WO2011069942A1 - Partially aromatic copolyamide molding compounds based on octamethylene diamine - Google Patents

Abstract

The invention relates to partially aromatic copolyamide molding compounds, comprising A) 35 to 100 wt% of a partially crystalline, partially aromatic copolyamide, made up of a₁) 60 to 95 mol% of units derived from 1,8-octamethylene diamine and terephthalic acid, a₂) 5 to 40 mol% of units derived from monomers forming further polyamides, different from a₁), wherein the combination of octamethylene diamine with suberic acid is excluded for the units a₂), B) 0 to 65 wt% of further additives, wherein the sum of the weight percentages A) and B) is 100%.

Description

 Partially aromatic copolyamide molding compositions based on octamethylenediamine

The invention relates to partially aromatic copolyamide molding compositions containing

A) 35 to 100 wt .-% of a partially crystalline, partially aromatic copolyamide composed of a-i) 60 to 95 mol% of units, which is derived from 1, 8-octamethylenediamine and

Derive terephthalic acid,

32) from 5 to 40 mol% of units which are derived from other polyamide-forming monomers, different from a-i), the combination of octamethylenediamine with suberic acid in the units a2) being excluded,

B) 0 to 65 wt .-% of other additives, wherein the sum of the weight percent A) and B) gives 100%.

Furthermore, the invention relates to the use of the copolyamides according to the invention for the production of fibers, films and moldings of any kind, as well as the moldings obtainable in this case.

High-temperature-resistant polyamides (HTPA) usually build up on the units 6T (hexamethylenediamine, terephthalic acid). However, pure 6T has a very high melting temperature and can not be processed without decomposition. Accordingly, copolymer systems have been developed to avoid this: e.g.

EP-A 299 444 (PA6 / 6T, PA66 / 6T), EP-A 19 94 075 (PA6T / 6I / MXD6), EP-A 667 367 (6T / 6l / cycloaliphatic diamine) and US Pat. No. 3,843,611 (PA8T / 88).

The reduction of the melting temperature with the amount of incorporated copolyamide has been studied systematically for the systems PA 6T / 6, 6T / 6I, 6T / 66 and 4T / 46 [G. Ajroldi, G. Stea, A. Mattiussi, F. Fumagalli, J. Appl. Poly. Be. 1973, 17, 3187-3197, H. Ludewig, Faserforschung und Textilchemie 1955, 6, 277; Gaymans et al., J. Polym. Be. A, Chem. 1989, 27, 423-430].

HTPA's, which have the highest possible glass transition temperature and a high melting temperature (without decomposition), are particularly desired for problem-free processing for many applications. In addition, the tendency to water absorption, which impairs many properties, should be minimized. It is an object of the present invention to provide partially aromatic, partially crystalline copolyamides which have a high T g and a high T _m (without decomposition) and a low water absorption. Accordingly, the Copolyamidformmassen defined above were found. Preferred embodiments are given in the dependent claims.

As component A), the copolyamide molding compositions of the invention comprise from 35 to 100, preferably from 35 to 95,% by weight of a copolyamide synthesized from a-i) from 60 to 95 mol% of units derived from 1,8-octamethylenediamine and terephthalic acid,

32) from 5 to 40 mol% of units which are derived from further polyamide-forming monomers, different from a-i), the combination of octamethylenediamine with suberic acid in units 32) being excluded. Preferred partially aromatic partially crystalline copolyamides A) are composed of: a-i) from 70 to 95 mol%, in particular from 80 to 95 mol%, of units a-1) and

32) 5 to 30 mol%, in particular 5 to 20 mol% units 32). A small proportion of up to 30 mol%, preferably up to 20 mol%, of the terephthalic acid units can be replaced by other aromatic carboxylic acids.

Suitable aromatic dicarboxylic acids are, for example, isophthalic acid, substituted terephthalic and isophthalic acids such as 3-t-butyl isophthalic acid, 3-sulfoisophthalic acid, 3-aminoisophthalic acid, polynuclear dicarboxylic acids, e.g. 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. 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 which have two carboxylic acid groups (carboxy groups) or derivatives thereof. As derivatives, in particular 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 anhydrides use. 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), C32-dimer fatty acid (commercial product from. Cognis Corp., USA) whose Methylester, for example Ethandisäuredimethylester, -propanedioic acid dimethyl ester, Butandisäuredimethylester, Pentandisäuredimethylester, Hexandisäuredimethylester, Heptandisäuredimethylester, Octandisäuredimethylester, Nonandisäuredimethylester, Decandisäuredimethylester, Undecandisäuredimethylester Dimethyl dodecanedioate, tridecanedioic acid diester, C32 dimer fatty acid dimethyl ester, their dichlorides, for example ethanedioic dichloride, propanedioic dichloride, butanedioic dichloride, pentanedioic dichloro idand, hexanedioic acid dichloride, heptanedioic dichloride, octanedioic acid dichloride, nonandic acid dichloride, decanedioic acid dichloride, undecanedioic acid dichloride, dodecanedioic acid tridecanedioic acid, C32 dimer 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, are particularly preferred.

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

Further possible units a2) are derived from aromatic or aliphatic or cycloaliphatic diamines having 4 to 16 carbon atoms and from aminocarboxylic acids.

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 alkyl-substituted xylylenediamines.

The following non-exhaustive list contains the mentioned possible units 32) in the sense of the invention and the monomers contained.

AA / BB-polymers

 PA 46 tetramethylenediamine, adipic acid

 PA 66 hexamethylenediamine, adipic acid (particularly preferred)

PA 69 hexamethylenediamine, azelaic acid

 PA 610 hexamethylenediamine, sebacic acid

PA 612 hexamethylenediamine, decanedicarboxylic acid PA 613 hexamethylenediamine, undecanedicarboxylic acid

 PA 1212 1, 12-dodecanediamine, decanedicarboxylic acid

 PA 1313 1, 13-diaminotridecane, undecanedicarboxylic acid

 PA 6T hexamethylenediamine, terephthalic acid

 PA MXD6 m-xylylenediamine, adipic acid

 AA / BB-polymers

 PA 6I hexamethylenediamine, isophthalic acid

 PA 6-3-T trimethylhexamethylenediamine, terephthalic acid

 PA 6 / 6T (see PA 6 and PA 6T)

 PA 6/66 (see PA 6 and PA 66)

 PA 6/12 (see PA 6 and PA 12)

 PA 66/6/610 (see PA 66, PA 6 and PA 610)

 PA 6I / 6T (see PA 61 and PA 6T)

 PA PACM 12 diaminodicyclohexylmethane, laurolactam

 PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane

 PA 12 / MACMI laurolactam, dimethyldiaminodicyclohexylmethane, isophthalic acid

PA 12 / MACMT laurolactam, dimethyldiaminodicyclohexylmethane, terephthalic acid

PA PDA-T phenylenediamine, terephthalic acid

Preferred units a2) are combinations of aromatic dicarboxylic acids having 8 to 16 C atoms with aliphatic or cycloaliphatic diamines having 4 to 16 C atoms or of aliphatic diamines having 4 to 16 C atoms with aliphatic dicarboxylic acids having 2 to 20 C atoms. atoms.

Particular preference is given to units 32)

Octamethylenediamine with isophthalic acid (PA8I)

Octamethylenediamine with adipic acid (PA86)

 Hexamethylenediamine with isophthalic acid (PA6I) and

Hexamethylenediamine with adipic acid (PA66).

The polyamides A) can be prepared by methods known per se (for example EP 129 195, US 3,948,862). It is likewise possible to use the process described in WO 2007/23108, in which the corresponding dinitriles of the diacids are used as acid equivalents or so-called direct polymerization in the presence of water, for example in DE-A 10313681, EP-A 1 198491 and EP 922065 described.

The preparation of the polyamides of the invention is preferably carried out in a discontinuous or continuous hydrolytic polycondensation reaction between the corresponding diamines and free dicarboxylic acids from aqueous solution or from an aqueous solution of a water-soluble hypophosphite salt (0.05 to 0.5% by weight). The prepolymer thus formed having a viscosity number (CV) of 40 to 120 ml / g (in concentrated sulfuric acid, 0.5% by weight, ISO 307) is subjected to a postcondensation either in solid phase or in the molten state in an extruder. until a VZ of at least 80 ml / g is reached, preferably from 90 to 160 ml / g.

Alternatively, the copolyamide according to the invention can be produced from a polyamide having units a-1 and a polyamide having units 32) by melting and transamidation in the melt, in particular in an extruder. The respective polyamides are supplied separately and, if appropriate, catalytically active additives and / or accelerators (for example hypophosphite compounds, organophosphites, organophosphonates) are added. The copolyamide thus produced has only a uniform glass transition temperature after transamidation and copolyamide formation. The copolyamides A) preferably have a glass transition temperature TG of greater than 104 ° C, especially greater than 1 10 ° C and in particular from 120 to 140 ° C.

The melting temperature T _m is preferably less than 330 ° C, in particular from 280 to 315 ° C. These parameters are usually measured by means of DSC (Diffusive Scanning Calorimetry) according to ISO 1 1357-2, 3 and 7 (20 K / min, 2nd heating curve).

As component B) molding compositions of the invention may contain up to 65, preferably up to 50 wt .-% of other additives. As fibrous or particulate fillers 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 of 1 to 50 wt .-%, 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 thermoplastic with a silane compound.

Suitable silane compounds are those of the general formula

n eine ganze Zahl von 2 bis 10, bevorzugt 3 bis 4 (X- (CH 2) n) k Si- (O-C _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 from 0.025 to 1, 0 and in particular from 0.05 to 0.5% by weight (based on B)) of the surface coating.

Also suitable are acicular mineral fillers.

In the context 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 1: 1: 1. The mineral filler may optionally be pretreated with the silane compounds mentioned above; however, pretreatment is not absolutely necessary.

As further fillers are kaolin, calcined kaolin, wollastonite, talc and chalk called as well as platelet or needle-shaped nanofillers 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 esters 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 1 - to 3-valent. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Correspondingly, preferred esters or amides are glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol 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 (l) halide, in particular in a mixture with an alkali metal halide, preferably KJ, in particular in the ratio 1: 4, or of 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 con- For example, concentrate consists of 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 1 1, 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). Preferably, e.g. Compounds of the formula

in which: R ¹ and R ^{2 are} an alkyl group, a substituted alkyl group or a substituted triazole group, where R ¹ and R ^{2 may be} identical 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 described, for example, in 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.

Particularly preferred compounds of this class are compounds of the formula

wobei R⁴, R⁵, R⁷ und R⁸ unabhängig voneinander Ci-Cs-Alkylgruppen darstellen, die ihrerseits substituiert sein können (mindestens eine davon ist eine sterisch anspruchs volle Gruppe) und R⁶ einen zweiwertigen aliphatischen Rest mit 1 bis 10 C-Atomen bedeutet, der in der Hauptkette auch C-O-Bindungen aufweisen kann.

wherein 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 full group) and R ^{6 is} a divalent aliphatic radical having 1 to 10 carbon atoms, which may also have CO bonds in the main chain.

Preferred compounds corresponding to these formulas 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 ], Pentaerytrityl 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-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-butylphenol), 1, 6-hexanediol bis (3,5-di-tert-butyl) butyl-4-hydroxyphenyl) -propionate (Irganox® 259), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], and N, N'-hexamethylene bis-propionate. 3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098) and the Irganox® 245 from BASF SE described above, which is particularly well suited. 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) to 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 of 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) which are useful in wool dyeing and printing, in the black dyeing of silks, for dyeing leather, shoe creams, varnishes, plastics, stoving lacquers, inks and the like, as well as being used as microscope dyes.

The nigrosine is technically obtained by heating nitrobenzene, aniline and aniline with anhydrous metal. Iron and FeC (name of Latin niger = black).

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

Further details on nigrosines can be found, for example, in the electronic lexicon Rompp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword "nigrosine".

Other customary additives B) are, for example, in amounts of up to 25, preferably up to 20 wt .-% rubber-elastic 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 esters with 1 to 18 C Atoms in the alcohol component.

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

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-methyltricyclo (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 e.g. Acrylic acid, methacrylic acid and its derivatives, e.g. Glycidyl (meth) acrylate, and called maleic anhydride.

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 contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Esters and anhydrides, and / or monomers containing epoxy groups. 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

R ⁴

 /

 IC

O

Chi ^,: CR ^■ COO - (CH ₂ ) _p CH- CHR ^! (IV)

O wherein R ¹ to R ^{9 are} hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 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 the 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 epoxy-containing monomers and / or methacrylic acid and / or acid-anhydride-containing monomers and the remaining amount of (meth) acrylic acid esters.

Particular preference is given to copolymers of from 50 to 98, in particular from 55 to 95,% by weight of ethylene,

0.1 to 40, in particular 0.3 to 20 wt .-% glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and

1 to 45, in particular 5 to 40 wt .-% 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, their preparation e.g. at Blackley in the monograph "Emulsion Polymerization". The usable emulsifiers and catalysts 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.

By way of example, as monomers for the preparation of the rubber portion of the elastomers, acrylates such as e.g. N-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and their mixtures called. These monomers can be reacted with other monomers such as e.g. 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 (with 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 acid esters and methacrylic acid esters 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: In some cases it has proven to be advantageous to use emulsion polymers which have reactive groups on the surface. Such groups are, for example, epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups obtained by concomitant use of monomers of the general formula

can be introduced, wherein the substituents may have the following meaning:

Hydrogen or a C 1 to C 4 alkyl group,

R ^{11 is} hydrogen, a C 1 - to C 5 -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 6 -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 -C 10 -alkylene or C 6 -C 12 -arylene group or

 O

O-Z or NH-Z and

Z is a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group. The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.

Further 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) ethyl acrylate.

Furthermore, the particles of the rubber phase can also be crosslinked. Examples of monomers acting as crosslinkers are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A 50 265. 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. Preference is given to using those compounds in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups), for example, polymerizes (polymerizes) much more slowly. 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 further details, reference is made here, for example, to US Pat. No. 4,148,846.

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 butane-1,3-diene, isoprene, n-butyl acrylate, styrene, acrylonitrile, methyl methacrylate, ethylhexyl acrylate or mixtures thereof

 II as I but with the concomitant use of Verwie I

 netzern

 III such as I or II n-butyl acrylate, ethyl acrylate, methyl acrylate, buta-1, 3-diene, isoprene, ethylhexyl acrylate

IV as I or II as I or III but with the concomitant use of monomers having reactive groups as described herein Type monomers for the core monomers for the shell

 V styrene, acrylonitrile, methyl methacrylate or first shell of monomers as described under I mixtures thereof and II for the core second

 Shell as described under I or IV for the shell

Instead of graft polymers having a multi-shell structure, homogeneous, i. 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 co-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 described elastomers may also be prepared by other conventional methods, e.g. by suspension polymerization.

Silicone rubbers, as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290, are likewise preferred. Of course, it is also possible to use mixtures of the rubber types listed above.

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

Examples of oxidation promoters 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 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.

The novel thermoplastic molding compositions can be prepared by processes known per se, in which the starting components are mixed in customary 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 230 to 320 ° C.

According to a further preferred procedure, the components B) can be mixed with a prepolymer, formulated and granulated. The resulting granules are then condensed in solid phase under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity.

The thermoplastic molding compositions according to the invention are distinguished by a good processability coupled with good mechanical properties, as well as by a high T g coupled with a high T _m , but without decomposition of the polymer during processing. The water absorption of the polyamides has been further reduced.

These are suitable for the production of fibers, films and moldings of any kind. Here are some examples: Cylinder head covers, motorcycle covers, intake pipes, intercooler caps, connectors, gears, fan wheels, cooling water boxes.

In the E / E field, with flow improved polyamides, plugs, connector parts, connectors, membrane switches, PCB assemblies, microelectronic components, coils, I / O connectors, PCB connectors, flexible printed circuit (FPC) connectors, flexible integrated circuit connectors (FFC), high-speed connectors, terminal strips, connectors, device connectors, wiring harness components, circuit carriers, circuit carrier components, three-dimensional injection-molded circuit carriers, electrical connection elements, mechatronic components are manufactured. Inside the car, there is use for dashboards, steering column switches, seat parts, headrests, center consoles, gear components and door modules, in the car exterior for door handles, exterior mirror components, windscreen wiper components, windscreen wiper housings, grilles, roof rails, sunroof frames, engine covers, cylinder head covers, intake manifolds (In particular intake manifold), windscreen wipers and body exterior parts possible.

For the kitchen and household sector, the use of flow-improved polyamides for the production of components for kitchen appliances, such. Fryers, irons, buttons, and garden leisure applications, e. Components for irrigation systems or garden tools and door handles possible.

Further applications include electronic components (lead-free soldering) and applications in the field of electronics, fuel supply and cooling systems under the bonnet (metal set), lamp sockets (also LED sockets), bobbins, power strips, chain tensioners, intercoolers, ignition coil plugs, components for lead-free soldering (eg SIM card holders, circuit boards, plugs, printed conductors, CPU sockets), water meter housings (also for hot water), housings of sensors in contact with water, fuel and / or oils.

Examples

Octamethylenediamine, terephthalic acid and other comonomers (a dicarboxylic acid and optionally another diamine) were weighed in a test tube together with an aqueous solution of sodium hypophosphite monohydrate ("NHP", 0.1% by weight) The reaction mixture was then introduced into an autoclave reactor and purged 3 times with 10 bar nitrogen each The autoclave was heated to 350 ° C outside temperature and maintained a pressure of 16 bar for a total of 2 hours Minutes, the autoclave was depressurized to ambient pressure and the postcondensation was carried out under nitrogen flow for 120 minutes at the same temperature After cooling under a nitrogen atmosphere, the removed, dry product was comminuted (for exact sample weights and data, see the following tables).

DSC Measurement: The DSC measurements were made on the Q-2000 FA. Waters GmbH

The initial weight was about 8.5 mg - the heating and cooling rate 20 K / min (2nd heating curve). The samples were measured on the basis of ISO 1 1357 - 2, 3, u. 7 Measurement in the 2nd heating run (after cooling the sample from 380 ° C with 20 K min)

Tg2: inflection point of the glass step

 ΔΗ2: Heat of fusion from area between trace and baseline

Explanations:

Tgi = glass transition temperature in delivery condition

 Tmi = melting point in delivery condition

ΔΗ1 = heat of fusion in delivery condition

 TKB = temperature of crystallization beginning

 TK = temperature of the crystallization peak

 Tg2 = glass transition temperature of a sample cooled from the melt at 20 ° C./min

Trri2 = melting point of a sample cooled from the melt at 20 ° C./min. ΔΗ2 = heat of fusion of a sample cooled from the melt at 20 ° C./min

The compositions and the results of the measurements are shown in the tables.

Claims

claims Partially aromatic copolyamide molding compositions containing A) from 35 to 100% by weight of a partially crystalline, partially aromatic copolyamide synthesized from a-i) from 60 to 95 mol% of units derived from 1,8-octamethylenediamine and terephthalic acid, 32) 5 to 40 mol% of units which are derived from other polyamide-forming monomers, different from a-i), the combination of octamethylenediamine with suberic acid being excluded in units a2), B) 0 to 65 wt .-% of other additives, wherein the sum of the weight percent A) and B) gives 100%. Copolyamide molding compositions according to claim 1, comprising a copolyamide A) composed of

a ₂ ) 5 to 30 mol%. Copolyamide molding compositions according to claims 1 or 2, containing as units 32) combinations of aromatic dicarboxylic acids having 8 to 16 carbon atoms with aliphatic or cycloaliphatic diamines having 4 to 16 carbon atoms or aliphatic diamines having 4 to 16 carbon atoms with aliphatic dicarboxylic acids with 2 to 20 carbon atoms. Copolyamide molding compositions according to claims 1 to 3, containing as units 32) PA8I, 86, 66, 61 or mixtures thereof. Copolyamide molding compositions according to claims 1 to 4, in which the copolyamide A) has a TG (glass transition temperature) measured by DSC according to ISO 1 1357 - 2, 3 and 7 of greater than 104 ° C. Copolyamide molding compositions according to claims 1 to 5, wherein component A) has a melting temperature T _m of less than 330 ° C measured by DSC according to ISO 1 1357 - 2, 3 and 7. Use of the copolyamide molding compositions according to claims 1 to 6 for the production of fibers, films and moldings. Shaped body obtainable from the copolyamide molding compositions according to claims 1 to 6.