Highly viscous, multimodal polyamide composition

Abstract

HIGHLY VISCOUS, MULTIMODAL POLYAMIDE COMPOSITION Abstract The invention relates to highly viscous, multimodal polyamide compositions containing chain extenders, the composition of which is described by an expansion factor and a polydispersity index (PDI). The PDI is at least 2.2 and the number-average molar mass, calculated on the basis of the chain ends, is at least 26,000. The composition is obtained by reacting an amine-terminated polyamide, having amine end groups at at least 70% of the termini, with the chain extender and a non-amine-terminated polyamide. The chain extender is a polyamide-polycarbonate block copolymer having a polycarbonate content of 25-75 wt.%.

Description

Full specification HIGHLY VISCOUS, MULTIMODAL POLYAMIDE COMPOSITION High-viscosity, multimodal polyamide compositions containing chain extenders whose composition is described by a spread factor and a polydispersity index. WO 2006 / 07989 A1 discloses high-viscosity polyamide moulding compounds. A theoretical correlation between the polydispersity index and the termination of the different polyamides is presented. A maximum PDI value of 2 is disclosed. The disclosed examples do not show any support for this theoretical approach. The entire document discloses only numbers of the end groups of the polyamides but no specification of the type of end groups. It also discloses the reaction of "low molecular weight" polyamide (molar mass < 30 000 g / mol) with "relatively high molecular weight" PA (MM > 30 000 g / mol, optionally with addition of different amounts of impact modifiers (IM) and optionally with addition of a viscosity elevator. The positive effect is said to be that of improving (increasing) the melt strength (MS). However, the examples show that the addition of the viscosity elevator does not increase the viscosity. The notched impact strength is clearly dependent on the IM amount. EP 1690889 A1 discloses polyamide compositions using the chain extender Brüggolen M1251. However, it discloses only particulars of production while corresponding product details about molar masses and thus the polydispersity index are not disclosed and cannot be estimated either.EP 3296345 A1 discloses polyamide mixtures using polyamine-polyamide graft copolymers which are particularly stable to hydrolysis. The examples show the disadvantages of using a chain extender. It is an object of the present invention to provide high-viscosity, multimodal polyamide compositions whose high-molecular-weight fraction markedly increases the polydispersity factor. It has surprisingly been found that a theoretical approach in which polyamide compositions can be generated by calculating certain stoichiometric values, wherein the so-called spread factor (S) exceeds a value of 2.5. In the process the object is achieved by mixing amine-terminated polyamides (A) with non-amine-terminated polyamides (B), wherein the non-amine-terminated polyamides (B) are admixed with a chain extender, when the spread factor (S) exceeds the value of 2.5. The spread factor (S) is determined by dividing the number-average molar mass () of the amine-terminated polyamides (final) with the number-average molar mass of the employed non-amine-terminated polyamide (B) according to formula 7.  The present invention provides high-viscosity, multimodal polyamide compositions having a number-average molar mass () of at least 26 000 g / mol consisting of:a) at least one amine-terminated polyamide (final) having an X-mer factor of at least 1.5,wherein the amine-terminated polyamides (final) represent the reaction product of the amine-terminated polyamides (A) with a chain extender,b) at least one non-amine-terminated polyamide (B), wherein the polyamide compositions have a polydispersity index calculated according to PDI = Mw / Mn a value of at least 2.2, wherein Mw and Mn are determined by GPC on the polyamide compositions, wherein the number-average molar mass () is determined according to the following formula 3Formula 3: where = is the percentage by mass of the amine-terminated polyamides (A) based on the total mass of the polyamides (A) and (B) = is the percentage by mass of the non-amine-terminated polyamides (B) based on the total mass of the polyamides (A) and (B) is the amount of the acid end groups in mmol / kg of the polyamides (A) is the amount of the acid end groups of the polyamides (B) in mmol / kg is the amount of the amino end groups in mmol / kg of the polyamides (A) = is the amount of the active groups in mmol / kg of the chain extender is the percentage by mass of the chain extender based on the mass of the polyamides (A) and (B),o wherein the percentages are fractions and are accordingly always less than 1 and + preferably sum to 1,   wherein the value of the X-mer parameter is calculated according to the following formula 4Formula 4: where the variables are as defined above,o wherein is calculated via the determination of the end groups of the amine-terminated polyamides (A) according to formula 5Formula 5: . The present invention further provides the process for producing high-viscosity, multimodal polyamide compositions, whereina) at least one amine-terminated polyamide (A) is provided,b) at least one non-amine-terminated polyamide (B) is provided and admixed with a chain extender,c) the polyamides (A) and (B) are selected such that a spread factor of 2.5 is exceeded, wherein the spread factor is determined by dividing the number-average molar mass () (formula 1) by the number-average molar mass (formula 2) of the employed non-amine-terminated polyamides (B),  wherein the number-average molar mass () is calculated according to formula 1Formula 1: where = is the percentage by mass of the amine-terminated polyamides (A) based on the total mass of the polyamides (A) and (B) = is the percentage by mass of the non-amine-terminated polyamides (B) based on the total mass of the polyamides (A) and (B) is the amount of the acid end groups in mmol / kg of the polyamides (A) is the amount of the amino end groups in mmol / kg of the polyamides (A) = is the amount of the active groups in mmol / kg of the chain extender is the percentage by mass of the chain extender based on the mass of the polyamides (A) and (B), wherein is calculated via determination of the end groups according to formula 2,Formula 2: where is the amount of the acid end groups in mmol / kg of the polyamides (B) is the amount of the amino end groups in mmol / kg of the polyamides (B) d) the components are heated together in a suitable apparatus with mixing,wherein the percentages are fractions and are accordingly always less than 1 and + preferably sum to 1. The present invention further provides moulding compounds containing the high-viscosity, multimodal polyamide compositions according to the invention and / or the products of the process in a proportion of at least 50% by weight, preferably in a proportion of at least 60% by weight, more preferably in a proportion of at least 70% by weight, particularly preferably at least 80% by weight, more particularly preferably at least 90% by weight, more particularly preferably at least 95% by weight and especially preferably in a proportion of at least 99% by weight.The present invention further provides shaped articles consisting of the moulding compounds according to the invention.The invention further provides for the use of the shaped articles according to the invention as a coating, covering, film, profile, pipe, corrugated pipe, hollow article, seal, trim piece, holder, housing, sheathing and as electrical and electronic components. The calculated / theoretical values of the present invention are based exclusively on the values of the employed polyamide-forming components, the polyamides formed and the chain-extending additive used. Possible further additives, for example impact modifiers, are not included.In the context of the invention the term "high-viscosity" is to be understood as meaning polyamide compositions having a solution viscosity according to DIN 307 of at least 250 ml / g.The term "high molecular weight" is to be understood as meaning polyamides having a weight-average molar mass Mw of at least 100 000 g / mol determined by GPC. The high-viscosity, multimodal polyamide compositions according to the invention, the products according to the process, the shaped articles containing the polyamide compositions according to the invention and the uses according to the invention are hereinbelow described by way of example, without any intention that the invention be restricted to these exemplary embodiments. Where ranges, general formulas, or classes of compound are stated hereinbelow, these are intended to encompass not just the corresponding ranges or groups of compounds that are explicitly mentioned, but also all subranges and subgroups of compounds that can be obtained by taking out individual values (ranges) or compounds. Where documents are cited in the context of the present description, the entire content thereof is intended to be part of the disclosure content of the present invention. Where percentage values are reported hereinbelow, these are values in % by weight unless otherwise stated. The percentage values for compositions are based on the total composition unless otherwise stated. Where average values are reported hereinbelow, these are mass averages (weight averages) unless otherwise stated. Where measured values are reported hereinbelow, these measured values were determined at a pressure of 101 325 Pa and a temperature of 25°C unless otherwise stated.The scope of protection includes finished and packaged forms that are conventionally used in commerce for the products of the invention, not only per se but also in possible comminuted forms to the extent that these are not defined in the claims.The optionally different units of the polyamides follow a statistical distribution. Statistical distributions are of blockwise construction with any desired number of blocks and with any desired sequence or they are subject to a randomized distribution; they may also have an alternating construction or else form a gradient over the polymer chain; in particular they can also form any mixed forms in which groups with different distributions may optionally follow one another. Specific embodiments may have the effect that statistical distributions are restricted as a consequence of the embodiment. For all regions unaffected by the restriction, there is no change in the statistical distribution. One advantage of the process according to the invention is that the multimodal, high-viscosity polyamides are producible directly in one process, preferably by extrusion. An otherwise customary post-condensation is not necessary.A further advantage of the polyamide compositions according to the invention is that shaped articles consisting of these compositions / moulding compounds exhibit an exceptionally high mechanical strength and toughness, especially at low temperatures, without plasticizers or / and without impact modifiers. Particularly the Charpy notched impact strength at 0°C demonstrates the advantages of these plasticizer- and impact modifier-free compositions. The polyamides of the compositions and moulding compounds according to the invention may be homopolymers, copolymers or blends of different polyamides. The differences in the polyamides may be manifested for example in the use of different monomers in the polymerization, different molar mass distribution (which can manifest, for example, in different viscosities) or different end groups.The polyamides are preferably selected from aliphatic and / or semiaromatic polyamides and suitable monomers may be ω-amino acids or lactams - this leads to so-called AB polyamides (so-called perlon-type) - or may be diamines and diacids - this leads to so-called AA.BB polyamides (so-called nylon-type). The monomers may optionally be substituted, but substituents must be inert in the context of the polymerization / polycondensation and preferably are not Brønsted acids or bases. In the case of the formation of AA.BB polyamides, the monomers may form what are known as semiaromatic polyamides, i.e. where only one of the two units, diamine or diacid, includes an aromatic ring. Preferred monomers are selected from aliphatic C4 to C12 lactams or ω-aminocarboxylic acids having 4 to 44 carbon atoms, preferably 4 to 18 carbon atoms, from at least one diamine from the group of aliphatic diamines having 4 to 18 carbon atoms, cycloaliphatic diamines having 7 to 22 carbon atoms and aromatic diamines having 6 to 22 carbon atoms in combination with at least one dicarboxylic acid from the group of aliphatic dicarboxylic acids having 4 to 44 carbon atoms, cycloaliphatic dicarboxylic acids having 8 to 24 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. The polyamides are more preferably selected from PA 8, PA 9, PA 10, PA 11, PA 12, PA 4.6, PA 6.10, PA 6.12, PA 6.13, PA 6.14, PA 6.16, PA 8.10, PA 8.13, PA 9.10, PA 9.12, PA 10.10, PA 10.12, PA 10.14, PA 10.16, PA 10.18, PA 12.12, PA DACH.6 (diaminocyclohexane), PA DACH.10, PA DACH.12, PA DACH.10 / 11PA PACM.6 (4,4-diaminodicyclohexylmethane), PA PACM.10, PA PACM.12, PA MACM.6 (3,3'-dimethyl-4,4'-diaminocyclohexylmethane), PA MACM.10, PA MACM.12,PA 6.T (T = terephthalic acid), PA 9.T, PA 10.T, PA 12.TPA 6.I (I = isophthalic acid, PA 9.I, PA 10.I, PA 12.IPA 6.N (2,6-naphthalenedicarboxylic acid), PA 10.N, PA 12.NPA MXD.6 (MXD = meta-xylenediamine), PA MXD.10, PA MXD.12PA IPD.6 (isophoronediamine), PA IPD.10, PA IPD.12, PA IND.6 (isononyldiamine, 1,6-diamino-2,4,4-trimethylhexane), PA IND.10, PA IND.12, PA ND.6 (nonyldiamine, 1,6-diamino-2,2,4-trimethylhexane), PA ND.10, PA ND.12.It is further preferable when the polyamides have at least 8 carbon atoms per amide unit in all monomer units. It is more preferable when the polyamides have, as a statistical average over the polymer, 8 to 16 carbon atoms, more preferably 9 to 14 carbon atoms, particularly preferably 10 to 12 carbon atoms per amide unit. The polyamides are particularly preferably selected from PA 6.12, PA 10.10, PA 10.12, PA 11 and PA 12 and especially preferably PA 11 and PA12. The polyamides of the compositions according to the invention contain at least one non-amine-terminated polyamide and one amine-terminated polyamide. Those skilled in the art are familiar with how to achieve defined synthesis of the termini of polyamides. This is done with so-called chain-transfer agents. In the case of nylon-type polyamides this may be a simple stoichiometric excess of one of the two components. Alternatively, a so-called external chain-transfer agent is added; this may be done for both polyamide types (perlon and nylon). These chain-transfer agents may be for example aliphatic or aromatic compounds that are monofunctionalized in the context of polyamide formation; this forms termini that are inert in the context of polyamide formation.  In the cases in which the carbon number per amide unit of the polyamides is defined as greater than 6 and in the cases in which the polyamides are specifically defined such that no PA 6 is present the following applies: The chain-extending additive is optionally distributed as a masterbatch in a polyamide or the chain-extending additive itself comprises a polyamide unit, wherein this polyamide may be outside the definition of the preferred polyamides of the high-viscosity, multimodal polyamide compositions and moulding compounds according to the invention. The resulting low content of polyamide 6 for example is in accordance with the invention. This low content is preferably in the range from 1 ppm to 5% calculated as mass fractions based on the total mass of the compositions according to the invention, more preferably of 1000 ppm to 3% and particularly preferably from 1 to 2.5%. The multimodal polyamide compositions according to the invention are produced by mixing amine-terminated polyamides (A) with non-amine-terminated polyamides (B), wherein the non-amine-terminated polyamides (B) are admixed with a chain extender. During the mixing process the chain extender reacts with the employed amine-terminated polyamide and forms a high-molecular weight and high-viscosity amine-terminated polyamide. The mixing process is also a reactive process for synthesis of a novel polyamide component. The non-amine-terminated polyamides (B) have no amino groups at at least 70% of all termini; these termini are inert in the context of polyamide formation or are carboxylic acid groups (collectively described as “non-amine terminus”). The non-amine-terminated polyamides (B) preferably have non-amine termini at at least 80%, more preferably at at least 85%, particularly preferably at at least 90% and especially preferably at at least 95%. These statistical values may be realized by mixing different polyamides (blends), wherein each component must have non-amine termini at at least half of all termini. The individual components of the non-amine-terminated polyamides (B) too preferably have non-amine termini at at least 60% of the termini, more preferably at at least 70%, yet more preferably at at least 80%, particularly preferably at at least 90%. Mixtures of distinctly terminated “non-amine-terminated” polyamides are also within the scope of protection.When two or more non-amine-terminated polyamides (B) are used the number-average molar mass is calculated from the sum of the individual values, in each case multiplied by the mass fraction thereof based on the sum of the non-amine-terminated polyamides (B). It is preferable when the non-amine-terminated polyamides (B) are acid-regulated polyamides; therefore, the non-amine termini are then carboxylic acid groups and are referred to as acid-terminated polyamides.The acid-terminated polyamides preferably have an amount of acid end groups of at least 50 mmol / kg, more preferably 60 mmol / kg, yet more preferably 70 mmol / kg, particularly preferably 80 mmol / kg, more particularly preferably at least 90 mmol / kg, yet more particularly preferably at least 100 mmol / kg, especially preferably at least 110 mmol / kg, more especially preferably at least 120 mmol / kg, yet more especially preferably at least 130 mmol / kg.In the acid-terminated polyamides it is preferable when less than 30% of the termini, preferably 20%, more preferably 15%, yet more preferably 10%, particularly preferably 8%, very particularly preferably 6% and especially preferably less than 4% are amino groups. In the acid-terminated polyamides it is preferable when at least 0.05%, more preferably 0.1%, more preferably 0.5% and particularly preferably at least 1% of the termini are amino groups.In the acid-terminated polyamides it is preferable when 0.05% to 20%, more preferably 0.1% to 10%, particularly preferably 0.5% to 8% and especially preferably 0.1% to 6% of the termini are amino groups.It is preferable when the process according to the invention employs amine-terminated polyamides (A) and acid-terminated polyamides. Theoretical number-average molar masses may be calculated using the termini of the polyamidesFormula 6: This is the general formula known to a person skilled in the art. In the context of the present invention the number-average molar masses of the “non-amine-terminated polyamides” are in principle likewise calculated according to this formula with the exception that in the denominator the term [COOH] + [R] is calculated as the sum of the acid end groups and the inert termini [R].  The amine-terminated polyamides (A) preferably have an amount of amine end groups of at least 40 mmol / kg, preferably at least 50 mmol / kg, more preferably at least 75 mmol / kg, yet more preferably at least 100 mmol / kg, particularly preferably at least 120 mmol / kg.The amine-terminated polyamides (A) have amine end groups at at least 70% of the termini, preferably at at least 80%, particularly preferably at at least 90% and especially preferably at at least 95%.In the amine-terminated polyamides (A) it is preferable when less than 30% of the termini, preferably 20%, more preferably 15%, yet more preferably 10%, particularly preferably 8%, very particularly preferably 6% and especially preferably less than 4% are amino groups. In the amine-terminated polyamides (A) it is preferable when at least 0.05%, more preferably 0.1%, more preferably 0.5% and particularly preferably at least 1% of the termini are non-amine termini.In the amine-terminated polyamides (A) it is more preferable when 0.05% to 20%, more preferably 0.1% to 10%, particularly preferably 0.5% to 8% and especially preferably 1% to 6% of the termini are non-amine termini.The termini of the amine-terminated polyamides (A) which are not amine termini are in particular acid termini.The polyamides of the compositions according to the invention preferably comprise acid-terminated polyamides (B) having an amount of acid end groups not less than the amount of amino end groups of the amine-terminated polyamides (A); particularly preferably, the amount of acid end groups of the acid-terminated polyamides (B) is greater than the amount of amino end groups of the amine-terminated polyamides (A).The methods of determining the end groups of polyamides are in principle familiar to those skilled in the art. Determination of the carboxyl end groups is preferably performed by dissolution of the polymer in benzyl alcohol and alkalimetric titration with alcoholic KOH (0.1 mol / l stock solution) against phenolphthalein. Determination of the amino end groups is preferably carried out in m-cresol by dissolution of the polyamide at elevated temperature. Potentiometric endpoint determination is carried out. Both methods are more particularly described below and are particularly preferably determined according to said description. Determination of the inert end groups is preferably carried out by NMR spectroscopy, in particular by coupled proton-carbon methods. The spread factor (S) is a theoretical value that must be adhered to in the process according to the invention. It is defined as the quotient (according to formula 7) of (according to formula 1) and (according to formula 2)  Formula 7 The spread factor is at least 2.5, preferably 3, more preferably 3.5, yet more preferably 4, particularly preferably 4.5, more particularly preferably 5, yet more particularly preferably 6, especially preferably at least 7. The spread factor is at most 30, preferably 25, more preferably 20, particularly preferably 15 and especially preferably at most 13. The spread factor is preferably from 2.5 to 30, more preferably from 3 to 25, particularly preferably from 3.5 to 20 and especially preferably from 4 to 15.The spread factor preferably has a value from 2.5 to 30, more preferably from 3 to 25, particularly preferably from 3.5 to 20 and especially preferably from 4 to 15 and relates to an acid-terminated polyamide as the non-amine-terminated polyamide (B).The polyamides of the compositions according to the invention preferably comprise acid-terminated polyamides having an amount of acid end groups not less than the amount of amino end groups of the amine-terminated polyamides, wherein the spread factor has a value of 2.5 to 30, more preferably of 3 to 25, particularly preferably of 3.5 to 20 and especially preferably of 4 to 15. The compositions according to the invention and the moulding compounds preferably contain no further polyamide in addition to the polyamides defined above. The non-amine-terminated polyamides (B) are admixed with a chain-extending additive (chain extender), such as carbonyl-bis-caprolactam (CBC), N-N'-terephthaloyl-bis-caprolactam, bisoxazolines, diisocyanates, capped diisocyanates, carbodiimides, epoxy-functionalized 5 oligomers or polymers or additives based on carbonate units. The preferred chain-extending additives have at least 5 carbonate units per molecule, preferably 10, more preferably 20, particularly preferably 30, more particularly preferably 40 and especially preferably at least 50 carbonate units per molecule. Particularly preferred chain-extending additives are disclosed in WO 2000 / 066650 and especially preferred chain-extending additives are block copolymers of formula PA.PC, wherein PA is polyamide and PC is polycarbonate. The polycarbonate has at least 5 carbonate units, preferably 10, more preferably 20, more preferably 30, particularly preferably 40 and in particular at least 50. The polycarbonate preferably comprises 2 to 100, particularly preferably 30 to 80 and especially preferably 40 to 70 carbonate units.The polyamide is an acid-terminated polyamide, wherein at least one terminus produces the bond to the polycarbonate.The chain-extending additive preferably comprises 25% to 75% by weight, more preferably 35% to 65% by weight and especially preferably 45% to 55% by weight of polycarbonate.The units of the polyamide and of the polycarbonate preferably have approximately identical molar masses; the molar masses more preferably diverge from one another by less than 20% by weight, more preferably 15% by weight, particularly preferably 10% by weight and especially preferably less than 5% by weight from one another.The molar masses of the blocks are preferably 5000 to 30 000 g / mol, particularly preferably 8000 to 20 000 g / mol and especially preferably 10 000 to 18 000 g / mol. The chain-extending additive is compounded into the non-amine-terminated polyamides (B); the concentration of the chain-extending additive in the non-amine-terminated polyamides (B) is preferably 2% to 30% by weight, more preferably 3% to 25% by weight, more preferably 4% to 22% by weight, especially preferably 5% to 20% by weight.It is more preferable when the chain-extending additive is employed in acid-terminated polyamides, particularly preferably in acid-terminated polyamides having an amount of acid end groups of at least 50 mmol / kg, preferably 60 mmol / kg, more preferably 70 mmol / kg, particularly preferably 80 mmol / kg, more particularly preferably at least 90 mmol / kg, yet more particularly preferably at least 100 mmol / kg, especially preferably at least 110 mmol / kg, more especially preferably at least 120 mmol / kg, yet more especially preferably at least 130 mmol / kg.The term may assume a negative or positive value. The concentration of chain extender is preferably selected such that the term assumes a positive value. Having regard to their amino end groups (polyamide (A)) the amine-terminated polyamides (A) are thus then present in excess relative to the groups of the chain extenders active in the context of chain extension. It is more preferable when the value of the term is between 0.5 and 35, more preferably between 1 and 30, particularly preferably between 2 and 25, more particularly preferably between 3 and 20 and especially preferably between 4 and 15. Should the term assume a negative value, it is set equal to zero for the calculations.The theoretical number-average molar mass is preferably greater than 40 000 g / mol, preferably greater than 50 000 g / mol, more preferably greater than 60 000 g / mol, particularly preferably greater than 70 000 g / mol, more particularly preferably greater than 80 000 g / mol, more particularly preferably greater than 90 000 g / mol and especially preferably greater than 100 000 g / mol.The theoretical number-average molar mass is not more than 500 000 g / mol, more preferably not more than 400 000 g / mol, yet more preferably not more than 300 000 g / mol, particularly preferably not more than 200 000 g / mol and especially preferably 100 000 g / mol.Preferred compositions according to the invention have a theoretical number-average molar mass of 40 000 to 400 000 g / mol and a spread factor of more than 2.5 to 30, more preferably a of 50 000 to 300 000 g / mol and a spread factor of 2.5 to 25, particularly preferably a of 60 000 to 200 000 g / mol and a spread factor of 2.5 to 25 and especially preferably a of 70 000 to 100 000 g / mol and a spread factor of 3.5 to 15.The multimodal, high-viscosity polyamide compositions according to the invention feature a high spread factor (S). There is thus also a difference in the molar masses of the non-amine-terminated polyamides (B) and the amine-terminated polyamides (final). The amine-terminated polyamides (final) are the sum of all amine-terminated polyamides after reaction of the amine-terminated polyamides (A) with the chain extender.This results in certain proportions of dimers or oligomers which comprise two or more molecules of amine-terminated polyamides (A) bridged by the chain extender. The value X according to formula 4 relates to this observation.Formula 4: where = is the percentage by mass of the amine-terminated polyamides (A) based on the total mass of the polyamides (A) and (B) = is the percentage by mass of the non-amine-terminated polyamides (B) based on the total mass of the polyamides (A) and (B) is the amount of the acid end groups in mmol / kg of the polyamides (A) is the amount of the amino end groups in mmol / kg of the polyamides (A) = is the amount of the active groups in mmol / kg of the chain extender is the percentage by mass of the chain extender based on the mass of the polyamides (A) and (B). The percentages relate to fractions and are thus always less than 1. + preferably sum to 1.The value of formula 4 is at least 1.5, preferably greater than 2, more preferably greater than 2.5, particularly preferably greater than 3, more particularly preferably greater than 5, more particularly preferably greater than 7 and especially preferably greater than 10.The value of formula 4 is preferably at most 20, more preferably 18, particularly preferably 16 and especially preferably at most 14.It is further preferable when the value of formula 4 is preferably 1.5 to 20, more preferably 2 to 18, yet more preferably 3 to 16 and especially preferably 7 to 14.The polyamide compositions according to the invention preferably have a spread factor (S) (of formula 7) of 2.5 to 30 and a value (of formula 4) of 1.5 to 20, particularly preferably a spread factor of 2.5 to 25 and a value (of formula 4) of 2 to 18 and especially preferably a spread factor of 3.5 to 15 and a value (of formula 4) of 3 to 16. The theoretical number-average molar mass of the high-viscosity multimodal composition according to the invention is calculated according to formula 3Formula 3: where all definitions are as defined above.According to the invention this theoretical number-average molar mass () is preferably greater than 29 000 g / mol, more preferably greater than 32 000 g / mol, more preferably greater than 34 000 g / mol, particularly preferably greater than 36 000 g / mol, more particularly preferably greater than 38 000 g / mol, more particularly preferably greater than 40 000 g / mol and especially preferably greater than 42 000 g / mol. The determinations of Mw and Mn are familiar to those skilled in the art and are preferably determined by GPC of the polyamide fraction, particularly preferably as described below. They are therefore experimental data of the product according to the invention. The PDI, as the quotient of Mw and Mn, is thus a likewise experimentally determined value.The actual polydispersity index is thus directly determinable from experimental data according to PDI = Mw / Mn. According to the invention the PDI is at least 2.2, preferably at least 2.3, more preferably at least 2.5, more preferably at least three, more preferably at least 3.5, more preferably at least 4, particularly preferably at least 4.5 and especially preferably at least 4.9. Maximum values for the PDI are 15, preferably 12, more preferably 9, particularly preferably 6. The PDI is preferably from 2.3 to 15, more preferably from 2.5 to 12, particularly preferably from 3 to 9 and especially preferably from 4 to 6. Optionally, the polyamide moulding compounds of the invention comprise customary processing aids such as stabilizers, oxidation retardants, other agents protecting against thermal decomposition and decomposition by ultraviolet light, lubricants and mould-release agents, colouring agents such as dyes and pigments, nucleating agents, plasticizers, etc.Optionally, the polyamide moulding compounds of the invention comprise, besides the described components, further additives selected from one or more representatives, optionally two or more of the same kind, such as stabilizers, other polymers, impact modifiers, plasticizers, colouring agents such as pigments and dyes, processing aids.Suitable oxidation stabilizers are aromatic amines, sterically hindered phenols, hydroquinones, phosphites, phosphonites, thiosynergists, hydroxylamines, benzofuranone derivatives, acryloyl-modified phenols etc. A great many types of such oxidation stabilizers are commercially available, for example under the trade names Naugard 445, Irganox 1010, Irganox 1098, Irgafos 168, P-EPQ or Lowinox DSTDP. In general, the moulding compounds comprise about 0.01% to about 2% by weight and preferably about 0.1% to about 1.5% by weight of oxidation stabilizers.In addition, the moulding compounds may also comprise UV stabilizers or light stabilizers. Suitable UV stabilizers are organic UV absorbers, for example benzophenone derivatives, benzotriazole derivatives, resorcinols, salicylates, oxalanilides and phenyltriazines. Light stabilizers of the HALS type are tetramethylpiperidine derivatives. UV stabilizers and light stabilizers may advantageously be used in combination. Both are commercially available in a multitude of types; the dosage can be as per the manufacturer’s instructions.In addition, the moulding compounds may comprise hydrolysis stabilizers, for instance a monomeric, oligomeric or polymeric carbodiimide or bisoxazoline.Examples of other polymers that may be present in the moulding compositions as additive are polyetheramides, or polytetrafluoroethylene (PTFE). Impact modifiers are known to those skilled in the art. They contain functional groups originating from unsaturated functional compounds that were either incorporated into the main chain by polymerization or grafted onto the main chain. The most commonly used are EPM rubber or EPDM rubber that has undergone free-radical grafting with maleic anhydride. Rubbers of this kind can also be used together with an unfunctionalized polyolefin, for example isotactic polypropylene, as described in EP-A-0 683 210.Plasticizers are known to those skilled in the art from Gächter / Müller, Kunststoffadditive, C. Hanser Verlag, 2nd edition, p. 296. Customary compounds suitable as plasticizers include so-called low-molecular weight plasticizers such as for example esters of p-hydroxybenzoic acid having 2 to 20 carbon atoms in the alcohol component or amides of arylsulfonic acids having 2 to 12 carbon atoms in the amine component, preferably amides of benzenesulfonic acid. More preferred plasticizers include, inter alia, ethyl p-hydroxybenzoate, octyl p-hydroxybenzoate, i-hexadecyl p-hydroxybenzoate, toluenesulphonic acid n-octylamide, benzenesulphonic acid n-butylamide or benzenesulphonic acid 2-ethylhexylamide. Examples of suitable pigments and / or dyes are mixed oxides, titanium dioxide, iron oxide, zinc sulfide, ultramarine, nigrosin, organic pigments, such as phthalocyanines, quinacridones, perylenes, nigrosin, anthraquinones, pearlescent pigments.Examples of suitable processing aids include paraffins, fatty alcohols, fatty acid amides, stearates such as calcium stearate, paraffin waxes, montanates or polysiloxanes. The polyamide moulding compounds according to the invention preferably comprise 0.01% to 2% by weight, more preferably 0.05% to 1.5% by weight and especially preferably 0.1% to 1% by weight of processing agent.However, the polyamide moulding compounds according to the invention preferably comprise no impact modifiers. Preferably, the polyamide moulding compounds according to the invention preferably comprise no BBSA, more preferably no low molecular weight plasticizers, and especially no plasticizers. The polyamide moulding compounds according to the invention more preferably comprise neither impact modifiers nor plasticizers.The polyamide moulding compounds according to the invention preferably have polyamides having an average numerical molar mass Mn measured by GPC of at least 45 000 g / mol, more preferably of 50 000 g / mol, more preferably of 55 000 g / mol, further more preferably of 60 000 g / mol, particularly preferably of 65 000 g / mol and especially of at least 70 000 g / mol.The polyamide moulding compounds according to the invention preferably have polyamides having an average numerical molar mass Mn measured by GPC of at least 50 000 g / mol and a PDI of 2.3 to 15, particularly preferably an Mn of at least 60 000 g / mol and a PDI of 2.5 to 12 and especially preferably an Mn of at least 70 000 g / mol and a PDI of 3 to 9.The polyamide moulding compounds according to the invention based on PA11 or PA 12 preferably have an average numerical molar mass Mn measured by GPC of at least 50 000 g / mol, more preferably of 55 000 g / mol, yet more preferably of 60 000 g / mol, particularly preferably of 65 000 g / mol and especially of at least 70 000 g / mol.The polyamide moulding compounds according to the invention based on PA11 or PA12 preferably have an average numerical molar mass Mn measured by GPC of at least 50 000 g / mol and a PDI of 2.3 to 15, particularly preferably an Mn of at least 60 000 g / mol and a PDI of 2.5 to 12 and especially preferably an Mn of at least 70 000 g / mol and a PDI of 3 to 9. The high-viscosity, multimodal polyamide moulding compounds according to the invention may be used for producing shaped articles containing these polyamide moulding compounds.The Charpy notched impact strength of the shaped articles increases due to the use of the chain-extending additives. As shown in the examples this effect is observable on shaped articles made of the high-viscosity, multimodal polyamide moulding compounds according to the invention themselves consisting of the high-viscosity, multimodal polyamide compositions according to the invention (optionally using a tiny amount of 0.1% by weight, based on the total composition, of demoulding agent which is preferably calcium stearate) {hereinbelow referred to as “consisting of”} when these are compared with shaped articles produced from the corresponding base polymers (BP). The Charpy impact strengths are used to calculate a quotient, the Charpy factor (), according to the following formula:Formula CF: where is the Charpy notched impact strength of a shaped article made of the amine-terminated polyamides (A) is the Charpy notched impact strength of a shaped article made of the non-amine-terminated polyamides (B) and are the percentages by mass (as defined in formula 3) of the polyamides (A) and (B) in the shaped article made of high-viscosity, multimodal polyamide compositions according to the invention; this shaped article has the Charpy notched impact strength .The Charpy factor for measurements at 0°C () is greater than 2, preferably greater than 3, yet more preferably greater than 4, particularly preferably greater than 5 and especially preferably greater than 6. A possible maximum value could be 10.The Charpy factors, including all subterms and parameters, are calculated to 2 decimal places and finally rounded to natural numerical values. Shaped articles consisting of the high-viscosity, multimodal polyamide moulding compounds / compositions according to the invention preferably have a Charpy notched impact strength at 0°C of at least 25 kJ / m2, more preferably of at least 30 kJ / m2, particularly preferably of at least 35 kJ / m2, especially preferably of at least 40 kJ / m2.Preferred shaped articles made of the high-viscosity, multimodal polyamide moulding compounds / compositions according to the invention having an average numerical molar mass Mn measured by GPC of at least 50 000 g / mol have a Charpy notched impact strength at 0°C of at least 25 kJ / m2; more preferred shaped articles made of the high-viscosity, multimodal polyamide moulding compounds / compositions according to the invention having an average numerical molar mass Mn measured by GPC of at least 60 000 g / mol have a Charpy notched impact strength at 0°C of at least 30 kJ / m2; particularly preferred shaped articles made of the high-viscosity, multimodal polyamide moulding compounds / compositions according to the invention having an average numerical molar mass Mn measured by GPC of at least 65 000 g / mol have a Charpy notched impact strength at 0°C of at least 35 kJ / m2; especially preferred shaped articles made of the high-viscosity, multimodal polyamide moulding compounds / compositions according to the invention having an average numerical molar mass Mn measured by GPC of at least 70 000 g / mol have a Charpy notched impact strength at 0°C of at least 40 kJ / m2.Shaped articles made of the high-viscosity, multimodal polyamide moulding compounds / compositions according to the invention whose polyamides comprise to an extent of more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, of PA11 or PA12 (based on PA11 or PA12) preferably have a Charpy notched impact strength at 0°C of at least 25 kJ / m2, more preferably of at least 30 kJ / m2, particularly preferably of at least 35 kJ / m2, especially preferably of at least 40 kJ / m2.Shaped articles made of the high-viscosity, multimodal polyamide moulding compounds / compositions according to the invention based on PA11 or PA12, optionally comprising 0.1% by weight of calcium stearate as demoulding agent, having an average numerical molar mass Mn measured by GPC of at least 50 000 g / mol preferably have a Charpy notched impact strength at 0°C of at least 25 kJ / m2; shaped articles made of the high-viscosity, multimodal polyamide moulding compounds / compositions according to the invention having an average numerical molar mass Mn measured by GPC of at least 60 000 g / mol more preferably have a Charpy notched impact strength at 0°C of at least 30 kJ / m2; shaped articles made of the high-viscosity, multimodal polyamide moulding compounds / compositions according to the invention having an average numerical molar mass Mn measured by GPC of at least 65 000 g / mol particularly preferably have a Charpy notched impact strength at 0°C of at least 35 kJ / m2; shaped articles made of the high-viscosity, multimodal polyamide moulding compounds / compositions according to the invention having an average numerical molar mass Mn measured by GPC of at least 70 000 g / mol especially preferably have a Charpy notched impact strength at 0°C of at least 40 kJ / m2. Methods: Gel permeation chromatography (GPC)GPC analyses were carried out using an Agilent system of modular construction. These include pumps, autosamplers and column combinations (PSG columns) and detectors (RI and UV detector). The samples are dissolved in hexafluoroisopropanol (HFIP) in a concentration of c = 5 g / l with addition of 0.05 mol / l of potassium trifluoroacetate. The measurements are run with HFIP and 0.05 mol / l potassium trifluoroacetate at a flow rate of 0.8 ml / min with RI detection. The calibration curve is undertaken with 12 narrowly distributed PMMA standards (Mp between 505 g / mol and 4 000 000 g / mol).Only signals corresponding to a molar mass of at least 1000 g / mol are evaluated. Determination of viscosity according to ISO 307:2019The relative solution viscosity ɳrel is determined at 25°C on a 0.5% (mass) solution in m-cresol. End group determinationsCarboxylate end groups:2.0 g (expected value below 15 mmol / kg) or 1.0 g (expected value above 15 mmol / kg) of the sample is weighed into a weighing container. The thermostatted titration vessel is initially charged with approx. 40 ml (or 20 ml) of benzyl alcohol. The sample is then transferred to the benzyl alcohol and dissolved with stirring under inert gas. The dissolution time is 10 min (or 15 min).After dissolution, 3 drops of indicator solution are added and the sample is quickly titrated with potassium hydroxide solution (aqueous KOH) (concentration 0.1 mol / l). Amino end groups:0.5 g of the sample is weighed out and 50 ml of m-cresol added. The sample is dissolved over the course of one hour by heating to 100°C (a temperature of 140°C is used if necessary). After cooling to room temperature, 5 ml of methanol is added and the potentiometric titration is started. A solvent mixture blank is subtracted for the evaluation. Determination of the inert end groups is carried out by NMR spectroscopy, especially by coupled proton-carbon methods. Measured values for Charpy notched impact strength, “Charpy” for short, were determined according to DIN 179 1-eA. Table 1a: Characterization of the base polymers, Mn calculated from the end groups, BP stands for base polymer TypeNH2 end groups[mmol / kg]COOH end groups[mmol / kg]Molar mass Mn [g / mol]BP1PA1250735087.7BP2PA12312016260.2BP3PA12120316260.2BP4PA101289719047.6BP5PA1012134614285.7 Example 1: General procedure for producing polyamide compositions The moulding compounds were produced in a co-rotating twin-screw extruder at 250 rpm. The solid components were metered via the main feed, and the liquid components downstream thereof, into the melt at 240°C; the mass throughput was 15 kg / h. Pelletization was by strand pelletization with subsequent drying in a dry air cabinet dryer for 12 hours at 80°C. Table 2: Composition of inventive polyamide compositions before production of shaped articles, reported in [% by wt.] BP (A)amineBP (B)acid  M1251 in BP acidM1251totalEx1BP1BP290109.00.9Ex2BP1BP270305.41.6Ex3BP3BP2802020.04.0Ex4BP3BP2802015.03.0Ex5BP3BP270309.02.7Ex6BP3BP2703013.03.9Ex7BP3BP260408.03.2Ex8BP5BP4703014.04.2 Table 3a: Molecular values of inventive compositionsMolar masses reported in g / mol, GPC: measured values of the products,calculated values: according to formula 3, according to formula 1, Spread factor according to formula 7, X-mer according to formula 4 M1251GPCcalculated values Mn MwPDI  Spread factor X-mer Ex10.9609001400002.3044150.1540543.321.54Ex21.6563001738003.1045977.018666711.485.32Ex34.0792003995005.0047269.886956.55.35.3Ex43.0468001016002.2032051.341666.72.62.6Ex52.7565001307002.3229368.6436142.682.68Ex63.9705002794003.9645351.4717284010.6310.63Ex73.2546001649003.0034602.1122449.07.57.5Ex84.2710003459004.9046728.971000004.807.00 Table 3b: Molecular values of composition of EP 1690889 A1, the amount of M1251 is reported in % by weight based on total mass, as in table 2. M1251 [%]calculated values    Spread factor (S) EP1690889Example 10.646082.952282.11.5 Measured GPC data were not published in EP 1690889 A1, nor can any Mn and Mw data determined using another method be found, thus preventing calculation of polydispersity (PDI).It is apparent from table 3a that the calculated data especially for Mw cannot be used to undertake an estimation. The claimed PDI is thus not disclosed in the prior art.The spread factor is also outside the claimed range.  Example 2: Production of the shaped articles / test specimens The test specimens were produced by injection moulding processes. The moulding compound temperature was between 235°C and 255°C, the die temperature was between 55°C and 83°C and the residence time was between 49 and 59 seconds.The measured values for Charpy notched impact strength, “Charpy” for short, were determined according to DIN 179 1-eA. Table 4: Charpy notched impact strength at 0°C of test specimens made of the base polymers Charpy [kJ / m2]0°CBP17.09BP24.15BP411.75BP59.08 Table 5: Charpy notched impact strength and Charpy factors at 0°C of test specimens according to example 2 Charpy [kJ / m2]Charpy factorCF0°C0°C Ex145.456.697Ex243.266.977Ex355.011.8812Ex456.012.1012Ex541.629.119Ex643.569.5310Ex725.05.546Ex828.452.883 

Claims

 1. High-viscosity, multimodal polyamide compositions having a number-average molar mass () of at least 26 000 g / mol, wherein the polyamide compositions have a spread factor (S) of 2.5 to 30 and a value X of formula 4 of 1.5 to 20, consisting of:a) at least one amine-terminated polyamide (final), wherein the amine-terminated polyamides (final) represent the reaction product of the amine-terminated polyamides (A) with a chain extender,b) at least one non-amine-terminated polyamide (B),  wherein the polyamide composition has a polydispersity index calculated according to PDI = Mw / Mn a value of at least 2.2, Mw and Mn are determined by GPC of the polyamide fraction of the composition and the PDI is carried out according to the process specified in the Methods section, wherein the number-average molar mass () is determined according to the following formula 3Formula 3:where = is the percentage by mass of the amine-terminated polyamides (A) based on the total mass of the polyamides (A) and (B) = is the percentage by mass of the non-amine-terminated polyamides (B) based on the total mass of the polyamides (A) and (B) is the amount of the acid end groups in mmol / kg of the polyamides (A) is the amount of the acid end groups in mmol / kg of the polyamides (B) is the amount of the amino end groups in mmol / kg of the polyamides (A) = is the amount of the active groups in mmol / kg of the chain extender is the percentage by mass of the chain extender based on the mass of the polyamides (A) and (B),o wherein the percentages are fractions and are accordingly always less than 1 and + preferably sum to 1,   wherein the value X is calculated according to the following formula 4Formula 4: where the variables are as defined above,o wherein is calculated via the determination of the end groups of the amine-terminated polyamides (A) according to formula 5Formula 5:  wherein the spread factor is determined by dividing the number-average molar mass () (formula 1) by the number-average molar mass (formula 2) of the employed non-amine-terminated polyamides (B), wherein the number-average molar mass () is calculated according to formula 1Formula 1: wherein is calculated via determination of the end groups according to formula 2,Formula 2:   wherein the term "high-viscosity" is polyamide compositions having a solution viscosity according to DIN 307 of at least 250 ml / g, determined as indicated in the Methods section in the examples, wherein the chain extender is a block copolymer of formula PA.PC, wherein PA stands for polyamide and PC stands for polycarbonate and the content of polycarbonate in the chain extender is 25% to 75% by weight, wherein the end groups of the polyamides are determined according to the methods of end group determination as elucidated in the Methods section in the examples,O wherein the polyamide (A) has amine end groups at least at 70% of the termini,O wherein the polyamide (B) has no amino groups at at least 70% of all termini.   2. High-viscosity, multimodal polyamide compositions according to Claim 1, wherein the PDI is from 2.3 to 15, more preferably from 2.5 to 12, more preferably from 3 to 9 and especially preferably from 4 to 6. 3. High-viscosity, multimodal polyamide compositions according to Claim 1 , wherein the value X of formula 4 is greater than 1.5, preferably greater than 2, more preferably greater than 2.5, yet more preferably greater than 3, particularly preferably greater than 5, more particularly preferably greater than 7 and especially preferably greater than 10.  4. High-viscosity, multimodal polyamide compositions according to Claim 1, wherein the polyamide compositions a spread factor (S) of 2.5 to 25 and a value X of formula 4 of 2 to 18 and preferably a spread factor of 3.5 to 15 and a value X of formula 4 of 3 to 16. 5. Process for producing high-viscosity, multimodal polyamide compositions according to Claim 1, whereina) at least one amine-terminated polyamide (A) is provided,b) at least one non-amine-terminated polyamide (B) is provided and admixed with a chain extender,c) the polyamides (A) and (B) are selected such that a spread factor (S) of 2.5 is exceeded, wherein the spread factor is determined by dividing the number-average molar mass () (formula 1) by the number-average molar mass (formula 2) of the employed non-amine-terminated polyamides (B),  wherein the number-average molar mass () is calculated according to formula 1Formula 1: where = is the percentage by mass of the amine-terminated polyamides (A) based on the total mass of the polyamides (A) and (B) = is the percentage by mass of the non-amine-terminated polyamides (B) based on the total mass of the polyamides (A) and (B) is the amount of the acid end groups in mmol / kg of the polyamides (A) is the amount of the amino end groups in mmol / kg of the polyamides (A) = is the amount of the active groups in mmol / kg of the chain extender is the percentage by mass of the chain extender based on the mass of the polyamides (A) and (B), wherein is calculated via determination of the end groups according to formula 2,Formula 2: where is the amount of the acid end groups in mmol / kg of the polyamides (B) is the amount of the amino end groups in mmol / kg of the polyamides (B) d) the components are heated together in a suitable apparatus with mixing,wherein the percentages are fractions and are accordingly always less than 1 and + preferably sum to 1, and further components may optionally be added and further process steps may optionally be performed.  6. Process according to Claim 5, wherein the spread factor is from more than 2.5 to 30, more preferably from 3 to 25, particularly preferably from 3.5 to 20 and especially preferably from 4 to 15.  7. Process according to Claim 5, wherein the theoretical number-average molar mass is greater than 40 000 g / mol, preferably greater than 50 000 g / mol, more preferably greater than 60 000 g / mol, particularly preferably greater than 70 000 g / mol, more particularly preferably greater than 80 000 g / mol, more particularly preferably greater than 90 000 g / mol and especially preferably greater than 100 000 g / mol.  8. Process according to claim 5, wherein the chain extender is compounded into the non-amine-terminated polyamides, wherein the concentration of the chain-extending additive in the non-amine-terminated polyamides (B) is 2% to 30% by weight, more preferably 3% to 25% by weight, more preferably 4% to 22% by weight, especially preferably 5% to 20% by weight.   9. Polyamide moulding compounds containing the high-viscosity, multimodal polyamide compositions according to claim 1 or the process products of claim 5 in a proportion of at least 50% by weight, preferably in a proportion of at least 60% by weight, more preferably in a proportion of at least 70% by weight, particularly preferably at least 80% by weight, more particularly preferably at least 90% by weight, more particularly preferably at least 95% by weight and especially preferably in a proportion of at least 99% by weight.  10. Polyamide moulding compounds according to Claim 9, wherein the polyamide moulding compounds comprise no BBSA, especially no plasticizer.  11. Polyamide moulding compounds according to Claim 9, wherein the polyamide moulding compounds contain no impact modifier.  12. Shaped articles made of the high-viscosity, multimodal polyamide molding compounds of Claim 9 , optionally using an amount of 0.1% by weight, based on the total molding compound, of demolding agent which is preferably calcium stearate, having a Charpy factor () according to the following formula CFFormula CF: where is the Charpy notched impact strength of a shaped article made of the amine-terminated polyamides and is the Charpy notched impact strength of a shaped article made of the non-amine-terminated polyamides, and are the percentages by mass (as defined in formula 3) of the polyamides (A) and (B) in the shaped article made of high-viscosity, multimodal polyamide moulding compounds according to the invention, this shaped article has the Charpy notched impact strength ; the Charpy factor for measurements at 0°C () is greater than 2, preferably greater than 3, more preferably greater than 4, particularly preferably greater than 5 and especially preferably greater than 6, wherein the Charpy notched impact strength is determined according to DIN 179 1-eA.  13. Shaped articles according to Claim 12, having a Charpy notched impact strength at 0°C of greater than 25 kJ / m2, preferably of greater than 30 kJ / m2, more preferably of greater than 35 kJ / m2, particularly preferably of greater than 40 kJ / m2.   14. Shaped articles according to Claim 12 configured as a coating, covering, film, profile, pipe, corrugated pipe, hollow article, seal, trim piece, holder, housing, sheathing and as electrical and electronic components.

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