derivative of phosphoric acid and a derivative of phosphinic acid.
  • the melamine derivative can preferably be a melamine cyanurate.
  • the present invention can also relate to a composition which, in addition to the thermoplastic polyurethane, contains, for example, a melamine cyanurate and a derivative of phosphoric acid, or a melamine cyanurate and a derivative of phosphinic acid or a melamine cyanurate, a derivative of phosphoric acid and a derivative of phosphinic acid .
  • the composition according to the invention contains at least one thermoplastic polyurethane, at least melamine cyanurate, at least one first phosphorus-containing flame retardant (F1) selected from the group consisting of derivatives of phosphoric acid and derivatives of phosphonic acid and at least one other Phosphorus-containing flame retardant (F2) selected from the group consisting of derivatives of phosphinic acid.
  • F1 first phosphorus-containing flame retardant
  • F2 Phosphorus-containing flame retardant
  • the composition preferably contains no further flame retardants.
  • the composition according to the invention further preferably contains exactly one melamine cyanurate containing phosphorus
  • Flame retardants (F1) selected from the group consisting of derivatives of
  • Flame retardants (F2) selected from the group consisting of derivatives of
  • the present invention also relates to a composition as described above, the phosphorus-containing flame retardant (F1) being a phosphinate.
  • the present invention also relates to a composition as described above, the phosphinate being selected from the group consisting of aluminum phosphinates or zinc phosphinates.
  • the present invention also relates to a composition as described above, the phosphorus-containing flame retardant (F2) being a phosphoric acid ester.
  • the present invention also relates to a
  • the flame retardant (F1) is selected from the group consisting of resorcinol bis-diphenyl phosphate (RDP), bisphenol A bis (diphenyl phosphate) (BDP), and diphenyl cresyl phosphate (DPK).
  • RDP resorcinol bis-diphenyl phosphate
  • BDP bisphenol A bis (diphenyl phosphate)
  • DPK diphenyl cresyl phosphate
  • the proportion of the flame retardant (F) in the composition is, for example, in the range from 2.5 to 40% by weight based on the total composition, preferably in the range from 5 to 30% by weight based on the total composition, more preferably in Range from 10 to 20% by weight based on the total composition.
  • the present invention accordingly also relates to a composition as described above, the flame retardant (F) being contained in an amount in the range from 2.5 to 40% by weight based on the total composition.
  • the composition can also contain further components, for example also further flame retardants.
  • Suitable additives and flame retardants are known per se to the person skilled in the art and are described, for example, in EP 2878630 B1 or WO 2017/063841.
  • flame retardants can be used in the context of the present invention, it also being possible to use mixtures of the flame retardants mentioned there.
  • Suitable flame retardants are also commercially available organic halogen compounds with synergists or commercially available organic nitrogen compounds or
  • organic / inorganic phosphorus compounds which are used individually or in a mixture with one another.
  • Mineral flame retardant additives such as magnesium hydroxide or Ca-Mg-carbonate flyrate can also be used.
  • Preferred halogen-containing, in particular brominated and chlorinated, compounds are ethylene-1,2-bistetrabromophthalimide,
  • Decabromodiphenylethane tetrabromobisphenol-A-epoxy-oligomer, tetrabromobisphenol-A-oligocarbonate, tetrachlorobisphenol-A-oligocarbonate, polypentabrombenzyl acrylate, brominated polystyrene or brominated polyphenylene ethers.
  • Suitable phosphorus compounds are, for example, the phosphorus compounds disclosed in WO-A 98/17720, preferably red phosphorus, metal phosphinates, in particular aluminum phosphinate or zinc phosphinate, metal phosphonates, in particular aluminum phosphonate, calcium phosphonate or zinc phosphonate, derivatives of 9,10-dihydro-9-oxa -10-phosphaphenanthrene-10-oxides (DOPO derivatives), triphenyl phosphate (TPP), resorcinol bis (diphenyl phosphate) (RDP), including oligomers and bisphenol A bis diphenyl phosphate (BDP) including
  • Oligomers also zinc bis (diethylphosphinate), aluminum tris (diethylphosphinate),
  • RDP diphenyl phosphate
  • BDP bisphenol-A-bis-diphenyl phosphate
  • BDP bisphenol-A-bis-diphenyl phosphate
  • BDP bisphenol-A-bis-diphen
  • melamine or melamine cyanurate are used as nitrogen compounds
  • Reaction products from trichlorotriazine, piperazine and morpholine according to CAS no. 1078142-02-5 e.g. MCA PPM Triazin H F from MCA Technologies GmbHFI, Biel-Benken, Switzerland.
  • Antimony compounds, in particular antimony trioxide or antimony pentoxide, zinc compounds, tin compounds, in particular zinc stannate or borates, in particular zinc borates, are preferred as synergists.
  • Tetrafluoroethylene polymers are added.
  • Flame retardants are particularly preferably brominated polystyrenes such as e.g. Firemaster® PBS64 (Great Lakes, West Lafayette, USA) or brominated phenylene ethers, in each case particularly preferably used in combination with antimony trioxide and / or zinc stannates, as synergists.
  • halogen-free flame retardants are particularly preferred
  • Aluminum tris (diethylphosphinate) in combination with melamine polyphosphate e.g. Melapur® 200/70 from BASF SE, Ludwigshafen, Germany
  • zinc borate e.g. Firebrake® 500 or Firebrake® ZB from RioTinto Minerals, Greenwood Village, USA
  • Aluminum phosphonate hydrate used.
  • aluminum tris (diethylphosphinate) (e.g. Exolit® OP1230 from Clariant International Ltd. Muttenz, Switzerland) (CAS No. 225789-38-8) in combination with melamine polyphosphate (Melapur 200/70) and zinc borate (Firebrake 500) is used as a flame retardant ) used.
  • diethylphosphinate e.g. Exolit® OP1230 from Clariant International Ltd. Muttenz, Switzerland
  • melamine polyphosphate Melapur 200/70
  • zinc borate Ferebrake 500
  • suitable flame retardants are phosphinic acid salts or their polymers.
  • Suitable flame retardants are also nitrogen-containing flame retardants such as
  • Melamine compounds Melamine cyanurates, for example, are suitable
  • Reaction products from preferably equimolar amounts of melamine and cyanuric acid or isocyanuric acid.
  • melamine cyanurate is advantageously used, its
  • Particle size distribution has, for example, ad50 value of less than 4.5 ⁇ m, preferably less than 3 ⁇ m.
  • a d50 value to be the particle size value at which 50% of the particles have a smaller particle size and 50% have a larger particle size.
  • the particle size distribution will
  • the present invention also relates to processes for preparing the compositions according to the invention.
  • compositions the copolyamide and flame retardant and optionally other components of the composition processed in one step.
  • compositions a copolyamide is first produced with a reactive extruder, a belt system or other suitable devices, preferably as granules, into which at least one further flame retardant is then introduced in at least one further working step, or also several working steps.
  • the components are mixed, for example, in a mixing device which is preferably an internal kneader or an extruder, preferably a twin-screw extruder.
  • a mixing device which is preferably an internal kneader or an extruder, preferably a twin-screw extruder.
  • this is introduced Flame retardant liquid at the temperature prevailing downstream in the flow direction after it has been added to the extruder.
  • composition according to the invention can furthermore contain a filler (FS1).
  • a filler FS1
  • the chemical nature and the shape of the filler (FS1) can vary within wide ranges, as long as there is sufficient compatibility with the composition (Z2).
  • the filler (FS1) should be chosen so that the shape and
  • Particle size of the filler allow sufficient miscibility and uniform distribution in the composition.
  • Suitable fillers are, for example, glass fibers, glass spheres, carbon fibers, aramid fibers, potassium titanate fibers, fibers made from liquid-crystalline polymers, organic fibers
  • the filler (FS1) is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, fibers made of liquid-crystalline polymers, metal fibers, polyester fibers, polyamide fibers, organic fibrous fillers and inorganic fibrous fillers.
  • the present invention accordingly also relates to a composition as described above, the filler (FS1) being selected from the group consisting of glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, fibers made from liquid-crystalline polymers, metal fibers, polyester fibers , Polyamide fibers, organic fibrous fillers and inorganic fibrous fillers.
  • the filler (FS1) being selected from the group consisting of glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, fibers made from liquid-crystalline polymers, metal fibers, polyester fibers , Polyamide fibers, organic fibrous fillers and inorganic fibrous fillers.
  • Fibrous fillers are preferred in the context of the present invention. According to a further embodiment, the present invention accordingly also relates to a
  • the filler (FS1) being fibrous.
  • the dimensions of the fillers used can vary within the usual ranges.
  • the filler used preferably has a length in the range from 3 mm to 4 mm and one
  • the present invention accordingly also relates to a composition as described above, the filler (FS1) having a length in the range from 3 mm to 4 mm mm and a diameter in the range from 1 ⁇ m to 20 ⁇ m, each determined in accordance with ASTM D578-98.
  • the fillers for example the fibrous fillers, can be pretreated for better compatibility with the thermoplastic, for example with a
  • Inorganic fibrous fillers are preferably used. When using inorganic fibrous fillers, a greater reinforcement effect and a higher thermal stability are found.
  • the composition can also contain two or more fillers.
  • the proportion of filler (FS1) in the composition is, for example, in the range from 40 to 60% by weight based on the total composition, preferably in the range from 45 to 55% by weight based on the total composition, more preferably in the range of 48 to 52% by weight based on the total composition.
  • the present invention accordingly also relates to a composition as described above, the filler (FS1) being contained in an amount in the range from 40 to 60% by weight based on the total composition.
  • composition 100% by weight unless otherwise stated.
  • the composition can contain further components, for example mold release agents, UV protection, antioxidants or color pigments.
  • the present invention also relates to a method for producing a composition (Z-2).
  • the present invention relates to a method for producing a composition (Z-2) comprising the steps
  • a flame retardant selected from the group consisting of melamine cyanurates, magnesium hydroxide and phosphorus-containing
  • the method according to the invention comprises at least steps (a) and (b).
  • the method can comprise further steps, for example drying steps or Temperature adjustments.
  • further components can also be added, for example the aforementioned auxiliaries and additives.
  • the present invention accordingly relates to a method as described above, wherein the components used are dried, for example at a temperature in the range from 80 to 100.degree.
  • drying can take place at a temperature in the range from 80 to 100 ° C. for a period of 2 to 4 hours.
  • the copolyamide (PA-1) and the flame retardant are mixed in step (b). This can be done in devices known per se to the person skilled in the art,
  • extruder for example in an extruder.
  • Suitable extruders and process conditions are known per se to the person skilled in the art.
  • mixing in an extruder can take place at a temperature in the range from 180 to 240 ° C, preferably at a temperature in the range from 190 ° C to 230 ° C, more preferably at a temperature in the range from 200 ° C to 225 ° C .
  • Suitable residence times in the extruder are, for example, in the range from 5 to 20 minutes, preferably 10 to 15 minutes.
  • Suitable processes for preparing the composition are known per se to the person skilled in the art. In the context of the present invention, methods known per se are usually used for compounding.
  • the composition can be produced in a manner known per se in an extruder, for example in a twin-screw extruder.
  • the temperature is preferably in the range from 160 to 230 ° C.
  • the extruder can be operated, for example, at a speed in the range from 150 to 300 revolutions per minute.
  • the present invention further relates to a composition obtained or obtainable by a method according to the invention.
  • the present invention also relates to the use of the composition according to the invention (Z2) or a composition obtained or obtainable after a
  • composition of the composition (Z-2) can vary within wide ranges.
  • the composition (Z-2) usually contains the
  • Flame retardants in an amount in the range from 2.5 to 40% by weight based on the total Composition, preferably in the range from 5 to 30% by weight based on the total composition, more preferably in the range from 10 to 20% by weight based on the total composition.
  • the present invention accordingly also relates to a composition (Z-2) as described above, the flame retardant (F) being contained in an amount in the range from 2.5 to 40% by weight based on the total composition.
  • the present invention also relates to a composition (Z-3) containing at least
  • Suitable copolyamides (PA-1) and suitable fillers (FS) are those described above.
  • composition of the composition (Z-3) can vary within wide ranges.
  • the composition can also contain two or more fillers.
  • the proportion of filler (FS) in the composition is, for example, in the range from 40 to 60% by weight based on the total composition, preferably in the range from 45 to 55% by weight based on the total composition, more preferably in the range of 48 to 52% by weight based on the total composition.
  • the present invention accordingly also relates to a composition as described above, the filler (FS) being contained in an amount in the range from 40 to 60% by weight based on the total composition.
  • the composition (Z-3) can also contain further components, for example flame retardants or other customary additives.
  • Suitable processes for producing the composition are known per se to the person skilled in the art. In the context of the present invention, methods known per se are usually used for compounding.
  • the present invention also relates to a method for producing a composition (Z-3) comprising the steps
  • A a copolyamide (PA-1), produced by polymerizing at least one lactam, and a monomer mixture (M) which contains components (B1) at least one C32-C40 dimer acid and (B2) at least one C4-C12 diamine ; and
  • the present invention also relates to molded articles containing a composition according to the invention or a composition obtained or obtainable by a method according to the invention.
  • the present invention also relates to the use of the inventive
  • Random nonwovens preferably seals, rollers, shoe soles, hoses, cables, cable plugs, cable sheathing, cushions, laminates, profiles, belts, saddles, foams,
  • Plug connections, trailing cables, solar modules, cladding in automobiles The use for the production of cable sheathing is preferred. Production takes place, preferably from granules, by injection molding, calendering, powder sintering, or extrusion and / or by additional foaming of the composition according to the invention.
  • thermoplastic polyurethanes according to the invention and those according to the invention are due to the good mechanical properties and the good temperature behavior
  • compositions in particular for the production of films, molded parts, rolls, fibers, Cladding in automobiles, hoses, cable plugs, bellows, trailing cables,
  • Cable sheathing, seals, belts or damping elements are suitable.
  • the present invention also relates to films, molded parts, rolls, fibers,
  • composition (Z-2) containing at least
  • a flame retardant selected from the group consisting of
  • composition according to embodiment 1 wherein the proportion of the copolyamide (PA-1) in the composition is in the range from 5 to 95% by weight, based on the sum of components (i) and (ii).
  • Composition according to one of embodiments 1 or 2 wherein the
  • Composition at least one first phosphorus-containing flame retardant (F1) selected from the group consisting of derivatives of phosphoric acid and derivatives of phosphonic acid and at least one further phosphorus-containing flame retardant (F2) selected from the group consisting of derivatives of phosphinic acid.
  • F1 first phosphorus-containing flame retardant
  • F2 further phosphorus-containing flame retardant
  • Flame retardant (F1) is a phosphinate.
  • Phosphorus-containing flame retardant (F2) is a phosphoric acid ester.
  • Flame retardant (F1) is selected from the group consisting of resorcinol bis-diphenyl phosphate (RDP), bisphenol A bis (diphenyl phosphate) (BDP), and
  • a method for producing a composition (Z-2) comprising the steps
  • a flame retardant selected from the group consisting of melamine cyanurates, magnesium hydroxide and phosphorus-containing
  • composition (b) mixing components (i) and (ii).
  • Composition (Z-3) containing at least
  • a method for producing a composition (Z-3) comprising the steps
  • A a copolyamide (PA-1), produced by polymerizing at least one lactam, and a monomer mixture (M) which contains components (B1) at least one C32-C40 dimer acid and (B2) at least one C4-C12 diamine ; and
  • Ultramid F X2298 Copolymer of polyamide 6 and polyamide 6.36 (PA 6 / 6.36) from BASF SE, 67056 Ludwigshafen, Germany, sold under the brand name Ultramid FtX 2298 with an MVR (275 ° C / 5kp) 115 cm3 / 10 ', a viscosity number according to DIN 53727 (0.005g / ml FI2S04) of 28 ml / g, a melting temperature (DSC, ISO 11357) of 200 ° C and a density of 1.054 g / ml.
  • Exolit OP 1230 Aluminum diethylphosphinate, CAS #: 225789-38-8, Clariant discipline (Deutschland) GmbH, Chemiepark Knapsack, 50351 Hürth, water content% (w / w) ⁇ 0.2, average particle size (D50) 20-40 pm.
  • Ultrabatch 590A Mixture of 63% by weight aluminum hypophosphite, CAS 7784-22-7 and 37% by weight melamine cyanurate, CAS 37640-57-6, Italmatch Chemicals SpA, Via Pietro Chiesa 7/13 (piano 8 °), Torri Piane-SanBenigno , 16149 Genoa, italy,
  • Phosphorus content (%) 26-27, nitrogen content (%) 17.6-18.6, average particle size (D50) 3.4pm, water content% (w / w) ⁇ 0.2.
  • Fyrolflex RDP Resorcinol bis (diphenyl phosphate), CAS #: 125997-21-9, Supresta Netherlands B.V., Office Park De Hoef, Hoefseweg 1, 3821 AE Amersfoort, The
  • Melapur MC 15 ED melamine cyanurate (1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, compound with 1,3,5-triazine-2,4,6-triamine (1 : 1)), CAS #: 37640-57-6, BASF SE, 67056
  • GT parts by weight
  • the mixtures were each produced with a ZE 40 A twin-screw extruder from Berstorff with a process part length of 35 D, divided into 10 housings.
  • the granulation was carried out by means of a customary underwater granulation from Gala (UWG).
  • test specimens for the cone measurements with dimensions of 100x100x5mm and the test specimens for determining the mechanical properties were injection molded on an Arburg 520S with a screw diameter of 30 mm.
  • the materials could be injection molded at low temperatures. They are exemplary
  • E-modules, impact strengths and notched impact strengths were determined on injection-molded test specimens.
  • test specimens were tempered at 100 ° C. for 20 hours. The test specimens then remained in the standard climate for 3 days before the mechanical ones
  • the examples according to the invention all have a more or less low total heat release (THR) and a significantly reduced maximum heat release (PH RR). These advantageous flame-retardant properties are particularly pronounced in example 3 according to the invention.
  • Density, Shore hardness, tensile strength, tear resistance, abrasion and elongation at break were determined on films with a thickness of 1.6 mm. The slides were with a
  • Burst pressures were determined on hoses with an outside diameter of 8.0 mm and an inside diameter of 5.5 mm. The hoses were connected to a

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyamides (AREA)

Abstract

La présente invention concerne une composition contenant au moins un copolyamide (PA-1) comme composant (I), fabriqué par polymérisation d'au moins un lactame et d'un mélange de monomères (M) qui contient au moins un acide dimère en C32-C40 et au moins une diamine en C4-C12 ; et un agent ignifuge (F1) choisi dans le groupe constitué par les cyanurates de mélamine, l'hydroxyde de magnesium et les agents ignifuges phosphorés comme composant (II). La présente invention concerne en outre un procédé de fabrication de compositions de ce type, ainsi que l'utilisation d'une composition selon l'invention pour la fabrication de corps façonnés
EP20721241.6A 2019-04-30 2020-04-29 Polyamide ignifugé Pending EP3962978A1 (fr)

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PCT/EP2020/061843 WO2020221785A1 (fr) 2019-04-30 2020-04-29 Polyamide ignifugé

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WO2024002869A1 (fr) 2022-06-27 2024-01-04 Basf Se Composition de polyuréthane thermoplastique (tpu) présentant des propriétés améliorées
WO2024104744A1 (fr) * 2022-11-14 2024-05-23 Henkel Ag & Co. Kgaa Composition adhésive thermofusible thermoplastique avec retardateur de flamme

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US20220213266A1 (en) 2022-07-07
WO2020221785A1 (fr) 2020-11-05
EP3962979A1 (fr) 2022-03-09
US20220363827A1 (en) 2022-11-17
CN113767132A (zh) 2021-12-07
JP2022531204A (ja) 2022-07-06
WO2020221786A1 (fr) 2020-11-05

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