DE102009035974A1 - Thermoplastic molded mass, useful to prepare e.g. foils, comprises amorphous polyamide from units derived from aliphatic dicarboxylic acid, tetraalkyl substituted cycloaliphatic diamine and further polyamide forming monomer, and additives - Google Patents

Abstract

Thermoplastic molded mass comprises (a) 35-100 wt.% of an amorphous polyamide from (a1) 30-100 wt.% of units that are derived from aliphatic dicarboxylic acid and tetraalkyl substituted cycloaliphatic diamine, and 0-70 wt.% of units, which are derived from further polyamide forming monomer that is different from (a1); and 0-75 wt.% of further additives.

Description

• A) 35 bis 100 Gew.-% eines amorphen Polyamids aufgebaut aus A₁) 30 bis 100 Gew.-% Einheiten, die sich von aliphatischen Dicarbonsäuren und tetraalkylsubstituierten cycloaliphatischen Diaminen ableiten, A₂) 0 bis 70 Gew.-% Einheiten, welche sich von weiteren Polyamid bildenden Monomeren ableiten, verschieden von A₁),
• B) 0 bis 75 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 ) 30 to 100 wt .-% of units derived from aliphatic dicarboxylic acids and tetraalkyl-substituted cycloaliphatic diamines, A ₂ ) 0 to 70 wt .-% of units which derived from other polyamide-forming monomers, different from A ₁ ),
• B) 0 to 75% by weight of further additives,

the sum of the weight percentages A) and B) being 100%.

Farther the invention relates to the use of the invention Molding compounds for the production of fibers, films, moldings and the fibers, films and moldings available in this case.

polyamides and copolyamides prepared by using 3-aminomethyl-3,5,5-trimethylcyclohexylamine (Isophorone diamine, IPDA), 4,4-diaminodicyclohexyl or diamines of the bis (4-aminocycohexyl) alkane type, which on the cyclohexyl radicals may be substituted by two methyl groups were 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 isophthalic 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-aminocyclohexyl) 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% 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 *** "" For high glass transition point transparent copolyamides employing 30 and more weight percent of an omega-aminocarboxylic acid of at least 11 carbon atoms to lower the high processing viscosity, a substantial amount of isophoronediamine is present in addition to 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-aminocyclohexyl) methane 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 homologues and also 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.

task The present invention was therefore thermoplastic molding compositions based on amorphous polyamides, which has a reduced water absorption and increased Have glass transition temperature. In addition, the starting materials easy to dose.

Accordingly, were Found the molding compounds defined above.

preferred Embodiments are the dependent claims remove.

• A₁) 30 bis 100 Gew.-% vorzugsweise 50 bis 100 Gew.-% Einheiten, die sich von aliphatischen Dicarbonsäuren und tetraalkylsubstituierten cyclo-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 tetraalkyl-substituted cyclo-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 with linear or branched alkyl radicals having 2 to 20 carbon atoms, preferably with 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, Tridecanedioic acid dimethylester, C ₃₂ -dimetic fatty acid dimethyl ester, their dichlorides, for example ethanedioic dichloride, propanedioic dichloride, butanedioic acid dichloride, pentanedioic dichloride, He xandisäuredichlorid, Heptandisäuredichlorid, Octandisäuredichlorid, Nonandisäuredichlorid, Decandisäuredichlorid, Undecandisäuredichlorid, Dodecandisäuredichlorid, 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 may also be mixtures of the above dicarboxylic acids be used.

wobei die Variablen folgende Bedeutung haben:
n = 0 bis 6
R¹, R², R³, R⁴ unabhängig voneinander lineare oder verzweigte Alkyreste mit 1 bis 6 C-Atomen,
R⁵, R⁶ unabhängig voneinander Wasserstoff oder einen Alkylrest mit 1 bis 10 C-Atomen.The tetraalkyl-substituted cycloaliphatic diamines preferably correspond to the general formula

where the variables have the following meaning:
n = 0 to 6
R ¹ , R ² , R ³ , R ⁴ independently of one another linear or branched alkyl radicals having 1 to 6 C atoms,
R ⁵ , R ⁶ independently of one another are hydrogen or an alkyl radical having 1 to 10 C atoms.

Prefers n = 1-3, preferably 1.

Preferred radicals R ¹ to R ⁴ are each independently butyl, iso-butyl, t-butyl, n-propyl, iso-propyl, methyl or ethyl, with methyl, ethyl or isopropyl being particularly preferred as alkyl radicals and methyl or ethyl being particularly preferred.

Preferred radicals R ⁵ , R ⁶ are each independently butyl, propyl radicals as described for R ¹ to R ⁴ , wherein the methyl or ethyl radical is particularly preferred as the alkyl radical.

oder ganz besonders bevorzugt als Substituenten in direkter Nachbarschaft der NH₂-Gruppen.The position of the substituents R ¹ to R ⁴ is preferably in the following positions

or most preferably as substituents in the immediate vicinity of the NH ₂ groups.

preferred Are monomers

As further polyamide-forming monomers A ₂ ) are first aromatic dicarboxylic acids into consideration.

aromatic Dicarboxylic acids preferably have 8 to 16 carbon atoms on. 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 especially is preferred.

Further Polyamide-forming monomers may be derived from dicarboxylic acids with 4 to 16 carbon atoms and aliphatic or cycloaliphatic Diamines with 4 to 16 carbon atoms and of aminocarboxylic acids or corresponding lactams with 7 to 12 carbon atoms derived. 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, Xylylenediamine, methylpentamethylenediamine and as the representative of Diamines and capryllactam, enanthlactam, omega-aminoundecanoic acid, Caprolactam and laurolactam as representatives of lactams or aminocarboxylic acids called.

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.

Particularly preferred are combinations of A ₁ ) with 4,4'-diaminodicyclohexylmethane (dicycan) or 3,3'-dimethyl-4,4'-diaminocyclohexylmethane (Laromin).

Dicycan usually has different isomers, according to the method in EP Appl. No. 0 815 0395.5 these preferably have the following composition:

Trans-trans

Trans-Cis

Cis-cis

In mixture with monomers A ₁ ), the melting temperature drops below room temperature and correspondingly easier is the dosage in the polymerization, since z. B. boilers omitted.

The thermoplastic molding compositions can 0 to 70, in particular up to 50, preferably up to 30% by weight of further additives B) contain.

When Component B), the inventive Molding compounds 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.

Prefers are Al, alkali, alkaline earth salts or ester or amides of fatty acids with 10 to 44 carbon atoms, preferably with 14 to 44 carbon atoms.

The Metal ions are preferably alkaline earth and Al, where Ca or Mg are particularly preferred.

preferred Metal salts are Ca-stearate and Ca-montanate as well as Al-stearate.

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

The Carboxylic acids can be 1- or 2-valent. When Examples are pelargonic acid, palmitic acid, lauric acid, Margarine acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids with 30 to 40 carbon atoms).

The Aliphatic alcohols can be 1 to 4 valent. Examples for alcohols are n-butanol, n-octanol, stearyl alcohol, Ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, wherein Glycerol and pentaerythritol are preferred.

The aliphatic amines can be monohydric to trihydric. Examples of these are stearylamine, ethylene diisocyanate min, 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 may also be mixtures of various esters or amides or Ester can be used in combination with amides, the mixing ratio is arbitrary.

When other components B), the inventive Molding Compounds Heat Stabilizers or Antioxidants or their mixtures, selected from the group of copper compounds, hindered phenols, 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.

When Salts of monovalent copper are preferably copper (I) acetate, Copper (I) chloride, bromide and iodide in question. They are in quantities from 5 to 500 ppm copper, preferably 10 to 250 ppm, based on Polyamide, included.

The advantageous properties are obtained in particular when the Copper is present in a molecular distribution in the polyamide. this will achieved by adding a concentrate to the molding compound, the polyamide, a salt of monovalent copper and an alkali halide in the form a solid, homogeneous solution. A typical one Concentrate consists z. B. from 79 to 95 wt .-% polyamide and 21 to 5% by weight of a mixture of copper iodide or bromide and potassium iodide. The concentration of 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.

When sterically hindered phenols are in principle all compounds with phenolic structure containing at least one phenolic ring have sterically demanding group.

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 ).

A Another group of preferred sterically hindered phenols are derived of substituted benzene carboxylic acids, in particular of substituted benzene propionic 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)Preferred compounds corresponding to this formula are

(Irganox ^® 245 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-hydroxyphenyl) -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-hydroxyhydrocinnamate, 3,5-di-tert-butyl-4-hydroxyphenyl 3,5-distearylthiotriazylamine, 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-hydroxybenzyldimethylamine.

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 BASF SE, which is particularly well suited described above.

The phenolic antioxidants 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 In some cases, sterically hindered phenols have no more than one sterically hindered group in ortho position to the phenolic hydroxy group proved to be particularly advantageous; especially in assessing color stability Storage in diffused light for extended periods of time.

When fibrous or particulate fillers B) 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 used in amounts of up to 40 wt .-%, in particular 1 to 15 wt .-% become.

When preferred fibrous fillers are carbon fibers, Aramid fibers and potassium titanate fibers called glass fibers are particularly preferred as E-glass. These can be called rovings or cut glass used in the commercial forms become.

The fibrous fillers can do better Compatibility with the thermoplastic with a silane compound be pretreated superficially.

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 from 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 used.

Suitable are also acicular mineral fillers.

Under acicular mineral fillers are used in the According to the invention, a mineral filler with strong pronounced needle-like character understood. An example is acicular wollastonite. Preferably the mineral has an L / D (length diameter) ratio from 8: 1 to 35: 1, preferably from 8: 1 to 11: 1. The mineral Filler may optionally with the above Be pretreated silane compounds; however, the pretreatment is not necessarily required.

When further fillers are kaolin, calcined kaolin, wollastonite, Talc and chalk, as well as platelet or acicular nanofillers preferably in Amounts between 0.1 and 10%. Boehmite, Bentonite, montmorillonite, vermicullite, hectorite and laponite used. To ensure good compatibility of the platelet-shaped To obtain nanofillers with the organic binder, become the platelet-shaped nanofillers organically modified according to the state of the art. The addition of the platelet or acicular nanofillers leads to the nanocomposites according to the invention to a further increase in 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 for impact modifiers as component C) are rubbers, which may have functional groups. It can also mixtures of two or more different impact modifiers Rubbers are used.

rubbers, which increase the toughness of the molding compositions generally an elastomeric moiety having a glass transition temperature less than -10 ° C, preferably less than -30 ° C, and they contain at least a functional group that can react with the polyamide. suitable functional groups are, for example, carboxylic acid, Carboxylic anhydride, carboxylic acid ester, carboxylic acid amide, Carboximide, amino, hydroxyl, epoxy, urethane or oxazoline groups, preferably carboxylic anhydride groups.

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, Second 0 to 50% by weight of a diene, Third 0 to 45 wt .-% of a C ₁ -C ₁₂ alkyl ester of acrylic acid or methacrylic acid or mixtures of such esters, 4th 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, 5th 0 to 40 wt .-% of a monomer containing epoxy groups, and 6th 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).

When Examples of suitable α-olefins may be Ethylene, propylene, 1-butylene, 1-pentylene, 1-hexylene, 1-heptylene, 1-octylene, 2-methylpropylene, 3-methyl-1-butylene and 3-ethyl-1-butylene may be mentioned, with ethylene and propylene are preferred.

When suitable diene monomers are, for example, conjugated dienes 4 to 8 C atoms, such as isoprene and butadiene, non-conjugated dienes with 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 dicyclopentadiene, and 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 mixtures thereof called. Preference is given to hexa-1,5-diene, 5-ethylidene-norbornene and Dicyclopentadiene.

Of the Diene content is preferably 0.5 to 50, in particular 2 to 20 and more 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 is particularly preferred.

Instead of the ester or in addition to these may be in the olefin polymers also acid functional and / or Latent acid-functional monomers ethylenically unsaturated Be contained mono- or dicarboxylic acids.

Examples for 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.

When Latent acid-functional monomers are said to be such compounds Under the polymerization conditions or in the incorporation of olefin polymers in the molding compositions free Form acid groups. As examples are Anhydrides of dicarboxylic acids having 2 to 20 carbon atoms, in particular Maleic anhydride and tertiary C1-C12 alkyl esters the abovementioned acids, in particular tert-butyl acrylate and tert-butyl methacrylate.

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

Especially preferred are olefin polymers from 50 to 98.9, in particular 60 to 94.85% by weight 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.

Especially 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 above-described polymers can be carried out per se known methods are carried out, preferably by random copolymerization under high pressure and elevated temperature.

Of 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).

When Rubbers are still commercial ethylene-α-olefin copolymers, which contain polyamide-reactive groups, into consideration. The preparation of the underlying ethylene-α-olefin copolymers carried out by transition metal catalysis in the gas phase or in solution. Comonomers used are the following α-olefins in question: 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, determined by GPC in 1,2,4-trichlorobenzene with PS calibration).

Of 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% by weight.

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.

When another group of suitable rubbers are core-shell graft rubbers to call. These are graft rubbers prepared in emulsion, which consist of at least one hard and one soft component. A hard component is usually understood a polymer having a glass transition temperature of at least 25 ° C, under a soft ingredient, a polymer with a Glass transition temperature of at most 0 ° C. These products have a structure of one core and at least a shell, whereby the structure by the order the monomer addition results. The soft ingredients are derived in general of butadiene, isoprene, alkyl acrylates, alkyl methacrylates or Siloxanes and optionally further comonomers. suitable For example, siloxane cores can be derived from cyclic oligomeric octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane getting produced. These can, for example, with γ-mercaptopropylmethyldimethoxysilane in a ring-opening cationic polymerization, preferably in the presence of sulfonic acids, to the soft siloxane cores be implemented. 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 carried out. As suitable comonomers here z. Styrene, acrylonitrile and crosslinking or grafting monomers with 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 from, here as Comonomers preferably acrylonitrile, methacrylonitrile and methyl methacrylate be listed.

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 GE 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 It is also possible to use mixtures of different rubbers become.

When further component B), the inventive thermoplastic molding compounds customary 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. included.

When Examples of oxidation inhibitors and heat stabilizers be phosphites and other amines (eg TAD), hydroquinones, various substituted representatives of these groups and their mixtures in concentrations up to 1 wt .-%, based on the weight of the thermoplastic molding compositions called.

When UV stabilizers, which are generally available in amounts of up to 2% by weight, are used, based on the molding composition, are different substituted resorcinols, salicylates, benzotriazoles and benzophenones.

It may include 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 dyes, such as nigrosine and anthraquinones are added as colorants.

When Nucleating agents may include sodium phenylphosphinate, alumina, Silica and preferably talc are used.

When Flame retardants are red phosphorus, P- and N-containing flame retardants as well as halogenated FS-agent systems and their synergists.

The thermoplastic molding compositions according to the invention can be prepared by methods known per se, in which the starting components in conventional mixing devices such as screw extruders, Grabender mills or Banbury mills mixed and then extruded. After the extrusion can the extrudate is cooled and comminuted. It can Also, individual components are premixed and then the remaining Starting materials are added individually and / or also mixed become. 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 min., preferably from 2 to 5 min.

The thermoplastic molding compositions according to the invention are characterized by reduced water absorption and higher T _G. The addition of the monomers for polymerization is facilitated.

These are suitable for the production of moldings of any kind for applications such. In the automotive, E.u.E.-, housewares, Film, fiber industry, especially for applications which requires high transparency, such as B. in the optical or automotive industry.

Examples

Preparation of polyamides A

According to the invention as TMDC was used (monomer A ₁ ):

sowieFor comparative examples or mixtures A ₁ / A ₂ , the following amines were used:

such as

DC had the following isomer proportions:

Trans-trans

Trans-Cis

Cis-cis

Example IV

In An 8 l stirred tank at room temperature 396.07 g TLC, 1038.58 g of DMDC and 1427.02 g of 1.10-decanedicarboxylic acid Weighed in 300 g of water. The batch was 0.25 g of sodium hypophosphite added as a catalyst.

Of the Boiler was closed and the outside temperature to 300 ° C set. After reaching an internal temperature of 100 ° C was the stirrer was switched on. From an Inndruck from 20 bar was slowly relaxed while keeping the internal temperature set to 290 ° C. This process lasted 100 min. At internal temperature 290 ° C under nitrogen flow was 25 after-condensed min. Subsequently, the melt was as Strand extended, cooled in a water bath and then granulated.

The Analysis results are summarized in the table.

Example 2V

In An 8 l stirred tank was at room temperature 689.00 g TLC, 1823.00 g DMDC and 1574.00 g adipic acid in 1000 g Water weighed. The batch was 0.35 g of sodium hypophosphite added as a catalyst.

Of the Boiler was closed and the outside temperature to 300 ° C set. After reaching an internal temperature of 100 ° C was the stirrer was switched on. From an Inndruck from 20 bar was slowly relaxed while keeping the internal temperature set to 307 ° C. After 112 min was at a pressure from 0.75 bar no further relaxation possible, as the approach heavily foamed.

The Analysis results are summarized in the table.

Example 3V

In An 8 l stirred tank was 661.98 g at room temperature TLC, 1750.58 g of DMDC and 1796.22 g of cork acid in 1500 g of water weighed. To the batch was added 0.63 g of sodium hypophosphite catalyst.

Of the Boiler was closed and the outside temperature to 300 ° C set. After reaching an internal temperature of 100 ° C was the stirrer was switched on. From an Inndruck from 20 bar was slowly relaxed while keeping the internal temperature set to 290 ° C. This process took 120 minutes. At internal temperature 290 ° C under nitrogen flow was 4 after-condensed min. Subsequently, the melt was as Strand extended, cooled in a water bath and then granulated.

Example 4

In a 100 ml test tube at room temperature gave 8.17 g of TMDC (OH-free), including 50 mmol / kg excess, and 6.91 g of 1.10-decanedicarboxylic acid weighed into 14.75 g of water. The batch was 0.15 g of sodium hypophosphite added as a catalyst.

The test tube was placed in an autoclave with two other test tubes. The autoclave was closed and the outside temperature was set to 210 ° C. After 1 h at 210 ° C, the temperature was set to reaction outside temperature. From 16 bar pressure was held for 2 hours this pressure by relaxing. After this time, the mixture was depressurized to normal pressure within 1 h, then condensed for 20 h under nitrogen flow 20 l / h. Thereafter, the boiler was closed and pressed under 5 bar nitrogen, and turned off the heater. After cooling overnight, the experiment was expanded.
Reaction outside temperature = 280 ° C.

Example 5

At room temperature, 8.71 g TMDC (OH-free), including 50 mmol / kg excess, and 6.47 g sebacic acid in 14.85 g water were weighed into a 100 ml test tube. To the batch was added 0.15 g of sodium hypophosphite catalyst.
Reaction outside temperature = 280 ° C.
The driving style corresponded to Example 4.

Example 6

9.77 g TMDC (OH-free), including 50 mmol / kg excess, and 5.26 g adipic acid in 14.70 g water were weighed into a 100 ml test tube at room temperature. To the batch was added 0.15 g of sodium hypophosphite catalyst.
Reaction outside temperature = 280 ° C.
The driving style corresponded to Example 4.

Example 7

In a 100 ml test tube at room temperature 7.27 g TMDC (OH-free), including 50 mmol / kg excess, and 2.54 g of TLC, including 50 mmol / kg of excess, and 5.55 g of adipic acid in 15.04 g sodium hypophosphite solution 0.1%.
Reaction outside temperature = 300 ° C.
The driving style corresponded to Example 4.

Example 8

In a 100 ml test tube at room temperature 6.33 g TMDC (OH-free), including 50 mmol / kg excess, 2.22 g of DC including 50 mmol / kg excess, and 6.67 g of sebacic acid in 14.91 g of sodium hypophosphite -Lsg weighed 0.1%.
Reaction outside temperature = 300 ° C.
The driving style corresponded to Example 4.

Example 9

In a 100 ml test tube at room temperature 5.96 g TMDC (OH-free), including 50 mmol / kg excess, 2.10 g of DC, including 50 mmol / kg of excess, and 7.14 g of 1.10-decanedicarboxylic acid in 14, 88 g of sodium hypophosphite solution 0.1% weighed
Reaction outside temperature = 300 ° C.
The driving style corresponded to Example 4.

Example 10

4.24 g of TMDC (OH-free), including 50 mmol / kg excess, 3.35 g of DC, including 50 mmol / kg excess, and 4.50 g of adipic acid in 11.84 g were placed in a 100 ml test tube at room temperature Sodium hypophosphite solution 0.1% weighed.
Reaction outside temperature = 300 ° C.
The driving style corresponded to Example 4.

Example 11

4.25 g TMDC (OH-free), including 50 mmol / kg excess, 3.35 g DC, including 50 mmol / kg excess, and 6.19 g sebacic acid in 13.48 g were placed in a 100 ml test tube at room temperature Sodium hypophosphite solution 0.1% weighed.
Reaction outside temperature = 300 ° C.
The driving style corresponded to Example 4.

Example 12

4.24 g of TMDC (OH-free), including 50 mmol / kg excess, 3.35 g of DC, including 50 mmol / kg excess, and 7.02 g of 1.10-decanedicarboxylic acid in 14, were placed in a 100 ml test tube at room temperature. 30 g sodium hypophosphite solution 0.1% weighed.
Reaction outside temperature = 300 ° C.
The driving style corresponded to Example 4.

Example 13V

9.20 g of DC, including 50 mmol / kg of excess, and 6.28 g of adipic acid in 15.33 g of sodium hypophosphite solution 0.1% were weighed into a 100 ml test tube at room temperature.
Reaction outside temperature = 320 ° C.
The driving style corresponded to Example 4.

Example 14V

At room temperature, 7.93 g of DC, including 50 mmol / kg of excess, and 7.48 g of sebacic acid in 15.27 g of sodium hypophosphite solution 0.1% were weighed into a 100 ml test tube.
Reaction outside temperature = 320 ° C.
The driving style corresponded to Example 4.

Example 15V

In a 100 ml test tube, 7.51 g of DC, including 50 mmol / kg excess, and 7.36 g of 1.10-decanedicarboxylic acid in 15.42 g of sodium hypophosphite solution 0.1% were weighed at room temperature.
Reaction outside temperature = 320 ° C.
The driving style corresponded to Example 4.

• Die VZ wurde gemäß ISO 307 bestimmt.
• AEG: Probe wurde in Phenol/Methanol (0,5 g in 30 ml) gelöst und mit HCl titriert (Mittelwert aus 8 Messungen).
• CEG: Probe wurde in Benzylalkohol gelöst und mit alkoholischer HCl titriert (Mittelwert aus 8 Messungen)
• Tg wurde gemäß ISO 11357/2 bestimmt.
• Tm wurde gemäß ISO 11357/3 bestimmt.

Tabelle 1 Beispiel VZ [ml/g] AEG CEG Tg [°C] Tm [00] 1V 79 79 62 145 - 2V 67 135 64 183 298 3V 68 113 55 165 - 4 87 33 40 171 - 5 96 60 46 181 - 6 46 28 231 197 - 7 63 121 21 193 - 8 56 156 36 167 - 9 67 106 24 159 - 10 109 57 25 190 - 11 87 104 30 164 - 12 88 83 16 153 - 13V 120 168 n. b. 165 294 14V 118 92 47 146 268 15V 90 98 46 136 248 The results of the measurements are summarized in Table 1.

• The VZ was according to ISO 307 certainly.
• AEG: Sample was dissolved in phenol / methanol (0.5 g in 30 ml) and titrated with HCl (mean of 8 measurements).
• CEG: sample was dissolved in benzyl alcohol and titrated with alcoholic HCl (mean of 8 measurements)
• Tg was according to ISO 11357/2 certainly.
• Tm was according to ISO 11357/3 certainly.

Table 1 example VZ [ml / g] AEG CEG Tg [° C] Tm [00] 1V 79 79 62 145 - 2V 67 135 64 183 298 3V 68 113 55 165 - 4 87 33 40 171 - 5 96 60 46 181 - 6 46 28 231 197 - 7 63 121 21 193 - 8th 56 156 36 167 - 9 67 106 24 159 - 10 109 57 25 190 - 11 87 104 30 164 - 12 88 83 16 153 - 13V 120 168 nb 165 294 14V 118 92 47 146 268 15V 90 98 46 136 248

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• GB 619707 [0004]
• - US 2494563 [0004]
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Cited non-patent literature

• - ISO 307 [0130]
• - ISO 11357/2 [0130]
• - ISO 11357/3 [0130]

Claims (10)

Thermoplastic molding compositions comprising A) 35 to 100% by weight of an amorphous polyamide synthesized from A ₁ ) 30 to 100% by weight of units derived from aliphatic dicarboxylic acids and tetraalkyl-substituted cycloaliphatic diamines, A ₂ ) 0 to 70% by weight Units which are derived from other polyamide-forming monomers, different from A ₁ ), B) 0 to 75 wt .-% of other 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 the claims 1 or 2, in which the aliphatic dicarboxylic acids are linear or branched alkyl radicals having 2 to 20 carbon atoms. Thermoplastic molding compositions according to claims 1 to 3, in which the tetraalkyl-substituted cycloaliphatic diamines correspond to the general formula

where the variables have the following meaning: n = 0 to 6 R ¹ , R ² , R ³ , R ⁴ independently of one another linear or branched alkyl radicals having 1 to 6 C atoms, R ⁵ , R ⁶ independently of one another hydrogen or an alkyl radical having 1 to 10 C atoms. Thermoplastic molding compositions according to claim 4, in which R ¹ to R ^{4 are arranged} as substituents in the immediate vicinity of the NH ₂ group. Thermoplastic molding compositions according to claim 4, in which R ⁵ , R ^{6 are} hydrogen or a methyl radical. Thermoplastic molding compositions according to claim 4, in which R ¹ to R ^{4 are} methyl or ethyl radicals. Thermoplastic molding compositions according to claims 1 to 6, in which the units A ₂ ) are composed of 4,4'-diaminodicyclohexylmethane or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane or mixtures thereof. Use of the thermoplastic molding compositions according to Claims 1 to 8 for the production of moldings, Fibers and foils. Shaped bodies, fibers and films available from the thermoplastic molding compositions according to the Claims 1 to.