DE102015215118A1 - Polyamides with 2,6-BAMP derivatives - Google Patents

Abstract

The invention relates to thermoplastic molding compositions comprising A) from 35 to 100% by weight of an amorphous polyamide composed of A1) from 20 to 100% by weight of units derived from aliphatic dicarboxylic acids and 2,6-bis (aminomethyl) piperidine Derivatives (2,6-BAMP derivatives) derived, A2) 0 to 80 wt .-% of units which are derived from other polyamide-forming monomers, different from A1), B) 0 to 65 wt .-% of other additives, wherein the sum of the weight percentages A) and B) is 100%.

Description

• A) 35 bis 100 Gew.-% eines amorphen Polyamids, aufgebaut aus
• A₁) 20 bis 100 Gew.-% Einheiten, die sich von aliphatischen Dicarbonsäuren und 2,6-bis-(Aminomethyl) piperidin-Derivaten (2,6-BAMP-Derivaten) ableiten,
• A₂) 0 bis 80 Gew.-% Einheiten, welche sich von weiteren Polyamid bildenden Monomeren ableiten, verschieden von A₁),
• B) 0 bis 65 Gew.-% weiterer Zusatzstoffe,

wobei die Summe der Gewichtsprozente A) und B) 100% ergibt.The invention relates to thermoplastic molding compositions containing

• A) 35 to 100 wt .-% of an amorphous polyamide, composed of
• A ₁ ) from 20 to 100% by weight of units derived from aliphatic dicarboxylic acids and 2,6-bis (aminomethyl) piperidine derivatives (2,6-BAMP derivatives),
• A ₂ ) from 0 to 80% by weight of units which are derived from other polyamide-forming monomers, different from A ₁ ),
• B) 0 to 65% by weight of other additives,

where the sum of the weight percent A) and B) is 100%.

Furthermore, the invention relates to the use of the molding compositions according to the invention for the production of fibers, films, moldings and the fibers, films and moldings obtainable in this case.

Polyamides which contain bicyclic aliphatic diamines are, inter alia, from DE-A 10 201 0051 726 known, see also the cited literature therein.

Such polyamides are transparent and usually amorphous, which is why they are particularly suitable for applications with transparency and good mechanics.

From the EP Application No. 13153262.4 Syntheses are known for 2,6-BAMP derivatives, which are also proposed as monomer units for polyamides, but without concrete composition ratios.

The object of the present invention was therefore to provide thermoplastic molding compositions based on amorphous polyamides which have good flowability and good processability.

Accordingly, the molding compositions defined above were found.

Preferred embodiments are given in the dependent claims.

• A₁) 20 bis 100 Gew.-%, insbesondere 30 bis 100 Gew.-%, vorzugsweise 50 bis 100 Gew.-% Einheiten, die sich von aliphatischen Dicarbonsäuren und 2,6-bis-(Aminomethyl) piperidin-Derivaten (2,6-BAMP-Derivaten) ableiten,
• A₂) 0 bis 80 Gew.-%, insbesondere 0 bis 70 Gew.-%, vorzugsweise 0 bis 50 Gew.-% Einheiten, welche sich von weiteren Polyamid bildenden Monomeren ableiten, verschieden von A₁),

wobei die Summe der Gewichtsprozente A₁) und A₂) 100% ergibt.As component A), the molding compositions according to the invention contain 30 to 100, preferably 50 to 100 and in particular 70 to 100 wt .-% of an amorphous polyamide, composed of

• A ₁₎ 20 to 100 wt .-%, in particular 30 to 100 wt .-%, preferably 50 to 100 wt .-% of units derived from aliphatic dicarboxylic acids and 2,6-bis- (aminomethyl) (piperidin-derivatives 2 Derive 6-BAMP derivatives),
• A ₂ ) 0 to 80% by weight, in particular 0 to 70% by weight, preferably 0 to 50% by weight, of units which are derived from further polyamide-forming monomers, different from A ₁ ),

where the sum of the weight percent A ₁ ) and A ₂ ) gives 100%.

Preferred aliphatic dicarboxylic acids are those having linear or branched alkyl radicals having 2 to 20 C atoms, preferably having 4 to 16 C atoms, very particularly preferably having 6 to 14 C atoms.

As dicarboxylic acids, there can be used those having two carboxylic acid groups (carboxy groups) or derivatives thereof. Particularly suitable derivatives are C ₁ -C ₁₀ -alkyl, preferably methyl, ethyl, n-propyl or isopropyl mono- or diesters of the abovementioned dicarboxylic acids, the corresponding dicarboxylic acid halides, in particular the dicarboxylic acid dichlorides and the corresponding dicarboxylic acid anhydrides. Examples of such compounds are ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid (brassylic acid), C ₃₂ -Dimerfettsäure (commercial product from. Cognis Corp., USA) whose Methylester, for example Ethandisäuredimethylester, -propanedioic acid dimethyl ester, Butandisäuredimethylester, Pentandisäuredimethylester, Hexandisäuredimethylester, Heptandisäuredimethylester, Octandisäuredimethylester, Nonandisäuredimethylester, Decandisäuredimethylester, Undecandisäuredimethylester, dodecanedioic acid dimethyl ester, Tridecanedi-di-methyl ester, C ₃₂ -dimer fatty acid dimethyl ester, the dichlorides thereof, for example ethanedioic dichloride, propanedioic dichloride, butanedioic acid dichloride, pentanedioic dichloride, H exanedioic acid dichloride, heptanedioic acid dichloride, Octanedioic dichloride, nonanedioic acid dichloride, decanedioic dichloride, undecanedioic dichloride, dodecanedioic acid diisocyanate, tridecanedisic acid, C ₃₂ -dimetic fatty acid dichloride and their anhydrides, for example butanedicarboxylic acid, pentanedicarboxylic acid, where tetradecanedioic acid (C14), pentadecanedioic acid (C15), hexadecanedioic acid (C16), heptadecanedioic acid (C17), octadecanedioic acid ( C18), 1,4-cyclohexanedioic acid, 1,4-cyclohexanedioic acid are particularly preferred.

Of course, mixtures of the above dicarboxylic acids can be used.

wobei:
A, B und D sind unabhängig voneinander CH₂, CHR² oder CR²R³;
R¹ ist Wasserstoff, unsubstituiertes oder zumindest monosubstituiertes C₁-C₃₀-Alkyl, unsubstituiertes oder zumindest monosubstituiertes C₂-C₁₀-Alkenyl oder unsubstituiertes oder zumindest monosubstituiertes Aryl,
wobei die Substituenten ausgewählt sind aus der Gruppe bestehend aus C₁-C₄-Alkyl, Aryl², -OR⁴, -C(O)R⁶, -C(O)OR⁴, -O-C(O)R⁶, -NR⁴R⁵ oder Halogen,
und Aryl² kann wiederum mit
C₁-C₄-Alkyl, -OR⁴, -C(O)R⁶, -C(O)OR⁴, -O-C(O)R⁶, -NR⁴R⁵ oder Halogen zumindest monosubstituiert sein;
R² und R³ sind unabhängig voneinander unsubstituiertes oder zumindest monosubstituiertes C₁-C₁₀-Alkyl oder unsubstituiertes oder zumindest monosubstituiertes Aryl, wobei die Substituenten ausgewählt sind aus der Gruppe bestehend aus C₁-C₄-Alkyl, -OR⁴, -C(O)R⁶, -C(O)OR⁴, -O-C(O)R⁶, -NR⁴R⁵ oder Halogen;
R⁴ und R⁵ sind unabhängig voneinander Wasserstoff oder unsubstituiertes C₁-C₄-Alkyl;
R⁶ ist unsubstituiertes C₁-C₁₀-Alkyl.The units A1) are derived from 2,6-BAMP derivatives of the following formula I:

in which:
A, B and D are independently CH ₂ , CHR ² or CR ² R ³ ;
R ¹ is hydrogen, unsubstituted or at least monosubstituted C ₁ -C ₃₀ -alkyl, unsubstituted or at least monosubstituted C ₂ -C ₁₀ -alkenyl or unsubstituted or at least monosubstituted aryl,
wherein the substituents are selected from the group consisting of C ₁ -C ₄ alkyl, aryl ² , -OR ⁴ , -C (O) R ⁶ , -C (O) OR ⁴ , -OC (O) R ⁶ , - NR ⁴ R ⁵ or halogen,
and aryl ² can turn with
C ₁ -C ₄ alkyl, -OR ⁴ , -C (O) R ⁶ , -C (O) OR ⁴ , -OC (O) R ⁶ , -NR ⁴ R ⁵ or halogen may be at least monosubstituted;
R ² and R ³ are each independently unsubstituted or at least monosubstituted C ₁ -C ₁₀ alkyl or unsubstituted or at least monosubstituted aryl, wherein the substituents are selected from the group consisting of C ₁ -C ₄ alkyl, -OR ⁴ , -C (O) R ⁶ , -C (O) OR ⁴ , -OC (O) R ⁶ , -NR ⁴ R ⁵ or halogen;
R ⁴ and R ⁵ are independently hydrogen or unsubstituted C ₁ -C ₄ alkyl;
R ⁶ is unsubstituted C ₁ -C ₁₀ alkyl.

The 2,6-BAMP derivatives according to the invention can be prepared advantageously at high conversion and / or high selectivity. Byproducts, such as the corresponding mono-aminomethylpiperidine derivative resulting from hydrogenolysis of either C-CN bond in the dicyanoduct hydrogenation, are only present in minor amounts or can be further reduced by controlling process parameters such as pressure, temperature or catalyst become. Thus, for example, the ratio of N-methyl-2,6-BAMP to the corresponding monoaminomethyl by-product (N-methyl-2-aminomethylpiperidine; N-methyl-2-BAMP) can be controlled between 1: 1 to 15: 1. In particular, the hydrogenation of 2,6-DCP to give the corresponding 2,6-BAMP as such (in the general formula (I) R ¹ is therefore hydrogen) can with high selectivity of preferably 70%, particularly preferably> 85%, performed become.

Furthermore, it is advantageous that the stereoisomer ratio of the 2,6-BAMP derivatives according to the general formula (I) can be regulated by adjusting the reaction conditions. If the 2,6-DCP derivatives used as starting materials are prepared from glutaric acid or glutaric acid derivatives by reaction with hydrocyanic acid and the corresponding amines, the starting materials can already be provided with cis / trans ratios in the range from 80:20 to> 99: 1 , These cis / trans ratios can be maintained in the subsequent hydrogenation to produce the 2,6-BAMP derivatives of the present invention.

The detailed production methods are the EP Application No. 13153262.4 which is why express reference is made to this document.

In the context of the present invention, definitions such as C ₁ -C ₃₀ -alkyl, as defined above for the radical R ¹ in formula (I), mean that this substituent (radical) is an alkyl radical having a carbon atom number of 1 to 30. The alkyl radical can be both linear and branched and optionally cyclic. Alkyl radicals having both a cyclic and a linear component are also covered by this definition. The same also applies to other alkyl radicals, such as, for example, a C ₁ -C ₄ -alkyl radical or a C ₁ -C ₁₀ -alkyl radical. Examples of alkyl radicals are methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, isobutyl, 2-ethylhexyl, tert-butyl (tert-Bu / t-Bu), pentyl, hexyl, heptyl , Cyclohexyl, octyl, nonyl or decyl.

In the context of the present invention, definitions such as C ₂ -C ₁₀ -alkenyl, as defined above for the radical R ¹ in formula (I), mean that this substituent (radical) is an alkenyl radical having a carbon atom number of 2 to 10. This carbon radical is preferably monounsaturated, but if appropriate it may also be mono- or polyunsaturated. With regard to linearity, branching and cyclic proportions, the statements made in this way apply as defined above on the basis of the C ₁ -C ₃₀ -alkyl radicals. In the context of the present invention, C ₂ -C ₁₀ -alkenyl is preferably vinyl, 1-allyl, 3-allyl, 2-allyl, cis- or trans-2-butenyl, ω-butenyl.

In the context of the present invention, the term "aryl" or the term "aryl ² ", as defined above for example for the radical R ¹ in formula (I), means that the substituent (radical) is an aromatic. The aromatic may be a monocyclic, bicyclic or optionally polycyclic aromatic. In the case of polycyclic aromatics, individual cycles may optionally be completely or partially saturated. Preferred examples of aryl are phenyl, naphthyl or anthracyl, in particular phenyl.

wobei:
R¹ ist Wasserstoff, unsubstituiertes oder zumindest monosubstituiertes C₁-C₁₀-Alkyl, unsubstituiertes oder zumindest monosubstituiertes C₂-C₁₀-Alkenyl oder unsubstituiertes oder zumindest monosubstituiertes Aryl,
wobei die Substituenten ausgewählt sind aus der Gruppe bestehend aus C₁-C₄-Alkyl, Aryl², -OR⁴, -NR⁴R⁵ oder Halogen,
und Aryl² kann wiederum mit C₁-C₄-Alkyl, -OR⁴, -NR⁴R⁵ oder Halogen zumindest monosubstituiert sein;
R⁴ und R⁵ sind unabhängig voneinander Wasserstoff oder unsubstituiertes C₁-C₄-Alkyl.Preferred units are 2,6-BAMP derivatives according to the general formula (Ia)

in which:
R ¹ is hydrogen, unsubstituted or at least monosubstituted C ₁ -C ₁₀ -alkyl, unsubstituted or at least monosubstituted C ₂ -C ₁₀ -alkenyl or unsubstituted or at least monosubstituted aryl,
wherein the substituents are selected from the group consisting of C ₁ -C ₄ alkyl, aryl ² , -OR ⁴ , -NR ⁴ R ⁵ or halogen,
and aryl ² may in turn be at least monosubstituted with C ₁ -C ₄ alkyl, -OR ⁴ , -NR ⁴ R ⁵ or halogen;
R ⁴ and R ⁵ are independently hydrogen or unsubstituted C ₁ -C ₄ alkyl.

Particularly preferred is the 2,6-BAMP derivative of the general formula (I) and even more preferred is the 2,6-BAMP derivative of the general formula (Ia), which is defined as follows:
R ¹ is hydrogen, unsubstituted or at least monosubstituted C ₁ -C ₄ alkyl, and the substituent is -NR ⁴ R ⁵ ;
R ⁴ and R ⁵ are independently hydrogen or unsubstituted C ₁ -C ₄ alkyl.

In particular, R ^{1 is} hydrogen. In the case of the general formula (Ia), this (more preferred) embodiment means that it is 2,6-BAMP as such.

As further polyamide-forming monomers A2) are first aromatic dicarboxylic acids into consideration.

Aromatic dicarboxylic acids preferably have 8 to 16 carbon atoms. Suitable aromatic dicarboxylic acids are, for example, terephthalic acid, isophthalic acid, substituted terephthalic and isophthalic acids such as 3-t-butylisophthalic acid, polynuclear dicarboxylic acids, eg. 4,4'- and 3,3'-diphenyldicarboxylic acid, phthalic acid, 4,4'- and 3,3'-diphenylmethanedicarboxylic acid, 4,4'- and 3,3'-diphenylsulfonedicarboxylic acid, 1,4- or 2,6-naphthalenedicarboxylic acid, phenoxyterephthalic acid, with isophthalic acid being particularly preferred.

Other polyamide-forming monomers may be derived from dicarboxylic acids having 4 to 16 carbon atoms and aliphatic or cycloaliphatic diamines having 4 to 16 carbon atoms and aminocarboxylic acids or corresponding lactams having 7 to 12 carbon atoms. Suitable monomers of these types are 1,4-butanediamine, 1,5-pentanediamine, piperazine, 4,4'-diaminodicyclohexylmethane, 2,3- (4,4'-diaminodicyclohexyl) propane or 3,3'-dimethyl-4 , 4'-diaminodicyclohexylmethane, hexamethylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 1,13-diaminotridecane, 2,2,4- or 2,4,4 Trimethylhexamethylenediamine, xylylenediamines, methylpentamethylenediamine and as representatives of the diamines and capryllactam, enanthlactam, ω-aminoundecanoic acid, caprolactam and laurolactam as representatives of lactams or aminocarboxylic acids.

The polyamides can be prepared by processes known per se (eg. EP 129 195 . US 3,948,862 ). Likewise, that can be done in WO 2007/23108 described methods are used in which the corresponding dinitriles of the diacids are used as acid equivalents.

The thermoplastic molding compositions may contain 0 to 65, in particular up to 50, preferably up to 30 wt .-% further additives B).

As component B), the molding compositions in amounts 0 to 40, preferably 1 to 30, in particular 2 to 20 wt .-% of elastomeric polymers (often also referred to as impact modifiers, elastomers or rubbers).

In general, these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters having 1 to 18 C atoms in the alcohol component.

Such polymers are z. In Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg Thieme Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph of CB Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977) described.

In the following some preferred types of such elastomers are presented.

Preferred types of such elastomers are the so-called ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.

EPM rubbers generally have practically no double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.

As diene monomers for EPDM rubbers, for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1,4-diene, hexa-1,5 -diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadienes and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene 2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof. Preference is given to hexa-1,5-diene, 5-ethylidenenorbornene and dicyclopentadiene. The diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.

EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives. Here are z. For example, acrylic acid, methacrylic acid and derivatives thereof, for. As glycidyl (meth) acrylate, and called maleic anhydride.

wobei R¹ bis R⁹ Wasserstoff oder Alkylgruppen mit 1 bis 6 C-Atomen darstellen und m eine ganze Zahl von 0 bis 20, g eine ganze Zahl von 0 bis 10 und p eine ganze Zahl von 0 bis 5 ist.Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids. In addition, the rubbers may still dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, eg. As esters and anhydrides, and / or containing epoxy groups monomers. These dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by addition of monomers containing dicarboxylic acid or epoxy groups of the general formulas I or II or III or IV to the monomer mixture R ¹ C (COOR ² ) = C (COOR ³ ) R ⁴ (I)

wherein R ¹ to R ^{9 represent} hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer of 0 to 20, g is an integer of 0 to 10 and p is an integer of 0 to 5.

The radicals R ¹ to R ⁹ preferably denote hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

Preferred compounds of formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to the free acids and are therefore termed monomers with latent carboxyl groups.

Advantageously, the copolymers consist of 50 to 98 wt .-% of ethylene, 0.1 to 20 wt .-% of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing acid anhydride groups and the remaining amount of (meth) acrylic acid esters.

Particularly preferred are copolymers of 50 to 98, in particular 55 to 95% by weight of ethylene, 0.1 to 40, in particular from 0.3 to 20% by weight of glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and 1 to 45, in particular 5 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.

Further preferred esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.

In addition, vinyl esters and vinyl ethers can also be used as comonomers.

The ethylene copolymers described above can be prepared by methods known per se, preferably by random copolymerization under high pressure and elevated temperature. Corresponding methods are generally known.

Preferred elastomers are also emulsion polymers whose preparation z. As described in Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts which can be used are known per se.

Basically, homogeneously constructed elastomers or those with a shell structure can be used. The shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this order of addition.

Only representative may be here as monomers for the preparation of the rubber part of the elastomers acrylates such. As n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof called. These monomers can with other monomers such. As styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.

The soft or rubber phase (with a glass transition temperature below 0 ° C) of the elastomers may be the core, the outer shell, or a middle shell (for elastomers having more than two shell construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase.

If, in addition to the rubber phase, one or more hard components (having glass transition temperatures of more than 20 ° C.) are involved in the construction of the elastomer, these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, acrylic esters and methacrylates such as methyl acrylate, ethyl acrylate and methyl methacrylate produced as main monomers. In addition, smaller proportions of other comonomers can also be used here.

eingeführt werden können,
wobei die Substituenten folgende Bedeutung haben können:
R¹⁰ Wasserstoff oder eine C₁- bis C₄-Alkylgruppe,
R¹¹ Wasserstoff, eine C₁- bis C₈-Alkylgruppe oder eine Arylgruppe, insbesondere Phenyl,
R¹² Wasserstoff, eine C₁- bis C₁₀-Alkyl-, eine C₆- bis C₁₂-Arylgruppe oder -OR¹³
R¹³ eine C₁- bis C₈-Alkyl- oder C₆- bis C₁₂-Arylgruppe, die gegebenenfalls mit O- oder N-haltigen Gruppen substituiert sein können,
X eine chemische Bindung, eine C₁- bis C₁₀-Alkylen- oder C₆-C₁₂-Arylengruppe oder

Y O-Z oder NH-Z und
Z eine C₁- bis C₁₀-Alkylen- oder C₆- bis C₁₂-Arylengruppe.In some cases it has proven to be advantageous to use emulsion polymers which have reactive groups on the surface. Such groups are for. For example, epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups by the concomitant use of monomers of the general formula

can be introduced
where the substituents may have the following meanings:
R ^{10 is} hydrogen or a C ₁ - to C ₄ -alkyl group,
R ^{11 is} hydrogen, a C ₁ - to C ₈ -alkyl group or an aryl group, in particular phenyl,
R ^{12 is} hydrogen, a C ₁ - to C ₁₀ -alkyl, a C ₆ - to C ₁₂ -aryl group or -OR ¹³
R ^{13 is} a C ₁ - to C ₈ -alkyl or C ₆ - to C ₁₂ -aryl group which may optionally be substituted by O- or N-containing groups,
X is a chemical bond, a C ₁ - to C ₁₀ -alkylene or C ₆ -C ₁₂ -arylene group or

Y OZ or NH-Z and
Z is a C ₁ - to C ₁₀ -alkylene or C ₆ - to C ₁₂ -arylene group.

Also in the EP-A 208 187 grafting monomers described are suitable for introducing reactive groups on the surface.

Other examples which may be mentioned are acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (Nt-butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) -methyl acrylate and (N, N-diethylamino) called ethyl acrylate.

Furthermore, the particles of the rubber phase can also be crosslinked. Examples of monomers acting as crosslinking agents are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate and those described in US Pat EP-A 50 265 described compounds.

Furthermore, it is also possible to use so-called graft-linking monomers, ie monomers having two or more polymerizable double bonds which react at different rates during the polymerization. Preferably, such compounds are used in which polymerized at least one reactive group at about the same rate as the other monomers, while the other reactive group (or reactive groups) z. B. polymerized much slower (polymerize). The different polymerization rates bring a certain proportion of unsaturated double bonds in the rubber with it. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the grafting monomers to form chemical bonds, ie the grafted-on phase is at least partially linked to the grafting base via chemical bonds.

Examples of such graft-crosslinking monomers are allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids. In addition, there are a variety of other suitable graft-linking monomers; for more details, for example, on the U.S. Patent 4,148,846 directed.

In general, the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.

In the following, some preferred emulsion polymers are listed. First, graft polymers having a core and at least one outer shell, which have the following structure: Type Monomers for the core Monomers for the shell I Buta-1,3-diene, isoprene, n-butyl acrylate, ethylhexyl acrylate or mixtures thereof Styrene, acrylonitrile, methylmethacrylate II like I but with the co-use of crosslinkers like I III like I or II n-butyl acrylate, ethyl acrylate, methyl acrylate, buta-1,3-diene, isoprene, ethylhexyl acrylate IV like I or II as I or III but with the concomitant use of monomers having reactive groups as described herein V Styrene, acrylonitrile, methyl methacrylate or mixtures thereof first shell of monomers as described under I and II for the core second shell as described under I or IV for the shell

Instead of graft polymers with a multi-shell structure can also homogeneous, d. H. single-shell elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or copolymers thereof are used. These products can also be prepared by concomitant use of crosslinking monomers or monomers having reactive groups.

Examples of preferred emulsion polymers are n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having an inner core of n-butyl acrylate or butadiene-based and an outer shell of the above copolymers and copolymers of ethylene with comonomers which provide reactive groups.

The elastomers described can also be prepared by other conventional methods, for. B. by suspension polymerization.

Silicone rubbers, as in DE-A 37 25 576 , of the EP-A 235 690 , of the DE-A 38 00 603 and the EP-A 319 290 are also preferred.

Particularly preferred rubbers B) are ethylene copolymers, as described above, which contain functional monomers, the functional monomers being selected from the group of the carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, carboxylic acid amide, carboxylic acid imide, amino, hydroxyl, epoxide , Urethane or oxazoline groups or mixtures thereof.

The proportion of the functional groups is 0.1 to 20, preferably 0.2 to 10 and in particular 0.3 to 3.5 wt .-%, based on 100 wt .-% B).

Particularly preferred monomers are composed of an ethylenically unsaturated mono- or dicarboxylic acid or a functional derivative of such an acid.

In principle, all primary, secondary and tertiary C ₁ -C ₁₈ -alkyl esters of acrylic acid or methacrylic acid, but esters having 1-12 C-atoms, in particular 2-10 C-atoms are preferred.

Examples thereof are methyl, ethyl, propyl, n-, i-butyl and t-butyl, 2-ethylhexyl, octyl and decyl acrylates or the corresponding esters of methacrylic acid. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.

Instead of or in addition to the esters, acid-functional and / or latent acid-functional monomers of ethylenically unsaturated mono- or dicarboxylic acids or monomers containing epoxy groups may also be present in the olefin polymers.

Acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular tert-butyl acrylate and dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids and their monoesters may be mentioned as further examples of monomers.

Suitable latent acid-functional monomers are those compounds which form free acid groups under the polymerization conditions or during the incorporation of the olefin polymers into the molding compositions. Examples which may be mentioned are anhydrides of dicarboxylic acids having up to 20 carbon atoms, in particular maleic anhydride and tertiary C ₁ -C ₁₂ -alkyl esters of the abovementioned acids, in particular tert-butyl acrylate and tert-butyl methacrylate.

The acid-functional or latent acid-functional monomers and the epoxy group-containing monomers are preferably incorporated into the olefin polymers by adding compounds of the general formulas I-IV to the monomer mixture.

The melt index of the ethylene copolymers is generally in the range of 1 to 80 g / 10 min (measured at 190 ° C and 2.16 kg load).

The molecular weight of these ethylene-α-olefin copolymers is between 10,000 and 500,000 g / mol, preferably between 15,000 and 400,000 g / mol (Mn as determined by GPC in 1,2,4-trichlorobenzene with PS calibration).

In a particular embodiment, ethylene-α-olefin copolymers produced by so-called "single site catalysts" are used. More details can the US 5,272,236 be removed. In this case, the ethylene-α-olefin copolymers have a polyolefin narrow molecular weight distribution less than 4, preferably less than 3.5.

Commercial products preferably used are B Exxelor ^® VA 1801 or 1803 Kraton ^® G 1901 or FX Fusabond ^® N NM493 D or Fusabond ^® A560 Exxon, and Kraton ^® DuPont and Tafmer MH 7010 from Mitsui companies.

Of course, it is also possible to use mixtures of the rubber types listed above.

Fibrous or particulate fillers B) which may be mentioned are carbon fibers, glass fibers, glass beads, amorphous silicic acid, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, which are present in amounts of from 1 to 50% by weight, in particular 5 to 40, preferably 10 to 40 wt .-% are used.

Preferred fibrous fillers are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or cut glass in the commercial forms.

The fibrous fillers can be surface-pretreated for better compatibility with the thermoplastics with a silane compound.

n eine ganze Zahl von 2 bis 10, bevorzugt 3 bis 4
m eine ganze Zahl von 1 bis 5, bevorzugt 1 bis 2
k eine ganze Zahl von 1 bis 3, bevorzugt 1Suitable silane compounds are those of the general formula (X- (CH ₂ ) _n ) _k -Si- (OC _m H _{2m + 1} ) _4-k in which the substituents have the following meanings:

n is an integer from 2 to 10, preferably 3 to 4
m is an integer from 1 to 5, preferably 1 to 2
k is an integer from 1 to 3, preferably 1

Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.

The silane compounds are generally used in amounts of 0.01 to 2, preferably 0.025 to 1.0 and in particular 0.05 to 0.5 wt .-% (based on B) for surface coating.

Also suitable are acicular mineral fillers.

For the purposes of the invention, needle-shaped mineral fillers are understood to mean a mineral filler with a pronounced needle-like character. An example is acicular wollastonite. Preferably, the mineral has an L / D (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1. The mineral filler may optionally be pretreated with the silane compounds mentioned above; however, pretreatment is not essential.

As further fillers are kaolin, calcined kaolin, wollastonite, talc and chalk called and additionally platelet or needle-shaped nanofilling preferably in amounts between 0.1 and 10%. Boehmite, bentonite, montmorillonite, vermicullite, hectorite and laponite are preferably used for this purpose. In order to obtain a good compatibility of the platelet-shaped nanofillers with the organic binder, the platelet-shaped nanofillers according to the prior art are organically modified. The addition of the platelet or needle-shaped nanofillers to the nanocomposites according to the invention leads to a further increase in the mechanical strength.

As component B), the molding compositions according to the invention may contain 0.05 to 3, preferably 0.1 to 1.5 and in particular 0.1 to 1 wt .-% of a lubricant.

Preference is given to Al, alkali metal, alkaline earth metal salts or ester or amides of fatty acids having 10 to 44 carbon atoms, preferably having 12 to 44 carbon atoms.

The metal ions are preferably alkaline earth and Al, with Ca or Mg being particularly preferred.

Preferred metal salts are Ca-stearate and Ca-montanate as well as Al-stearate.

It is also possible to use mixtures of different salts, the mixing ratio being arbitrary.

The carboxylic acids can be 1- or 2-valent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids having 30 to 40 carbon atoms).

The aliphatic alcohols can be 1 to 4 valent. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.

The aliphatic amines can be monohydric to trihydric. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Accordingly, preferred esters or amides are glycerin distearate, glycerol tristearate, ethylenediamine distearate, glycerin monopalmitate, glycerol trilaurate, glycerin monobehenate and pentaerythritol tetrastearate.

It is also possible to use mixtures of different esters or amides or esters with amides in combination, the mixing ratio being arbitrary.

As component B), the molding compositions of the invention 0.05 to 3, preferably 0.1 to 1.5 and in particular 0.1 to 1 wt .-% of a Cu stabilizer, preferably a Cu (I) halide, in particular Mixture with an alkali metal halide, preferably KJ, in particular in the ratio 1: 4, or a sterically hindered phenol or mixtures thereof.

Suitable salts of monovalent copper are preferably copper (I) acetate, copper (I) chloride, bromide and iodide. These are contained in amounts of 5 to 500 ppm of copper, preferably 10 to 250 ppm, based on polyamide.

The advantageous properties are obtained in particular when the copper is present in molecular distribution in the polyamide. This is achieved by adding to the molding compound a concentrate containing polyamide, a salt of monovalent copper and an alkali halide in the form of a solid, homogeneous solution. A typical concentrate is z. B. from 79 to 95 wt .-% polyamide and 21 to 5 wt .-% of a mixture of copper iodide or bromide and potassium iodide. The concentration of the solid homogeneous solution of copper is preferably between 0.3 and 3, in particular between 0.5 and 2 wt .-%, based on the total weight of the solution and the molar ratio of copper (I) iodide to potassium iodide is between 1 and 11.5, preferably between 1 and 5.

Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular polyamide 6 and polyamide 6.6.

In principle, all compounds having a phenolic structure and having at least one sterically demanding group on the phenolic ring are suitable as sterically hindered phenols B).

in Betracht, in der bedeuten:
R¹ und R² eine Alkylgruppe, eine substituierte Alkylgruppe oder eine substituierte Triazolgruppe, wobei die Reste R¹ und R² gleich oder verschieden sein können und R³ eine Alkylgruppe, eine substituierte Alkylgruppe, eine Alkoxigruppe oder eine substituierte Aminogruppe.Preferably z. B. Compounds of the formula

into consideration, in which mean:
R ¹ and R ^{2 are} an alkyl group, a substituted alkyl group or a substituted triazole group, wherein the radicals R ¹ and R ^{2 may be the} same or different and R ^{3 is} an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.

Antioxidants of the type mentioned are, for example, in the DE-A 27 02 661 ( US 4,360,617 ).

Another group of preferred sterically hindered phenols are derived from substituted benzenecarboxylic acids, especially substituted benzenepropionic acids.

wobei R⁴, R⁵, R⁷ und R⁸ unabhängig voneinander C₁-C₈-Alkylgruppen darstellen, die ihrerseits substituiert sein können (mindestens eine davon ist eine sterisch anspruchsvolle Gruppe) und R⁶ einen zweiwertigen aliphatischen Rest mit 1 bis 10 C-Atomen bedeutet, der in der Hauptkette auch C-O-Bindungen aufweisen kann.Particularly preferred compounds of this class are compounds of the formula

where R ⁴ , R ⁵ , R ⁷ and R ⁸ independently of one another are C ₁ -C ₈ -alkyl groups which in turn may be substituted (at least one of which is a sterically demanding group) and R ^{6 is} a bivalent aliphatic radical having 1 to 10C Atom, which may also have CO bonds in the main chain.

(Irganox^® 245 der Firma BASF SE)

(Irganox^® 259 der Firma BASF SE)Preferred compounds corresponding to this formula are

(Irganox ^® 245 from BASF SE)

(Irganox ^® 259 from BASF SE)

By way of example, the following may be mentioned by way of example as sterically hindered phenols:
2,2'-methylenebis (4-methyl-6-tert-butylphenol), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate ], Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxy-phenyl) -propionate], distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2, 6,7-Trioxa-1-phosphabicyclo [2.2.2] oct-4-ylmethyl-3,5-di-tert-butyl-4-hydroxyhydro-cinnamate, 3,5-di-tert-butyl 4-hydroxyphenyl-3,5-distearyl-thiotriazylamine, 2- (2'-hydroxy-3'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,6-di- tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 4,4'-methylene bis- (2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyl-dimethylamine.

Have been found to be particularly effective and therefore preferably be used 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 1,6-hexanediol bis (3,5-di-tert. -butyl-4-hydroxyphenyl] propionate (Irganox ^® 259), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and N, N'-hexamethylene-bis -3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox ^® 1098), and Irganox ^® 245 from BASF SE, which is particularly well suited described above.

The antioxidants B), which can be used individually or as mixtures, are in an amount of 0.05 to 3 wt .-%, preferably from 0.1 to 1.5 wt .-%, in particular 0.1 to 1 Wt .-%, based on the total weight of the molding compositions A) and B).

In some cases, sterically hindered phenols having no more than one sterically hindered group ortho to the phenolic hydroxy group have been found to be particularly advantageous; especially when assessing color stability when stored in diffused light for extended periods of time.

As component B), the molding compositions according to the invention may contain 0.05 to 5, preferably 0.1 to 2 and in particular 0.25 to 1.5 wt .-% of a nigrosine.

Nigrosines are generally understood to mean a group of black or gray indulene-related phenazine dyes (azine dyes) in various embodiments (water-soluble, fat-soluble, gas-soluble) used in wool dyeing and printing, in black dyeing of silks, for dyeing of leather, shoe creams, varnishes, plastics, stoving lacquers, inks and the like, as well as being used as microscopy dyes.

Technically, nigrosine is obtained by heating nitrobenzene, aniline, and aniline with anhydrous metal. Iron and FeCl ₃ (name of Latin niger = black).

Component B) can be used as free base or else as salt (for example hydrochloride).

Further details of Nigrosinen are for example the electronic dictionary Römpp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword "Nigrosin" refer to.

As component B) the thermoplastic molding compositions of the invention may contain conventional processing aids such as stabilizers, antioxidants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, flame retardants, etc.

Examples of oxidation inhibitors and heat stabilizers are sterically hindered phenols and / or phosphites and amines (eg TAD), hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, called based on the weight of the thermoplastic molding compositions.

As UV stabilizers, which are generally used in amounts of up to 2 wt .-%, based on the molding composition, various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned.

It is possible to add inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as anthraquinones as colorants.

As nucleating agents, sodium phenylphosphinate, alumina, silica and preferably talc may be used.

As flame retardants red phosphorus, P- and N-containing flame retardants and halogenated FS-agent systems and their synergists may be mentioned.

The thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed. The mixing temperatures are usually at 150 to 320 ° C, preferably at 200 to 250 ° C. The residence time is usually from 1 to 10 minutes, preferably from 2 to 5 minutes.

The thermoplastic molding compositions according to the invention are characterized by better flowability and processability.

These are suitable for the production of moldings of any kind for applications z. B. in the automotive, E. u. E., Houseware, film, fiber industry, especially for applications where high transparency is required, such. B. in the optical or automotive industry.

Examples

DSC measurement

The enthalpy of fusion delta H (2), the glass transition temperature T _g (2) and the melting temperature T _m (2) were determined in a manner known per se by means of differential scanning calorimetry (DSC) ( DIN EN ISO 11357, parts 1 and 3 or after ISO 11357-2: 2013 ). The DSC measurement was carried out on thermally conditioned samples. For this purpose, the DSC measurement on one and the same sample was expediently repeated once or twice. After the first heating, the sample was melted for 5 minutes to quench the thermal history of the polyamide and thus to ensure a defined thermal history of the respective polyamide (thermally conditioned polyamide). The index (2) at enthalpy of fusion delta H (2), glass transition temperature T _g (2) and melting temperature T _m (2) means that the evaluation was made on the basis of the second heating curve (1st repetition).

The melting enthalpy delta H (2), glass transition temperature T _g (2) and melting temperature T _m (2) are determined under nitrogen in open aluminum crucibles at a heating rate and cooling rate of 20 K / min. Measurement and evaluation took place after DIN EN ISO 11357-3 or after ISO 11357-2: 2013 ,

The melting temperature T _m (2) is the endothermic peak maximum of the DSC curve during the second heating according to a defined thermal history (see above). To determine the enthalpy of fusion Delta H (2), a baseline was applied to the endothermic melting peak by connecting the peak initial temperature to the peak end temperature. The melting enthalpy delta H (2) was obtained by determining the area between the baseline and the endothermic melting peak. The glass transition temperature T _g (2) was after ISO 11357-2: 2013 certainly. This is the temperature of the midline intersection between the extrapolated baselines before and after the glass transition with the DSC trace.

viscosity measurement

The viscosity number (VZ) was after EN-ISO 1628-1 measured as 0.5% polymer solution in 96% sulfuric acid at 25 ° C.

I. M1: Preparation of 2,6-bis (aminomethyl) piperidine (2,6-BAMP)

• a) 62 g of water were introduced and cooled to 5 ° C. Subsequently, 175.0 g of 25% strength by weight aqueous ammonia, 250.0 g of a 50% by weight aqueous glutaraldehyde solution and 68.3 g of hydrocyanic acid were added in parallel within 60 minutes, the feed of hydrocyanic acid being about 10 Minutes started earlier. The feeds were made so that a temperature of 10 ° C was not exceeded. After an after-reaction of 12 hours at a maximum of 10 ° C, the resulting precipitate was filtered off with suction. 156 g of a water-moist, white solid were obtained. To remove the water, this was taken up in 700 ml of tetrahydrofuran, dried with sodium sulfate and filtered. Concentration of the filtrate on a rotary evaporator gave 109 g of a white solid, which was characterized by means of 13 C-NMR as 2,6-dicyanopiperidine.
• b) Hydrogenation (Semi-Batch) In a 270 ml autoclave with baffles and disk stirrer 5 g (dry) Raney cobalt and 40 g of THF were submitted. The autoclave was heated to 120 ° C and hydrogen pressed to a total pressure of 100 bar. Within 5.5 hours, a mixture of 8 g of 2,6-dicyanopiperidine (prepared according to Example a)) in 72 g of THF was added. The reaction mixture was stirred for a further 60 minutes under reaction conditions. The hydrogenation effluent contained 90% 2,6-bis (aminomethyl) piperidine (GC area%). The rest were unknown minor components.

II. M2: Preparation of 1-methyl-2,6-bis- (aminomethyl) -piperidine (m-2,6-BAMP)

The preparation of m-2,6 - BAMP was carried out analogously to Example M1 using methylamine instead of ammonia.

III. Production of the polyamides

Experiments with m-2,6 - BAMP:

• A1: To a 100 ml test tube was added 8.19 g of adipic acid, 8.81 g of m-2,6-BAMP and 11.33 g of distilled water. The reaction mixture was purged with nitrogen 10 times and the temperature increased to 200 ° C. The pressure was kept at 16 bar for 60 minutes. Subsequently, the temperature was increased to 250 ° C and held at 20 bar for a further 60 min. The mixture was then depressurized to atmospheric pressure within 60 minutes and condensed under nitrogen flow (16 l / h) for a further 60 min. After pressing 5 bar nitrogen pressure, the polymer was cooled to RT and removed.
• A2: To a 100 ml test tube were added 9.56 g of sebacic acid, 7.44 g of m-2,6-BAMP and 11.33 g of distilled water. The reaction mixture was purged with nitrogen 10 times and the temperature raised to 200 ° C. The pressure was kept at 16 bar for 60 minutes. Subsequently, the temperature was increased to 250 ° C and held at 20 bar for a further 60 min. The mixture was then depressurized to atmospheric pressure within 60 minutes and condensed under nitrogen flow (16 l / h) for a further 60 min. After pressing 5 bar nitrogen pressure, the polymer was cooled to RT and removed.
• A3: Into a 100 ml test tube were added 10.10 g of dodecanedioic acid, 6.90 g of m-2,6-BAMP and 11.33 g of distilled water. The reaction mixture was purged with nitrogen 10 times and the temperature raised to 200 ° C. The pressure was kept at 16 bar for 60 minutes. Subsequently, the temperature was increased to 250 ° C and held at 20 bar for a further 60 min. Subsequently, it was depressurized to atmospheric pressure within 60 minutes and condensed under nitrogen flow (16 L / h) for a further 60 minutes. After pressing 5 bar nitrogen pressure, the polymer was cooled to RT and removed.

Experiments with 2,6 - BAMP:

• B1: To a 100 ml test tube were added 8.59 g of adipic acid, 8.42 g of m-2,6-BAMP and 11.33 g of distilled water. The reaction mixture was purged with nitrogen 10 times and the temperature raised to 200 ° C. The pressure was kept at 16 bar for 60 minutes. Subsequently, the temperature was increased to 250 ° C and held at 20 bar for a further 60 min. The mixture was then depressurized to atmospheric pressure within 60 minutes and condensed under nitrogen flow (16 l / h) for a further 60 min. After pressing 5 bar nitrogen pressure, the polymer was cooled to RT and removed.
• B2: To a 100 ml test tube were added 9.95 g of sebacic acid, 7.05 g of m-2,6-BAMP and 11.33 g of distilled water. The reaction mixture was purged with nitrogen 10 times and the temperature raised to 200 ° C. The pressure was kept at 16 bar for 60 minutes. Subsequently, the temperature was increased to 250 ° C and held at 20 bar for a further 60 min. The mixture was then depressurized to atmospheric pressure within 60 minutes and condensed under nitrogen flow (16 l / h) for a further 60 min. After pressing 5 bar nitrogen pressure, the polymer was cooled to RT and removed.
• B3: Into a 100 ml test tube were placed 10.48 g of dodecanedioic acid, 6.82 g of m-2,6-BAMP and 11.33 g of distilled water. The reaction mixture was purged with nitrogen 10 times and the temperature raised to 200 ° C. The pressure was kept at 16 bar for 60 minutes. Subsequently, the temperature was increased to 250 ° C and held at 20 bar for a further 60 min. The mixture was then depressurized to atmospheric pressure within 60 minutes and condensed under nitrogen flow (16 l / h) for a further 60 min. After pressing 5 bar nitrogen pressure, the polymer was cooled to RT and removed.

Comparative tests:

• V1: To a 100 ml test tube was added 8.62 g of adipic acid, 8.39 g of 1,3-cyclohexane bis (methylamine) and 11.33 g of distilled water. The reaction mixture was purged with nitrogen 10 times and the temperature raised to 200 ° C. The pressure was kept at 16 bar for 60 minutes. Subsequently, the temperature was increased to 250 ° C and held at 20 bar for a further 60 min. The mixture was then depressurized to atmospheric pressure within 60 minutes and condensed under nitrogen flow (16 l / h) for a further 60 min. After pressing 5 bar nitrogen pressure, the polymer was cooled to RT and removed.
• V2: To a 100 ml test tube was added 9.98 g of sebacic acid, 7.02 g of 1,3-cyclohexane bis (methylamine) and 11.33 g of distilled water. The reaction mixture is purged with nitrogen 10 times and the temperature raised to 200 ° C. The pressure was kept at 16 bar for 60 minutes. Subsequently, the temperature was increased to 250 ° C and held at 20 bar for a further 60 min. The mixture was then depressurized to atmospheric pressure within 60 minutes and condensed under nitrogen flow (16 l / h) for a further 60 min. After pressing 5 bar nitrogen pressure, the polymer was cooled to RT and removed.
• V3: Into a 100 ml test tube were placed 10.51 g of dodecanedioic acid, 6.49 g of 1,3-cyclohexane bis (methylamine) and 11.33 g of distilled water. The reaction mixture was purged with nitrogen 10 times and the temperature raised to 200 ° C. The pressure was kept at 16 bar for 60 minutes. Subsequently, the temperature was increased to 250 ° C and held at 20 bar for a further 60 min. The mixture was then depressurized to atmospheric pressure within 60 minutes and condensed under nitrogen flow (16 l / h) for a further 60 min. After pressing 5 bar nitrogen pressure, the polymer was cooled to RT and removed.

Table I attempt Tg (2) [° C] Tm (2) [° C] Delta H (2) [Y / g] VZ [ml / g] A1 73 amorphous amorphous 33 A2 52 amorphous amorphous 35 A3 40 amorphous amorphous 33 B1 85 amorphous amorphous 52 B2 75 amorphous amorphous 51 B3 72 amorphous amorphous 62 V1 99 amorphous amorphous 38 V2 82 amorphous amorphous 72 V3 75 amorphous amorphous 89

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102010051726 A [0003]
• EP 13153262 [0005, 0016]
• EP 129195 [0026]
• US 3948862 [0026]
• WO 2007/23108 [0026]
• EP 208187A [0050]
• EP 50265A [0052]
• US 4148846 [0054]
• DE 3725576A [0060]
• EP 235690A [0060]
• DE 3800603A [0060]
• EP 319290A [0060]
• US 5272236 [0072]
• DE 2702661 A [0099]
• US Pat. No. 4,360,617 [0099]

Cited non-patent literature

• Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg Thieme Verlag, Stuttgart, 1961). Pages 392 to 406 [0030]
• CB Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977). [0030]
• electronic dictionary Römpp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword "Nigrosine" [0111]
• DIN EN ISO 11357, parts 1 and 3 [0121]
• ISO 11357-2: 2013 [0121]
• DIN EN ISO 11357-3 [0122]
• ISO 11357-2: 2013 [0122]
• ISO 11357-2: 2013 [0123]
• EN-ISO 1628-1 [0124]

Claims (8)

Thermoplastic molding compositions comprising A) from 35 to 100% by weight of an amorphous polyamide synthesized from A ₁ ) from 20 to 100% by weight of units derived from aliphatic dicarboxylic acids and 2,6-bis (aminomethyl) piperidine derivatives (2 , 6-BAMP derivatives), A ₂ ) 0 to 80 wt .-% of units which are derived from other polyamide-forming monomers, different from A ₁ ), B) 0 to 65 wt .-% of other additives, wherein the Sum of the weight percent A) and B) 100% results. Thermoplastic molding compositions according to Claim 1, in which the units A ₁ ) are 30 to 100% by weight and A ₂ ) 0 to 70% by weight. Thermoplastic molding compositions according to claims 1 or 2, in which the aliphatic dicarboxylic acids have linear or branched alkyl radicals having 2 to 20 C atoms. Thermoplastic molding compositions according to claims 1 to 3, in which the units A1) are derived from 2,6-BAMP derivatives of the general formula I:

wherein: A, B and D are independently CH ₂ , CHR ² or CR ² R ³ ; R ¹ is hydrogen, unsubstituted or at least monosubstituted C ₁ -C ₃₀ -alkyl, unsubstituted or at least monosubstituted C ₂ -C ₁₀ -alkenyl or unsubstituted or at least monosubstituted aryl, where the substituents are selected from the group consisting of C ₁ -C ₄ Alkyl, aryl ² , -OR ⁴ , -C (O) R ⁶ , -C (O) OR ⁴ , -OC (O) R ⁶ , -NR ⁴ R ⁵ or halogen, and aryl ² may in turn be substituted with C ₁ -C ₄ alkyl, -OR ⁴ , -C (O) R ⁶ , -C (O) OR ⁴ , -OC (O) R ⁶ , -NR ⁴ R ⁵ or halogen may be at least monosubstituted; R ² and R ³ are each independently unsubstituted or at least monosubstituted C ₁ -C ₁₀ alkyl or unsubstituted or at least monosubstituted aryl, wherein the substituents are selected from the group consisting of C ₁ -C ₄ alkyl, -OR ⁴ , -C (O) R ⁶ , -C (O) OR ⁴ , -OC (O) R ⁶ , -NR ⁴ R ⁵ or halogen; R ⁴ and R ⁵ are independently hydrogen or unsubstituted C ₁ -C ₄ alkyl; R ⁶ is unsubstituted C ₁ -C ₁₀ alkyl. Thermoplastic molding compositions according to claims 1 to 4, in which the units A1) are derived from 2,6-BAMP derivatives of the general formula (Ia):

where: R ¹ is hydrogen, unsubstituted or at least monosubstituted C ₁ -C ₁₀ -alkyl, unsubstituted or at least monosubstituted C ₂ -C ₁₀ -alkenyl or unsubstituted or at least monosubstituted aryl, where the substituents are selected from the group consisting of C ₁ - C ₄ alkyl, aryl ² , -OR ⁴ , -NR ⁴ R ⁵ or halogen, and aryl ² may in turn be at least monosubstituted with C ₁ -C ₄ alkyl, -OR ⁴ , -NR ⁴ R ⁵ or halogen; R ⁴ and R ⁵ are independently hydrogen or unsubstituted C ₁ -C ₄ alkyl. Thermoplastic molding compositions according to claims 1 to 5, in which the units A1) derive 2,6-BAMP derivatives of the general formula (Ia) where R ¹ is hydrogen, unsubstituted or at least monosubstituted C ₁ -C ₄ -alkyl and Substituent is -NR ⁴ R ⁵ ; R ⁴ and R ⁵ are independently hydrogen or unsubstituted C ₁ -C ₄ alkyl. Use of the thermoplastic molding compositions according to claims 1 to 6 for the production of moldings, fibers and films. Shaped bodies, fibers and films obtainable from the thermoplastic molding compositions according to claims 1 to 6.