DE102010051726A1 - Thermoplastic molding composition useful for preparing molding, fiber and film, comprises amorphous polyamide constructed from units derived from aliphatic dicarboxylic acid and units derived from bicyclic aliphatic diamine, and additives - Google Patents

Abstract

Thermoplastic molding composition comprises (in wt.%): (a) an amorphous polyamide (35-100) constructed from (a1) units derived from aliphatic dicarboxylic acids and bicyclic aliphatic diamines (30-100) and (a2) units derived from further polyamide-forming monomers (0-70), which are different from (a1); and (b) further additives (0-65), where the sum of the weights of the components (a) and (b) is 100 wt.%. An independent claim is also included for moldings, fibers and films produced by the above thermoplastic molding composition.

Description

• A) 35 bis 100 Gew.-% eines amorphen Polyamids aufgebaut aus
• A₁) 30 bis 100 Gew.-% Einheiten, die sich von aliphatischen Dicarbonsäuren und bicyclischen aliphatischen Diaminen ableiten,
• A₂) 0 bis 70 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% ergeben.The invention relates to thermoplastic molding compositions containing

• A) 35 to 100 wt .-% of an amorphous polyamide composed of
• A ₁ ) from 30 to 100% by weight of units derived from aliphatic dicarboxylic acids and bicyclic aliphatic diamines,
• A ₂ ) 0 to 70% 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,

the sum of the weight percentages A) and B) being 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 and copolyamides prepared by using 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine, IPDA), 4,4-diaminodicyclohexyl or bis (4-aminocycohexyl) alkane-type diamines which are attached to the cyclohexyl radicals by two methyl groups are prepared, are known.

The in the GB-PS 6 19 707 and in the US-PS 24 94 563 described polyamides of 4,4-diaminodicyclohexyl or from the diamines of bis (4-aminocyclohexyl) methane type and from dicarboxylic acids such as adipic acid or sebacic acid are transparent, if used for their preparation at 25 ° C liquid isomer mixtures of diamines. The processability and certain properties such as the transparency and resistance to hydrolysis of boiling water, the resistance to stress cracking in organic solvents of these transparent polyamides are unsatisfactory for certain applications.

That in the US-PS 26 96 482 described transparent polyamide from the liquid at 25 ° C isomer mixtures of 4,4-diaminodicyclohexylmethane and iso-phthalic acid has a good resistance to hot water. For an advantageous sequence of the polycondensation, however, one must start from the diphenyl ester of isophthalic acid or add phenol as the solvent or plasticizer to the polycondensation mixture. Due to the high softening temperature and the high melt viscosity of this transparent polyamide, whose maximum water absorption is 7.75%, processing temperatures around 330 ° C are required.

Similar disadvantages also in the US-PS 25 16 585 described transparent polyamide of bis (4-amino-3-methylcyclohexyl) methane and terephthalic acid.

In the U.S. Patent No. 3,847,877 described transparent copolyamides of 4,4, -Diaminodicyclohexylmethan, from terephthalic acid and / or isophthalic acid and from caprolactam show a similar high water absorption capacity and tend when heated with boiling water after a few days to opacification. In addition, they still contain amounts of unreacted monomeric caprolactam, which limits their utility in many areas or impossible.

The latter also applies to those in the DE-OS 15 95 354 described transparent copolyamides of 2,2-bis (4-amino-cyclohexyl) -propane, dicarboxylic acids with more than 20 wt .-% caprolactam and / or another conventional polyamide former, for. Hexamethylenediammonium adipate which are soluble in methanol.

As far as in the DE-OS 15 95 354 described transparent polyamides are composed only of 2,2-bis (4-aminocyclohexyl) propane and a dicarboxylic acid such as adipic acid, they have better solvent resistance, but are difficult to process because of their very high softening points. It is not possible to produce from them stress-free molded parts.

The in the US-PS 35 97 400 described transparent copolyamides of 4,4-diaminodicyclohexylmethane, hexamethylenediamine, terephthalic acid and isophthalic acid have a large water absorption capacity. Therefore, when these transparent copolyamides are stored in water, their softening points are lowered to 50 to 60 ° C.

The in the US-PS 38 42 045 described transparent copolyamides, the polycondensation products of 4,4-diaminodicyclohexylmethane, which is only 40% to 54% in the trans / trans configuration, and a mixture of 50 to 70 mol% of decanedicarboxylic acid-1, 10 and 30 to 50 mol% of cork or azelaic acid, contain neither aromatic dicarboxylic acid nor an additional polyamide-forming component. This also applies to the transparent copolyamides of 2,2-bis (4-amino-cyclohexyl) -propane and / or its methyl derivatives and of dicarboxylic acid mixtures containing from 20 to 65 mol% of adipic acid and from 35 to 80 mol% made of suberic acid, azelaic acid, sebacic acid and / or decanedicarboxylic acid-1,10, according to the teaching of US-PS 38 40 501 ,

Also the CH-PS 4 49 257 refers to transparent polyamides of decanedicarboxylic acid-1,10 and from dicyan-type diamines, including bis (4-amino-3-methylcyclohexyl) methane or 2,2-bis (4-amino-cyclohexyl) -propane with similar structure.

The in the DE-OS 24 05 985 mentioned flame-retardant thermoplastic molding compositions contain, in addition to red phosphorus, a transparent polyamide or mixtures of two or more transparent polyamides. Also known as transparent polyamides are those which consist of 35 mol% of 4,4-diaminodicyclohexylmethane or 2,2-bis (4-aminocyclohexyl) -propane, 35 mol% of isophthalic acid and 30 mol% of omega-aminolauric acid ( or the corresponding lactam) or a stoichiometric mixture of dodecanemethylenediamine and decanedicarboxylic acid-1,10. The monomer mixtures to be used for the preparation of these polyamides consist of 33 or 31.5% by weight of omega-aminolauric acid or of the stoichiometric mixture of dodecanemethylenediamine and decanedicarboxylic acid-1,10.

The DE-OS 29 36 759 In the case of high glass transition point transparent copolyamides employing 30 and more wt.% of an omega-aminocarboxylic acid of at least 11 carbon atoms to lower the high processing viscosity, a substantial amount of isophoronediamine is present besides a di-cyano-diamine. This, however, promotes brittleness and discoloration of the copolyamide.

In the EP 0 012 931 transparent copolyamides are described, which are composed inter alia of adipic acid, hexamethylenediamine and as a further diamine component of a mixture of bis (4-aminocyclohexyl) methane. At these an insufficient hot water resistance is detected.

The in the DE-PS 26 42 244 listed transparent copolyamides of omega-aminocarboxylic acid, isophthalic acid and a methyl derivative of bis (4-aminocyclo-hexyl) -methans have insufficient heat resistance, stress corrosion cracking resistance, toughness, transparency and hydrolysis resistance in boiling water and have the disadvantage of a relatively high processing viscosity.

In the US-PS 42 93 687 the general class of cyclic diamines used according to the invention and their preparation are mentioned. However, it is not recognized that especially the methylethyl homologue and not that only specially selected isomeric mixtures are reactive to the extent desired. In addition, the teaching of the cited patent describes selected crystalline linear polyamides and no amorphous copolyamides.

It is an object of the present invention to provide thermoplastic molding compositions based on amorphous polyamides which have a reduced water absorption and an elevated glass transition temperature.

Accordingly, the molding compositions defined above were found.

Preferred embodiments are given in the dependent claims.

• A₁) 30 bis 100 Gew.-%, vorzugsweise 50 bis 100 Gew.-% Einheiten, die sich von aliphatischen Dicarbonsäuren und bicyclischen aliphatischen Diaminen ableiten,
• A₂) 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 from 30 to 100, preferably from 50 to 100, and in particular from 70 to 100,% by weight of an amorphous polyamide synthesized from

• A ₁ ) from 30 to 100% by weight, preferably from 50 to 100% by weight, of units derived from aliphatic dicarboxylic acids and bicyclic aliphatic diamines,
• A ₂ ) 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 exandisäuredichlorid, Heptandisäuredichlorid, Octandisäuredichlorid, Nonandisäuredichlorid, Decandisäuredichlorid, Undecandisäuredichlorid, Dodecandisäuredi chloride, Tridecandisäuredichlorid, C ₃₂ -Dimerfettsäuredichlord and anhydrides thereof, for example, butanedicarboxylic acid, pentanedicarboxylic acid, wherein tetradecanedioic acid (C14), pentadecanedioic acid (C15), hexadecanedioic (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 die Variablen folgende Bedeutung haben:
R¹, R², R³, R⁴, R⁵, R⁶ unabhängig voneinander Wasserstoff oder lineare oder verzweigte Alkyreste mit 1 bis 6 C-Atomen,
Bevorzugte Reste R¹ bis R⁶ sind unabhängig voneinander Wasserstoff, Butyl, iso-Butyl, t-Butyl, n-Propyl, iso-Propyl, Methyl oder Ethyl, wobei Methyl, Ethyl oder Isopropyl als Alkylreste besonders und Methyl oder Ethyl ganz besonders bevorzugt sind.The bicyclic aliphatic diamines preferably correspond to the general formula

where the variables have the following meaning:
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ independently of one another denote hydrogen or linear or branched alkyl radicals having 1 to 6 C atoms,
Preferred radicals R ¹ to R ⁶ are, independently of one another, hydrogen, butyl, isobutyl, t-butyl, n-propyl, isopropyl, methyl or ethyl, with methyl, ethyl or isopropyl being particularly preferred as alkyl radicals and methyl or ethyl being particularly preferred are.

Particularly preferred radicals R ¹ to R ⁶ are hydrogen.

As further polyamide-forming monomers A ₂ ) 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 the representatives of Diamines and capryllactam, Önanthlactam, ω-aminoundecanoic acid, caprolactam and laurolactam called 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 of the invention may contain 0 to 3, preferably 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 esters or amides of fatty acids having 10 to 44 carbon atoms, preferably having 14 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 further components B), the molding compositions according to the invention may contain heat stabilizers or antioxidants or mixtures thereof selected from the group of copper compounds, sterically hindered phenols, sterically hindered aliphatic amines and / or aromatic amines.

Copper compounds are in the polyamide molding compositions according to the invention to 0.05 to 3, preferably 0.1 to 1.5 and in particular 0.1 to 1 wt .-%, preferably as Cu (I) halide, in particular in admixture with an alkali halide, preferably KJ, in particular in the ratio 1: 4, or a sterically hindered phenol or an amine stabilizer or mixtures thereof.

Suitable salts of monovalent copper are preferably copper (I) acetate, copper (I) chloride, bromide and iodide. They are contained in amounts of 5 to 500 ppm 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.

Suitable hindered phenols are in principle all compounds having a phenolic structure which have at least one sterically demanding group on the phenolic ring.

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 Pat. No. 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 Ciba SC)Preferred compounds corresponding to this formula are

(Irganox ^® 245 from Ciba SC)

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-hydroxyphenol) -propionate ], Pentaerytrityl 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'-methylenebis (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-butylphenyl), 1,6-hexanediol bis (3,5-di-tert. -butyl-4-hydroxyphenyl] -propionate, 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 Ciba SC, which is particularly well suited described above.

The phenolic antioxidants, which can be used singly 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 fibrous or particulate fillers B) are carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar called in amounts up to 40 wt .-%, in particular 1 to 15 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 thermoplastic 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 -Sk (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 the fibrous fillers) 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.

In particular, talc is used which is a hydrated magnesium silicate of the composition Mg _{3 [} (OH) ₂ / Si ₄ O ₁₀ ] or 3MgO.4SiO ₂ .H ₂ O. These so-called three-layer phyllosilicates have a triclinic, monoclinic or rhombic crystal structure with a platelet-like appearance. On further trace elements Mn, Ti, Cr, Ni, Na and K may be present, wherein the OH group may be partially replaced by fluoride.

Examples of impact modifiers as component B) are rubbers which may have functional groups. It is also possible to use mixtures of two or more different impact-modifying rubbers.

Rubbers which increase the toughness of the molding compositions generally contain an elastomeric moiety which has a glass transition temperature of less than -10 ° C, preferably less than -30 ° C, and contain at least one functional group capable of reacting with the polyamide , Suitable functional groups are, for example, carboxylic acid, carboxylic acid anhydride, carboxylic ester, carboxamide, carboxylic imide, amino, hydroxyl, epoxide, urethane or oxazoline groups, preferably carboxylic anhydride groups.

• 1. 40 bis 99 Gew.-% mindestens eines alpha-Olefins mit 2 bis 8 C-Atomen,
• 2. 0 bis 50 Gew.-% eines Diens,
• 3. 0 bis 45 Gew.-% eines C₁-C₁₂-Alkylesters der Acrylsäure oder Methacrylsäure oder Mischungen derartiger Ester,
• 4. 0 bis 40 Gew.-% einer ethylenisch ungesättigten C₂-C₂₀-Mono- oder Dicarbonsäure oder einem funktionellen Derivat einer solchen Säure,
• 5. 0 bis 40 Gew.-% eines Epoxygruppen enthaltenden Monomeren, und
• 6. 0 bis 5 Gew.-% sonstiger radikalisch polymerisierbarer Monomerer,

wobei die Summe der Komponenten 3) bis 5) mindestens 1 bis 45 Gew.-% beträgt, bezogen auf die Komponenten 1) bis 6).Preferred functionalized rubbers include functionalized polyolefin rubbers composed of the following components:

• 1. 40 to 99 wt .-% of at least one alpha-olefin having 2 to 8 carbon atoms,
• 2. 0 to 50% by weight of a diene,
• 3. 0 to 45 wt .-% of a C ₁ -C ₁₂ alkyl ester of acrylic acid or methacrylic acid or mixtures of such esters,
• 4. 0 to 40% by weight of an ethylenically unsaturated C ₂ -C ₂₀ -mono- or dicarboxylic acid or a functional derivative of such an acid,
• 5. 0 to 40 wt .-% of a monomer containing epoxy groups, and
• 6. 0 to 5 wt .-% of other radically polymerizable monomers,

wherein the sum of the components 3) to 5) is at least 1 to 45 wt .-%, based on the components 1) to 6).

As examples of suitable α-olefins, there may be mentioned ethylene, propylene, 1-butylene, 1-pentylene, 1-hexylene, 1-heptylene, 1-octylene, 2-methylpropylene, 3-methyl-1-butylene and 3-ethyl-1. butylene, with ethylene and propylene being preferred.

Examples of suitable diene monomers are conjugated dienes having 4 to 8 C atoms, such as isoprene and butadiene, non-conjugated dienes having 5 to 25 C 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 dicyclopentadiene, as well as alkenylnorbornene such as 5-ethylidene-2 norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyltricyclo- (5.2.1.0.2.6) -3,8-decadiene, or their Called mixtures. Preference is given to hexa-1,5-diene, 5-ethylidene-norbornene and dicyclopentadiene.

The diene content is preferably 0.5 to 50, in particular 2 to 20 and particularly preferably 3 to 15 wt .-%, based on the total weight of the olefin polymer. Examples of suitable esters are methyl, ethyl, propyl, n-butyl, i-butyl and 2-ethylhexyl, octyl and decyl acrylates or the corresponding esters of methacrylic acid. Of these, methyl, ethyl, propyl, n-butyl and 2-ethylhexyl acrylate or methacrylate 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 may also be present in the olefin polymers.

Examples of ethylenically unsaturated mono- or dicarboxylic acids are 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.

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 of these are anhydrides of dicarboxylic acids having 2 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.

As other monomers come z. As vinyl esters and vinyl ethers into consideration.

Particularly preferred are olefin polymers from 50 to 98.9, in particular 60 to 94.85 wt .-% of ethylene, and 1 to 50, in particular 5 to 40 wt .-% of an ester of acrylic or methacrylic acid 0.1 to 20.0 , in particular 0.15 to 15 wt .-% glycidyl acrylate and / or glycidyl methacrylate, acrylic acid and / or maleic anhydride.

Particularly suitable functionalized rubbers are ethylene-methyl methacrylate-glycidyl methacrylate, ethylene-methyl acrylate-glycidyl methacrylate, ethylene-methyl-acrylate-glycidyl acrylate and ethylene-methyl methacrylate-glycidyl acrylate polymers.

The preparation of the polymers described above can be carried out by processes known per se, preferably by random copolymerization under high pressure and elevated temperature.

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

Other suitable rubbers are commercial ethylene-α-olefin copolymers which contain polyamide-reactive groups. The preparation of the underlying ethylene-α-olefin copolymers is carried out by transition metal catalysis in the gas phase or in solution. Suitable comonomers are the following α-olefins: propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 Undecene, 1-dodecene, styrene and substituted styrenes, vinyl esters, vinyl acetates, acrylic esters, methacrylic esters, glycidyl acrylates and methacrylates, hydroxyethyl acrylates, acrylamides, acrylonitrile, allylamine; Serve, such as. B. butadiene isoprene.

Particularly preferred are ethylene / 1-octene copolymers, ethylene / 1-butene copolymers; Ethylene-propylene copolymers, wherein compositions of From 25 to 85% by weight, preferably 35 to 80% by weight of ethylene, 14.9 to 72% by weight, preferably from 19.8 to 63% by weight of 1-octene or 1-butene or propylene or mixtures thereof 0.1 to 3% by weight, preferably 0.2 to 2% by weight of an ethylenically unsaturated mono- or dicarboxylic acid or a functional derivative of such an acid. are particularly preferred.

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).

The proportion of ethylene in the ethylene-α-olefin copolymers is between 5 and 97, preferably between 10 and 95, in particular between 15 and 93 wt .-%.

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.

Another group of suitable rubbers are core-shell graft rubbers. These are graft rubbers made in emulsion, which consist of at least one hard and one soft component. A hard component is usually understood to mean a polymer having a glass transition temperature of at least 25 ° C., and a polymer having a glass transition temperature of at most 0 ° C. under a soft component. These products have a structure of a core and at least one shell, the structure resulting from the order of monomer addition. The soft components are generally derived from butadiene, isoprene, alkyl acrylates, alkyl methacrylates or siloxanes and optionally further comonomers. Suitable siloxane cores can be prepared, for example, starting from cyclic oligomeric octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane. These can be reacted, for example, with γ-mercaptopropylmethyldimethoxysilane in a ring-opening cationic polymerization, preferably in the presence of sulfonic acids, to the soft siloxane cores. The siloxanes can also be crosslinked by z. B. the polymerization reaction in the presence of silanes with hydrolyzable groups such as halogen or alkoxy groups such as tetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane is performed. As suitable comonomers here z. As styrene, acrylonitrile and crosslinking or graft-active monomers having more than one polymerizable double bond such as diallyl phthalate, divinylbenzene, butanediol diacrylate or triallyl (iso) cyanurate to call. The hard constituents are generally derived from styrene, alpha-methylstyrene and their copolymers, in which case comonomers are preferably acrylonitrile, methacrylonitrile and methyl methacrylate.

Preferred core-shell graft rubbers include a soft core and a hard shell or hard core, a first soft shell and at least one other hard shell. The incorporation of functional groups such as carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic acid ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups is preferably carried out here by the addition of suitably functionalized monomers in the polymerization of the last shell. Examples of suitable functionalized monomers are maleic acid, maleic anhydride, mono- or diesters or maleic acid, tert-butyl (meth) acrylate, acrylic acid, glycidyl (meth) acrylate and vinyloxazoline. The proportion of monomers having functional groups is generally from 0.1 to 25 wt .-%, preferably 0.25 to 15 wt .-%, based on the total weight of the core-shell graft rubber. The weight ratio of soft to hard components is generally 1: 9 to 9: 1, preferably 3: 7 to 8: 2.

Such rubbers are known per se and for example in the EP-A-0 208 187 described. The incorporation of oxazine groups for functionalization may, for. B. according to EP-A-0 791 606 respectively.

Another group of suitable impact modifiers are thermoplastic polyester elastomers. Polyester elastomers are understood as meaning segmented copolyether esters which contain long-chain segments which are generally derived from poly (alkylene) ether glycols and short-chain segments which are derived from low molecular weight diols and dicarboxylic acids. Such products are known per se and in the literature, for. B. in the US 3,651,014 , described. Also commercially available are corresponding products under the names Hytrel ™ (Du Pont), Arnitel ™ (Akzo) and Pelprene ™ (Toyobo Co. Ltd.).

Of course, mixtures of different rubbers can be used.

As a further component B) thermoplastic molding compositions of the invention may contain conventional processing aids such as stabilizers, antioxidants, other 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 antioxidants and heat stabilizers include phosphites and further amines (eg TAD), hydroquinones, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, 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 and / or graphite, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as nigrosine and 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 reduced water absorption and higher T _G.

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

I. Preparation of 1,5-Decalinediamine (NaDa) (Component A ₁ )

In a 3.5 liter pressure reactor, 10 g of the Ru catalyst were suspended in 1.9 kg of a 16% solution of 1,5-naphthalene diamine in THF. The hydrogenation was carried out with pure hydrogen at a constant pressure of 200 bar and a temperature of 170 ° C. It was hydrogenated until hydrogen was no longer absorbed (30 hours). The reactor was subsequently depressurized. The conversion of naphthalenediamine was 100%. The selectivity to decalindiamine was 89.1%. The effluent was purified by distillation (1 m column, Sulzer DX packing, reflux ratio 1: 1-2: 1, 10 mbar top pressure, 124-130 ° C transition temperature). The purity of the distillate was> 99.8%

II. Preparation of the polyamides A

A / 1 Polyamide from NaDa and adipic acid

In a 100 ml test tube, 7.97 g of NaDa, 7.01 g of adipic acid and 15 g of distilled water + 15 ml of Na hypophosphite were added. The reaction mixture was purged well with nitrogen 10 times and the temperature was raised to 200 ° C. The pressure was kept constant at 17 bar at this temperature for 1 hour. The pressure was then relieved to atmospheric pressure and the temperature of the reaction mixture was raised to 270 ° C and condensed under nitrogen flow for a further 70 minutes. The polymer thus obtained has a VZ (viscosity number) of 124 ml / g. VZ measured as 0.5% polymer solution in 96% sulfuric acid (after EN-ISO 1628-1 ) and glass transition temperature (Tg) of 197 ° C (acc ISO 11357-2 ).

A / 2 Polyamide from NaDa and sebacic acid

In a 100 ml test tube, 6.65 g NaDa, 8.09 g sebacic acid and 15 g distilled water +14.74 ml Na hypophosphite were added. The reaction mixture was purged well with nitrogen 10 times and the temperature was raised to 200 ° C. The pressure was constant at 17 bar at this temperature for Held for 1 hour. The pressure was then relieved to atmospheric pressure and the temperature of the reaction mixture was raised to 270 ° C and condensed under nitrogen flow for a further 70 minutes. The polymer thus obtained has a VZ (viscosity number) of 102 ml / g. VZ measured as 0.5% polymer solution in 96% sulfuric acid (after EN-ISO 1628-1 ) and glass transition temperature (Tg) of 163 ° C (after ISO 11357-2 ).

A / 3 Polyamide from NaDa and dodecanedioic acid

In a 100 ml test tube, 6.15 g of NaDa, 8.52 g of dodecanedioic acid and 15 g of distilled water + 14.67 ml of Na-hydrophosphite were added. The reaction mixture was purged well with nitrogen 10 times and the temperature was raised to 200 ° C. The pressure was kept constant at 17 bar at this temperature for 1 hour. The pressure was then relieved to atmospheric pressure and the temperature of the reaction mixture was raised to 270 ° C and condensed under nitrogen flow for a further 70 minutes. The polymer thus obtained has a VZ (viscosity number) of 94 ml / g. VZ measured as 0.5% polymer solution in 96% sulfuric acid (after EN-ISO 1628-1 ) and glass transition temperature (Tg) of 152 ° C (after ISO 11357-2 ).

sowie

zur Herstellung von Vergleichspolyamiden (1V bis 8V) eingesetzt. As a comparison were mentioned above acids and as amines

such as

used for the preparation of comparative polyamides (1V to 8V).

Measurement of the glass transition temperature according to ISO 11357-2

Table 1 Tg [° C] DC DMDC NaDa adipic acid 171 (IV) 182 (5V) 197 (A / 1) sebacic 145 (2V) 156 (6V) 163 (A / 2) dodecanedioic 138 (3V) 148 (7V) 152 (A / 3)

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

• GB 619707 [0004]
• US 2494563 [0004]
• US 2696482 [0005]
• US 2516585 [0006]
• US 3847877 [0007]
• DE 1595354 [0008, 0009]
• US 3597400 [0010]
• US 3842045 [0011]
• US 3840501 [0011]
• CH 449257 [0012]
• DE 2405985 [0013]
• DE 2936759 [0014]
• EP 0012931 [0015]
• DE 2642244 [0016]
• US 4293687 [0017]
• EP 129195 [0030]
• US 3948862 [0030]
• WO 2007/23108 [0030]
• DE 2702661 A [0048]
• US 4360617 A [0048]
• US 5272236 [0084]
• EP 0208187 A [0087]
• EP 0791606 A [0087]
• US 3651014 [0088]

Cited non-patent literature

• EN ISO 1628-1 [0100]
• ISO 11357-2 [0100]
• EN ISO 1628-1 [0101]
• ISO 11357-2 [0101]
• EN ISO 1628-1 [0102]
• ISO 11357-2 [0102]

Claims (7)

Thermoplastic molding compositions comprising A) from 35 to 100% by weight of an amorphous polyamide synthesized from A ₁ ) from 30 to 100% by weight of units derived from aliphatic dicarboxylic acids and bicyclic aliphatic diamines, A ₂ ) from 0 to 70% by weight Units which are derived from further polyamide-forming monomers, different from A ₁ ), B) 0 to 65 wt .-% of further additives, wherein the sum of the weight percent A) and B) give 100%. Thermoplastic molding compositions according to claim 1, wherein the units A ₁ ) 50 to 100 wt .-% and A ₂ ) 0 to 50 wt .-% amount. 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 bicyclic aliphatic diamines correspond to the general formula

where the variables have the following meaning: R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ independently of one another are hydrogen or linear or branched alkyl radicals having 1 to 6 C atoms Thermoplastic molding compositions according to claim 4, in which R ¹ to R ^{6 are} hydrogen. Use of the thermoplastic molding compositions according to claims 1 to 5 for the production of moldings, fibers and films. Shaped bodies, fibers and films obtainable from the thermoplastic molding compositions according to claims 1 to 5.