DE102008058246A1 - Thermoplastic molding composition, useful to produce fibers, films and moldings including e.g. intake manifolds, intercooler and circuit board components, comprises thermoplastic polyamide, polyethyleneimine homo or copolymer and additives - Google Patents

Abstract

Thermoplastic molding composition comprises: (a) 29 to (100 wt.% minus 1 ppb) of at least one thermoplastic polyamide, (b) 1 ppb to 2 wt.% of at least one polyethyleneimine homo or copolymer, and (c) 0-70 wt.% of additives. An independent claim is included for increasing the molecular weight of polyamides comprising adding 1 ppb to 2 wt.% of polyethyleneimine homo or copolymer to the components (a).

Description

• A) 29 bis (100 Gew.-% minus 1 ppb) mindestens eines thermoplastischen Polyamids,
• B) 1 ppb bis 2 Gew.-% mindestens eines Polyethyleniminhomo- oder -copolymerisates, sowie darüber hinaus
• C) 0 bis 70 Gew.-% weiterer Zusatzstoffe,

wobei die Gewichtsprozente der Komponenten A) bis C) stets 100% ergeben.The invention relates to thermoplastic molding compositions comprising

• A) 29 to (100% by weight minus 1 ppb) of at least one thermoplastic polyamide,
• B) 1 ppb to 2 wt .-% of at least one Polyethyleniminhomo- or -copolymerisates, and beyond
• C) 0 to 70% by weight of further additives,

the weight percent of components A) to C) always being 100%.

Farther the invention relates to the use of the invention Molding compounds for the production of fibers, films and moldings of any kind, as well as the moldings available here and methods for increasing the molecular weight of Polyamides.

thermoplastic Polyamides such as PA6 and PA66 are often in the form of glass fiber reinforced molding compounds as construction materials for components that during exposed to elevated temperatures during their lifetime, used, resulting in thermo-oxidative damage. By adding known heat stabilizers can Although the occurrence of thermo-oxidative damage delayed but not be permanently prevented, what z. In one Fall of the mechanical characteristics expresses. The Improvement of heat aging resistance (WAB) Of polyamides is highly desirable, since thereby longer Lifetimes achieved for thermally loaded components or their default risk can be reduced can. Alternatively, an improved WAB can also use the Allow components at higher temperatures.

From the Kunststoff Handbuch 3. Technical Thermoplastics, 4. Polyamides, 1998 Carl Hanser Verlag Munich Vienna, publisher L. Bottenbruch, R. Binsack is the use of various heat stabilizers in polyamides known.

The use of hyperbranched polyethyleneimines in thermoplastic polymers is z. B. off DE-A 10030553 known. Examples are given there only for unreinforced polyoxymethylene molding compositions, the diesel fuel resistance is improved.

From the EP-A 1065236 Unreinforced polyamides are known in which polyethyleneimines and oligocarboxylic acids are used during the polymerization. The molding compositions described have improved solvent resistance, but the WAB is in need of improvement.

From the DE 102005005847 Stabilized polyamides containing polyethyleneimines and stabilizers are known. However, the Bindenahtfestigkeit the molding materials is in need of improvement.

task The present invention was therefore stabilized polyamide molding compounds to provide an increased molecular weight and have better stability. The processing properties should also be improved.

Accordingly, were Found the molding compounds defined above. Preferred embodiments are to refer to the dependent claims.

As component A), the molding compositions according to the invention contain from 29% by weight to (100% by weight minus 1 ppb) of at least one thermoplastic polyamide. Preferably, the proportion of A) is 40 wt .-% to (100 wt .-% minus 1 ppm), and in particular 50 to 98 wt .-%. These details are based on the molding compositions A) to C). It means ppb parts per billion (weight) = 1:10 ⁹ and ppm parts per million (weight) = 1:10 ⁶ .

The Notation "(100% by weight minus 1 ppb)" for the percentage by weight obtained if subtract 1 ppb from 100% by weight. The chosen spelling appeared clearer than the specification in the format "99,999 ..." with many nines after the decimal point. The same applies to the notations "(100% by weight minus 1 ppm) and" (100 Wt% minus 500 ppm) ".

The polyamides of the molding compositions according to the invention have a viscosity number of at least 140, preferably 150 to 350 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. ISO 307.

Semicrystalline or amorphous resins having a weight average molecular weight of at least 5,000, as described, for. Tie US Pat. No. 2,071,250 . 2 071 251 . 2 130 523 . 2,130,948 . 2 241 322 . 2 312 966 . 2 512 606 and 3 393 210 are described are preferred.

Examples These are polyamides, ranging from lactams with 7 bis Derive 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam and polyamides obtained by reacting dicarboxylic acids to be obtained with diamines.

When Dicarboxylic acids are alkanedicarboxylic acids with 6 to 12, especially 6 to 10 carbon atoms and aromatic Dicarboxylic acids used. Here are only adipic acid, Azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acids as acids called.

When Diamines are particularly suitable alkanediamines with 6 to 12, in particular 6 to 8 carbon atoms and m-xylylenediamine, di- (4-aminophenyl) methane, Di (4-aminocyclohexyl) methane, 2,2-di- (4-aminophenyl) -propane, 2,2-di- (4-aminocyclohexyl) -propane or 1,5-diamino-2-methylpentane.

preferred Polyamides are Polyhexamethylenadipinsäureamid, Polyhexamethylensebacinsäureamid and Polycaprolactam and copolyamides 6/66, in particular with a proportion from 5 to 95% by weight of caprolactam units.

Further suitable polyamides are obtainable from ω-aminoalkyl nitriles such as, for example, aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by so-called direct polymerization in the presence of water, for example in US Pat DE-A 10313681 . EP-A 1198491 and EP 922065 described.

In addition, polyamides are also mentioned, the z. B. by condensation of 1,4-diaminobutane with adipic acid at elevated temperature are available (polyamide 4.6). Manufacturing process for polyamides of this structure are z. Tie EP-A 38 094 . EP-A 38 582 and EP-A 39 524 described.

Farther are polyamides obtained by copolymerization of two or more the aforementioned monomers are obtainable, or mixtures more suitable polyamides, wherein the mixing ratio is arbitrary.

Furthermore, such partially aromatic copolyamides as PA 6 / 6T and PA 66 / 6T have proven to be particularly advantageous, the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444 ).

The production of the preferred partially aromatic copolyamides having a low triamine content can be carried out according to the methods described in US Pat EP-A 129 195 and 129 196 described method.

The following non-exhaustive list contains the mentioned, as well as other polyamides A) in the context of the invention and the monomers contained. AB-polymers: PA 4 pyrrolidone PA 6 ε-caprolactam PA 7 Ethanolactam PA 8 capryllactam PA 9 9-amine Opel argon acid PA 11 11-aminoundecanoic PA 12 laurolactam AA / BB-polymers PA 46 Tetramethylenediamine, adipic acid PA 66 Hexamethylenediamine, adipic acid 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 61 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 6I and PA 6T) PA PACM 12 Diaminodicyclohexylmethane, laurolactam PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane PA 12 / MACMI Laurinlactam, dimethyldiaminodicyclohexylmethane, isophthalic acid PA 12 / MACMT Laurinlactam, dimethyl-diaminodicyclohexylmethane, terephthalic acid PA PDA-T Phenylenediamine, terephthalic acid

The thermoplastic molding compositions contained as component B) according to the invention. 1 ppb to 2 wt .-% of at least one polyethyleneimine homopolymer or copolymers. Preferably, the proportion of B) 1 ppm to 1.5% by weight and in particular 500 ppm to 1.5% by weight based on A) to C), with branched polyethyleneimines being preferred are.

For the purposes of the present invention, polyethyleneimines are to be understood as meaning both homopolymers and copolymers which are synthesized, for example, by the processes in Ullmann Electronic Release under the heading "aziridines" or in accordance with US Pat WO-A 94/12560 are available.

The homopolymers are generally obtainable by polymerization of ethyleneimine (aziridine) in aqueous or organic solution in the presence of acid-releasing compounds, acids or Lewis acids. Such homopolymers are branched polymers, which usually contain primary, secondary and tertiary amino groups in the ratio of about 30% to 40% to 30%. The distribution of the amino groups can generally be determined by means of ¹³ C-NMR spectroscopy. This is preferably 1 / 0.8 / 0.5 to 1 / 1.3 / 0.8, in particular from 1 / 1.1 / 0.8 to 1 / 1.2 / 0.8

When Comonomers are preferably used compounds which at least have two amino functions. As suitable comonomers are, for example Alkylenediamines having 2 to 10 carbon atoms in the alkylene radical, wherein Ethylenediamine and propylenediamine are preferred. Furthermore suitable Comonomers are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.

Polyethyleneimines typically have a weight average molecular weight of from 100 to 3,000,000, preferably from 800 to 2,000,000 (as determined by light scattering). The preferred M _w is from 900 to 50,000, especially from 1100 to 25,000.

In addition, crosslinked polyethyleneimines obtained by reaction of polyethyleneimines with bi- or polyfunctional crosslinkers are available which have as a functional group at least one halohydrin, glycidyl, aziridine, isocyanate unit or a halogen atom. As examples, its epichlorohydrin or bischlorohydrin of polyalkylene glycols having 2 to 100 ethylene oxide and / or propylene oxide units and in the DE-A 19 93 17 20 and US 4,144,123 called compounds listed. Processes for the preparation of crosslinked polyethyleneimines are, inter alia, from the above-mentioned publications as well EP-A 895 521 and EP-A 25 515 known.

Furthermore, grafted polyethyleneimines are suitable, it being possible for all compounds which can react with the amino or imino groups of the polyethyleneimines to be used as the grafting agent. Suitable grafting agents and processes for the preparation of grafted polyethyleneimines are, for example, the EP-A 675 914 refer to.

As well suitable polyethyleneimines according to the invention are amidated Polymers, usually by reaction of polyethyleneimines with carboxylic acids, their esters or anhydrides, carboxamides or carboxylic acid halides are available. ever according to the proportion of amidated nitrogen atoms in the polyethyleneimine chain The amidated polymers can subsequently be crosslinked with the crosslinkers mentioned. Preferably in this case up to 30% of the amino functions amidated, thus for a subsequent cross-linking reaction still sufficient primary and / or secondary nitrogen atoms for To be available.

Furthermore are suitable alkoxylated polyethyleneimines, for example, by Reaction of polyethyleneimine with ethylene oxide and / or propylene oxide are available. Also such alkoxylated polymers are then networked.

When further suitable polyethyleneimines according to the invention are hydroxyl-containing polyethyleneimines and amphoteric polyethyleneimines (Incorporation of anionic groups) and lipophilic polyethyleneimines, usually by incorporation of long-chain hydrocarbon radicals be obtained in the polymer chain. Process for the preparation of such Polyethyleneimines are known to those skilled in the art, so that further details to spare this.

When Component C), the inventive Molding compounds 0 to 70, preferably up to 45 wt .-% of other additives contain.

When Component C), the inventive Molding compounds 0.05 to 3, preferably 0.1 to 1.5 and in particular Contain 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 C-atoms, preferably with 12 to 44 C-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 1 to 3 valent. Examples these are stearylamine, ethylenediamine, propylenediamine, Hexamethylenediamine, di (6-aminohexyl) amine, wherein ethylenediamine and Hexamethylenediamine are particularly preferred. Preferred esters or Amides are accordingly 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 can be used, wherein the mixing ratio is arbitrary.

When Component C), the inventive Molding compounds 0.05 to 3, preferably 0.1 to 1.5 and in particular 0.1 to 1% by weight of a Cu stabilizer, preferably a Cu (I) halide, especially in admixture with an alkali halide, preferably KJ, in particular in the ratio 1: 4 included.

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 fibrous or particulate fillers C) 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 in amounts of 1 to 50 wt .-%, in particular 1 to 40, preferably 10 to 90 wt .-% are used.

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 1

Suitable 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

an integer from 2 to 10, preferably 3 to 4

m

an integer from 1 to 5, preferably 1 to 2

k

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 C)) used for surface coating.

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.

Kaolin, calcined kaolin, wollastonite, talc and chalk are mentioned as further fillers and additionally 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.

When Component C), the inventive Molding compounds 0.1 to 5, preferably 0.1 to 2 and in particular 0.25 to 1 wt .-% of a nigrosine.

Under Nigrosines are generally understood as a group of black ones or gray, induline-related phenazine dyes (azine dyes) in various embodiments (water-soluble, fat-soluble, spar-soluble), 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 microscopic dyes use.

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

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

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

When Component C), the inventive Molding compounds 0 to 30, in particular up to 20 wt .-% of other additives and processing aids.

Other usual Additives C) are, for example, in amounts of up to 25, preferably Up to 20 wt .-% of elastomeric polymers (often as Impact modifier, elastomers or rubbers).

All in general, these are copolymers which are preferred are made up of at least two of the following monomers: ethylene, Propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, Acrylonitrile and acrylic or methacrylic acid esters with 1 to 18 C atoms in the alcohol component.

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

in the Some preferred types of such elastomers are presented below.

preferred Types of such elastomers are the so-called ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers.

EPM rubbers generally have virtually no double bonds while EPDM rubbers 1 to 20 double bonds / 100 carbon atoms may have.

When Diene monomers for EPDM rubbers are for example conjugated dienes 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 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 with reactive Carboxylic acids or derivatives thereof may be grafted. Here be z. As acrylic acid, methacrylic acid and their Derivatives, e.g. As glycidyl (meth) acrylate, and maleic anhydride called.

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

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

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

preferred Compounds of formulas I, II and IV are maleic acid, Maleic anhydride and epoxy group-containing esters 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, but in their behavior they approach the free acids and are therefore termed monomers having latent carboxyl groups.

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

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

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

Besides Vinyl esters and vinyl ethers may also be used as comonomers become.

The The above-described ethylene copolymers can according to be prepared per se known methods, preferably by statistical copolymerization under high pressure and elevated Temperature. Corresponding methods are generally known.

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

in principle can be homogeneously constructed elastomers or with such be used a shell structure. The shell-like construction is determined by the order of addition of the individual monomers; the morphology of the polymers is also determined by this order of addition affected.

Just are representative here as monomers for the production the rubber part of the elastomers acrylates such. B. n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and Isoprene and their mixtures called. These monomers can with other monomers such. As styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, Methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.

The Soft or rubber phase (with a glass transition temperature below 0 ° C) of the elastomers may be the core, the outer Shell or a middle shell (in elastomers with more as a two-shell construction); with multi-shell elastomers can also consist of several shells of a rubber phase.

are in addition to the rubber phase, one or more hard components (with glass transition temperatures of more than 20 ° C) involved in the construction of the elastomer, so these are in general 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 as major monomers produced. In addition, smaller shares can also be used here be used on other comonomers.

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

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

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

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

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

When other examples are acrylamide, methacrylamide and substituted Esters of acrylic acid or methacrylic acid such as (N-t-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 crosslinking agents are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate and those described in US Pat EP-A 50 265 described compounds.

Further may also be so-called graft-linking monomers (graft-linking monomers) are used, d. H. Monomers with two or more polymerisable Dop pelbindungen that in the polymerization with different Speeds respond. Preferably, such compounds used in which at least one reactive group with about the same Speed polymerized like the other monomers, while the other reactive group (or reactive groups) z. B. polymerized much slower (polymerize). The different ones Polymerization rates bring a certain proportion with unsaturated double bonds in the rubber. Is then on such a rubber another Grafted phase, so react the double bonds present in the rubber at least partially with the graft monomers to form chemical bonds, d. H. the grafted phase is at least partly via chemical bonds with the graft base connected.

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

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

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

Instead of of graft polymers having a multi-shell structure also homogeneous, d. H. single-shell elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or their copolymers are used. Also These products can be made by using cross-linking Monomers or monomers are prepared with reactive groups.

Examples for 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 with an inner core of n-butyl acrylate or butadiene-based and an outer shell of the above mentioned copolymers and copolymers of ethylene with comonomers, provide the reactive groups.

The described elastomers may also be other customary Method, for. B. by suspension polymerization.

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

Of course may also be mixtures of those listed above Rubber types are used.

When Component C), the inventive thermoplastic molding compounds customary processing aids such as stabilizers, antioxidants, agents against Heat decomposition and decomposition by ultraviolet light, Lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, flame retardants etc. included.

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

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, furthermore organic pigments, such as phthalocyanines, Quinacridones, perylenes and dyes, such as anthraquinones as colorants be added.

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

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, Brabender 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 230 to 320 ° C.

To Another preferred mode of operation may include the components B) to F) and optionally C) with a prepolymer mixed, compounded and granulated. The granules obtained then becomes continuous in inert phase under inert gas or discontinuously at a temperature below the melting point of component A) to the desired viscosity condensed.

According to the process according to the invention for increasing the molecular weight (M _w ) of the polyamides, the polyethyleneimine polymers are added to component A). The initial VZ of the polyamides is at least 80 ml / g, preferably at least 140 ml / g.

Preferably the addition of B) "hot-feed" occurs in zone 3 or 6 of an extruder into the polyamide melt.

The Residence time in the melt is preferably from 0.2 to 2 min, in particular from 0.5 to 1 min.

The Residence time can be selected depending on the desired molecular weight become.

The Shear stress here is preferably from 0.1% to 20%, in particular from 1% to 10%.

The Difference of the final to the initial viscosity number is at least 20 ml / g, preferably at least 50 ml / g.

The thermoplastic molding compositions according to the invention are characterized by good processability at the same time good mechanics, as well as a much higher molecular weight and thermal stability.

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

In the E / E area, flow-improved polyamides can be used to connect plugs, connector parts, connectors, wiring harness components, circuit boards, circuit carrier components, three-dimensional injection-molded Circuit board, electrical connectors, mechatronic components are manufactured.

in the Car Interior is a 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 protective housing, Grille, roof rails, sunroof frames, engine covers, cylinder head covers, Intake pipes (in particular intake manifold), windscreen wipers as well as body exterior parts possible.

For the kitchen and household area is the use flow improved Polyamides for the manufacture of components for kitchen appliances, such as As fryers, irons, buttons, and Applications in the garden leisure area, z. B. Components for Irrigation systems or garden tools and door handles possible.

Examples

It the following components were used:

Component A / 1:

• Polyamide 6 (polycaprolactam) with a viscosity number VZ of 150 ml / g, measured as 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C after ISO 307 , (It was Ultramid ^® B 32 by BASF SE used).

Component A / 2:

• PA 6 with a VZ of 170 ml / g.

Component A / 3:

• PA 6 with a VZ of 200 ml / g.

B) Polyethyleneimines Table 1: Lupasol ^® G20 (B / 1) WF (B / 2) M _w 1 300 25,000 Prim / sec / tert amines 1 / 0.91 / 0.64 1 / 1.20 / 0.76 Lupasol ^® ≙ registered trademark of BASF SE

The ratio of primary / secondary / tertiary amines was determined by ¹³ C NMR spectroscopy.

C) Glass fibers

The Molding compounds were applied on a ZSK 25 at a throughput of 3 to 10 kg / h and about 260 to 290 ° C flat temperature profile produced.

The Components B) were added (see table) either in zone 3 or 6.

It Films were extruded and circular discs and after drying in one Rotation rheometer transferred.

The Films were in round discs of 25 mm diameter and 1 mm in height cut and dried under vacuum at 80 ° C for 4 days.

The following measurements were carried out:
The rheological investigations were carried out at 260 ° C on a shear stress controlled Rotationsrhe ometer carried out.

The Areas of angular frequencies were from 100 to 2 rad / s.

The predetermined amplitude of the shear stress was 100 Pa.

The determination of M _{w was} carried out by means of size exclusion chromatography (SEC) with hexafluoroisopropanol / K trifluoroacetate as solvent. All samples were pre-filtered. The columns were conditioned at 40 ° C in the oven. Each sample was injected with 25 μl.

The Compositions of the molding compositions and the measurement results are the Tables 2 and 3 can be seen.

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

• - DE 10030553 A [0005]
• - EP 1065236 A [0006]
• - DE 102005005847 [0007]
• US 2071250 [0013]
• - US 2071251 [0013]
• US 2130523 [0013]
• US 2130948 [0013]
• US 2241322 [0013]
• - US 2312966 [0013]
• - US 2512606 [0013]
• - US 3393210 [0013]
• - DE 10313681 A [0018]
• - EP 1198491 A [0018]
• - EP 922065 [0018]
• EP 38094A [0019]
• - EP 38582A [0019]
• - EP 39524A [0019]
• EP 299444 [0021]
• - EP 129195A [0022]
• - EP 129196 [0022]
• WO 94/12560 [0025]
• - DE 19931720 [0029]
• US 4144123 [0029]
• - EP 895521 [0029]
• - EP 25515 A [0029]
• - EP 675914 [0030]
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• - DE 3725576A [0095]
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Cited non-patent literature

• - Kunststoff Handbuch 3. Engineering thermoplastics, 4. Polyamides, 1998 Carl Hanser Verlag Munich Vienna, publisher L. Bottenbruch, R. Binsack [0004]
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• Monograph by CB Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977) [0065]
• - Blackley in the monograph "Emulsion Polymerization" [0079]
• - ISO 307 [0115]

Claims (9)

Thermoplastic molding compositions containing A) 29 to (100 wt% minus 1 ppb) of at least one thermoplastic polyamide, B) 1 ppb to 2 wt .-% of at least one Polyethyleniminhomo- or copolymers, as well as beyond C) 0 to 70% by weight of other additives, where the weight percent of components A) to C) always give 100%. Thermoplastic molding compositions according to claim 1, wherein the polyethyleneimine polymers are selected from homopolymers of ethyleneimine, Copolymers of ethyleneimine and amines with at least two amino groups, crosslinked polyethyleneimines, grafted Polyethylenmininen, amidated polymers available by reaction of polyethyleneimines with carboxylic acids or carboxylic acid esters, anhydrides, amides or halides, alkoxylated polyethyleneimines, hydroxyl-containing polyethyleneimines, amphoteric Polyethyleneimines, and lipophilic polyethylenimines. Thermoplastic molding compositions according to the claims 1 or 2, in which component B) has a ratio of primary / secondary / tertiary amines from 1 / 0.8 / 0.5 to 1 / 1.3 / 0.8. Process for increasing the molecular weight of polyamides, characterized in that a polyamide A) 1 ppb to 2 wt .-% of a Polyethyleniminhomo- or copolymer inflicts. Method according to claim 4, characterized in that that the polyamide A) has a viscosity number VZ of at least 140 ml / g. Method according to claims 4 or 5, characterized in that component B) is "hot-fed" in Zone 3 or 6 of the extruder is added to the polyamide melt. Process according to claims 4 to 6, characterized characterized in that the residence time in the melt from 0.2 to 2 min. Use of thermoplastic molding compositions according to the Claims 1 to 3 or obtainable according to the Process conditions of claims 4 to 7 for the production of fibers, films and moldings of any kind. Fibers, films and moldings, available from the molding compositions according to the claims 1 to 3 or according to the process conditions of Claims 4 to 7.