WO2009050094A1

WO2009050094A1 - Thermoplastic polyester molding compounds comprising highly branched polyether amines

Info

Publication number: WO2009050094A1
Application number: PCT/EP2008/063507
Authority: WO
Inventors: Claudia Mettlach; Bernd Bruchmann; Chirag Tejuja; Andreas Eipper; Mark VÖLKEL; Michael Dietz
Original assignee: Basf Se
Priority date: 2007-10-10
Filing date: 2008-10-09
Publication date: 2009-04-23

Abstract

The invention relates to thermoplastic molding compounds comprising A) 10 to 99 weight % of at least one thermoplastic polyester, B) 0.01 to 30 weight % of at least one hyper-branched polyether amine, C) 0 to 60 weight % of further additives, wherein the sum of the weight percentages of components A) through C) is 100%.

Description

POLYETHERAMINE INCLUDED

description

The invention relates to thermoplastic molding compositions comprising

A) 10 to 99% by weight of at least one thermoplastic polyester,

B) 0.01 to 30% by weight of at least one highly branched or hyperbranched polyether amine,

C) 0 to 60% by weight of other additives,

wherein the sum of the weight percentages of components A) to C) is 100%.

Furthermore, the invention relates to the use of polyetheramines to improve the flowability of polyesters, the production of fibers, films and moldings of any kind and the fibers, films and moldings obtainable in this case.

Polyetheramine (polyols) are usually prepared from trialkanolamines, e.g. Triethanol- amine, tripropanolamine, triisopropanolamine, optionally in admixture with mono- or dialkanolamines obtained by catalysis of these monomers, e.g. acidic or basic catalysis, etherified with elimination of water. The preparation of these polymers is e.g. in US Pat. No. 2,178,173, US Pat. No. 2,290,415, US Pat. No. 2,407,895 and DE 40 03 243. The polymerization can be carried out either statistically or block structures can be prepared from individual alkanolamines which are linked together in a further reaction (see also US Pat. No. 4,404,362).

The in the o.g. Literature described polyetheramine (polyols) are in free or quaternized form, e.g. used as demulsifiers for oil / water mixtures, as a post-treatment agent for dyed leather (DE 41 04 834) or as a lubricant for metal processing (CS 265 929).

Lubricants are generally added for the flow improvement of thermoplastic polyesters and polycarbonates (see Gächter, Müller: Kunststoffadditive, 3rd ed. P. 479, 486-488, Carl Hanser Verlag 1989). Disadvantages here are in particular the blooming of the additives during processing.

WO 97/45474 and EP-A 14 24 360 and WO 2006/18127 with WO 2005/075565 disclose dendritic polymers and dendrimers as additives for improving the flowability of thermoplastics. The disadvantage here is a very reduced gerte effectiveness, depending on the matrix polymer and / or high molecular weight thermoplastics.

The object of the present invention was therefore to increase the flowability of polyester molding compositions, wherein the decrease in the viscosity number should be as low as possible. Furthermore, the additive should be present in small amounts in the matrix. The mechanics of the molding compounds should be preserved as much as possible and the additive should not bloom during processing.

Accordingly, the thermoplastic molding compositions mentioned above, their use, and the moldings, films and fibers obtainable from them were found. Preferred embodiments of the invention can be found in the subclaims.

Note on the amounts given below: in the case of the thermoplastic molding composition, the amounts of components A) to C) within the ranges mentioned are selected such that the sum of components A) and B) and optionally C) is 100% by weight. % added; Component C) is optional.

As component A), the molding compositions according to the invention contain from 10 to 99.9, preferably from 20 to 99, and in particular from 30 to 98,% by weight of at least one thermoplastic polyester A).

Generally, polyesters A) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are used. A first group of preferred polyesters are polyalkylene terephthalates, in particular those having 2 to 10 carbon atoms in the alcohol part.

Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid. The aromatic ring may also be substituted, e.g. by halogen, such as chlorine and bromine, or by C 1 -C 4 -alkyl groups, such as methyl, ethyl, isopropyl or n-propyl and n, i and t-butyl groups.

These polyalkylene terephthalates can be prepared by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds in a manner known per se.

Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids are replaced.

Of the aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol , 1, 4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof.

Particularly preferred polyesters A) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 C atoms. Of these, particularly preferred are polyethylene terephthalate (PET), polypropylene terephthalate and polybutylene terephthalate (PBT) or mixtures thereof.

Particularly preferred are thermoplastic molding compositions, characterized in that the polyester A) is selected from polybutylene terephthalate and polyethylene terephthalate. Further preferred are PET and / or PBT containing up to 1 wt .-%, preferably up to 0.75 wt .-% 1, 6-hexanediol and / or 2-methyl-1, 5-pentanediol as further monomer units.

The viscosity number of the polyesters A) is generally in the range from 50 to 220, preferably from 80 to 160, measured in a 0.5 wt .-% solution of the polyester in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 ) at 25 ⁰ C according to ISO 1628.

Particular preference is given to polyesters whose carboxyl end group content is up to

100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg polyester. Such polyesters can be prepared, for example, by the process of DE-A 44 01 055. The carboxyl end group content is usually determined by titration methods (e.g., potentiometry).

Very particularly preferred molding compositions contain, as component A), a mixture of PBT and polyesters which are different from PBT, for example polyethylene terephthalate (PET). The proportion e.g. of the polyethylene terephthalate in the mixture is preferably up to 50, in particular 10 to 35 wt .-%, based on 100 wt .-% of component A).

Furthermore, one can use PET recyclates (also called scrap PET), optionally mixed with polyalkylene terephthalates such as PBT.

In general, recyclates are understood as either 1) so-called post-industrial recycled pulp: this refers to production waste during polycondensation or during processing, for example, sprues in injection molding processing, starting goods at the Injection molding or extrusion, or edge portions of extruded sheets or foils; or 2) post consumer recyclate: these are plastic items that are collected and processed after use by the end user; By far the most dominant articles in terms of volume are blow molded PET bottles for mineral water, soft drinks and juices.

Both types of recycled material can be present either as regrind or in the form of granules. In the latter case, the slag cyclates after separation and purification are melted in an extruder and granulated. This usually facilitates the handling, the flowability and the metering for further processing steps.

Both granulated and regrind recyclates can be used, with the maximum edge length being 10 mm, preferably less than 8 mm. Traces of moisture favor the hydrolytic cleavage of polyesters during processing. Therefore, it is recommended to pre-dry the recyclate. The residual moisture content after drying is preferably <0.2%, in particular <0.05%.

Another group of suitable polyesters A) are fully aromatic polyesters derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.

Suitable aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preference is given to mixtures of 5 to

100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid, in particular mixtures of about 80% terephthalic acid with 20% isophthalic acid to about equivalent mixtures of these two acids used.

The aromatic dihydroxy compounds preferably have the general formula

in which Z represents an alkylene or cycloalkylene group having up to 8 C atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m the value 0 to 2 has. The compounds may also carry C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.

As a parent of these compounds are, for example Dihydroxydiphenyl, di (hydroxyphenyl) alkane, di (hydroxyphenyl) cycloalkane, di (hydroxyphenyl) sulfide, di (hydroxyphenyl) ether, di (hydroxyphenyl) ketone, di (hydroxyphenyl) sulfoxide, α, α'-di - (hydroxyphenyl) -dialkylbenzene, di- (hydroxyphenyl) sulfone, di- (hydroxybenzoyl) benzene, resorcinol and hydroquinone and their nuclear alkylated or ring-halogenated derivatives called.

Of these will be

4,4'-dihydroxydiphenyl, 2,4-di- (4'-hydroxyphenyl) -2-methylbutane α, α'-di- (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-di- (3'-) methyl-4'-hydroxyphenyl) propane and 2,2-di (3'-chloro-4'-hydroxyphenyl) propane,

and in particular

2,2-di- (4'-hydroxyphenyl) propane

2,2-di- (3 ', 5-dichlordihydroxyphenyl) propane,

1, 1-di- (4'-hydroxyphenyl) cyclohexane,

3,4'-dihydroxybenzophenone,

4,4'-dihydroxydiphenylsulfone and 2,2-di (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane

or mixtures thereof are preferred.

Of course, it is also possible to use as polyester A) mixtures of polyalkylene terephthalates and wholly aromatic polyesters. These generally contain from 20 to 98% by weight of the polyalkylene terephthalate and from 2 to 80% by weight of the wholly aromatic polyester.

It is likewise possible to use polyester block copolymers, such as copolyether esters. Such products are known per se and described in the literature, for example in US Pat. No. 3,651,014. (Hytrel® DuPont). Mixtures of different partially aromatic polyesters are also possible. In particular, under partly aromatic polyesters products such as Ecoflex ^® (BASF Aktiengesellschaft), Eastar ^® Bio and Origo-Bi understand (Novamont).

Particularly preferred partially aromatic polyesters include polyesters as essential components

a) an acid component

a1) 35 to 99 mol% of at least one aliphatic or at least one cycloaliphatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof

a2) 1 to 65 mol% of at least one aromatic dicarboxylic acid or its ester-forming derivative or mixtures thereof and

a3) 0 to 5 mol% of a sulfonate group-containing compound,

b) a diol component selected from at least one C2 to C12 alkanediol and at least one C to Cio cycloalkanediol or mixtures thereof

and, if desired, moreover one or more components selected from

c) a component selected from

d) at least one dihydroxy compound of the formula I containing ether functions

where n is 2, 3 or 4 and m is an integer from 2 to 250

c2) at least one hydroxycarboxylic acid or formula IIa or IIb

in which p is an integer from 1 to 1500 and r is an integer from 1 to 4, and G is a radical selected from the group consisting of phenylene, - (CH ₂ ) _q -, where q is an integer from 1 to 5, -C (R) H- and -C (R) HCH ₂ , where R is methyl or ethyl

c3) at least one amino-C 2 -C 12 -alkanol or at least one amino-C 6 -C 10 -cycloalkanol or mixtures thereof

c4) at least one diamino-d-bis-Cs alkane

c5) at least one 2,2'-bisoxazoline of the general formula III

wherein R ^{1 represents} a single bond, a (CH ₂ ) _Z alkylene group, with z = 2, 3 or 4, or a phenylene group

c6) at least one aminocarboxylic acid selected from the group consisting of the natural amino acids, polyamides obtainable by polycondensation of a dicarboxylic acid having 4 to 6 C atoms and a diamine having 4 to 10 C atoms, compounds of the formulas IV a and Ivb

in which s is an integer from 1 to 1500 and t is an integer from 1 to 4, and T is a radical selected from the group consisting of phenylene, - (CH ₂ ) U-, where u is an integer Number from 1 to 12 means -C (R ² ) H and -C (R ² ) HCH ₂ , where R ^{2 is} methyl or ethyl,

and polyoxazolines having the repeating unit V

in which R ^{3 is} hydrogen, C ¹ -C 6 -alkyl, C ³ -C 5 -cycloalkyl, phenyl which is unsubstituted or substituted up to three times by C ¹ -C 4 -alkyl groups or is tetrahydrofuryl,

or mixtures of d to c6 and

d) a component selected from

d1) at least one compound having at least three groups capable of ester formation,

d2) at least one isocyanate

d3) at least one divinyl ether

or mixtures of d1) to d3).

In a preferred embodiment, the acid component a) of the partially aromatic polyesters contains from 35 to 70, in particular from 40 to 60, mol% of a1 and from 30 to 65, in particular from 40 to 60, mol% of a2.

Particularly preferred as component A) is a copolymer of

aa-i) from 40 to 60% by weight, based on the total weight of components a1) and a2), of at least one succinic, adipic or sebacic acid or their ester-forming derivatives or mixtures thereof, aa2) 40 to 60% by weight, based on the total weight of the components a1) and a2) terephthalic acid or its ester-forming derivatives or mixtures thereof, from) 100 mol% based on the components a1) and a2) 1, 4-butanediol or 1, 3

Propanediol or mixtures thereof as diol component, adi) 0 to 1 wt .-% of a compound having at least three ester-capable groups as branching; ad2) 0 to 2 wt .-% of a diisocyanate as a chain extender.

The mentioned partly aromatic polyesters A are generally biodegradable.

For the purposes of the present invention, the characteristic "biodegradable" for a substance or a mixture of substances is fulfilled if this substance or the mixture of substances in at least one of the three methods defined in DIN V 54900-2 (pre-standard, September 1998) a percentage degree of biodegradation of at least 60%.

The preferred partially aromatic polyesters are characterized by a molecular weight (M _n ) in the range from 1000 to 100 000, in particular in the range from 9000 to 75000 g / mol, preferably in the range from 10 000 to 50 000 g / mol and a melting point in the range of 60 to 170, preferably in the range of 80 to 150 ^° C. The abovementioned partially aromatic polyesters may have hydroxyl and / or carboxyl end groups in any ratio. The abovementioned partially aromatic polyesters can also be end-group-modified. For example, OH end groups can be acid-modified by reaction with phthalic acid, phthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid or pyromellitic anhydride.

Preference is given to mixtures of such biodegradable polyesters with polyalkylene terephthalates A) in a ratio of 30:70, preferably 10:90, and in particular 6:94. (Weight percent, based on 100% A).

As a polyester to be understood according to the invention also halogen-free polycarbonates. Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula (2)

wherein Q is a single bond, a C 1 to C 5 alkylene, a C 2 to C 3 alkylidene, a C 3 to C 6 cycloalkylidene group, a C 6 to C 12 arylene group, and -O-, -S- or -SO 2 - and m is an integer from 0 to 2. The diphenols can also carry substituents on the phenylene radicals, for example C 1 - to C 6 -alkyl or C 1 - to C 6 -alkoxy.

Preferred diphenols of the above formula (2) are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,4-bis- (4-hydroxyphenyl) 2-methylbutane and 1, 1-bis (4-hydroxyphenyl) cyclohexane. Particularly preferred are 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 1, 1-bis (4-hydroxyphenyl) cyclohexane, and 1, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane (= bisphenol TMC). The diphenols of the general formula (2) are known per se or can be prepared by known processes.

Both homopolycarbonates and copolycarbonates are suitable as component A) of the molding compositions according to the invention. In addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.

The suitable polycarbonates may be branched in a known manner, preferably by the incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having three or more than three phenolic compounds OH groups. Particularly suitable polycarbonates have proven, the relative viscosities ηrei of 1, 10 to 1, 50, in particular from 1, 25 to 1, 40 have. This corresponds to average molecular weights M _w (weight average) of 10,000 to 200,000, preferably from 20,000 to 80,000 g / mol.

The polycarbonates can be prepared, for example, by reacting the diphenones with phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators , With regard to polydiorganosiloxane-containing polycarbonates, see, for example, DE-OS 33 34 782.

Suitable chain terminators include phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1, 3-tetramethyl-butyl) -phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06 472, such as p-nonylphenol, 3,5-di-t-butylphenol, pt-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- (3, 5-dimethylheptyl) -phenol.

Halogen-free polycarbonates in the context of the present invention means that the polycarbonates are composed of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of minor ppm amounts of saponifiable chlorine, resulting, for example, from the preparation of the polycarbonates with phosgene by the interfacial process, is not to be regarded as halogen-containing in the context of the invention. Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the context of the present invention.

As further suitable components A) may be mentioned amorphous polyester carbonates, wherein phosgene was replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units in the preparation. For further details, reference is made to EP-A 71 1 810.

Further suitable copolycarbonates with cycloalkyl radicals as monomer units are described in EP-A 365 916.

Furthermore, bisphenol A can be replaced by bisphenol TMC. Such polycarbonates are available under the trademark APEC HT® from Bayer. As component B), the molding compositions according to the invention contain 0.01 to 30, preferably 0.05 to 10 and in particular 0.05 to 5 wt .-% of at least one hyperbranched polyetheramine.

Component B) is obtainable by reacting at least one tertiary amine with hydroxy functional groups, preferably at least one di-, tri- or tetraalkanolamine with optionally secondary amines which carry hydroxyl groups as a substituent, in particular dialkanolamines or optionally with di- or higher-functional polyether polyols, preferably in Presence of a transetherification and etherification catalyst.

Preferred tertiary dialkanolamines having hydroxy functional groups are

Diethanolalkylamines with C1 to C30, in particular C1 to C18, diethanolamine,

dipropanolamine

diisopropanolamine,

dibutanolamine,

Dipentanolamine, dihexanolamine,

N-methyl-diethanolamine,

N-methyl-dipropanolamine,

N-methyl-diisopropanolamine,

N-methyl-dibutanolamine, N-methyl-dipentanolamine,

N-methyl-dihexanolamine,

N-ethyl-diethanolamine,

N-ethyl-dipropanolamine,

N-ethyl-diisopropanolamine, N-ethyl-dibutanolamine,

N-ethyl-Dipentanolamin,

N-ethyl-dihexanolamine,

N-propyl diethanolamine,

N-propyl-dipropanolamine, N-propyl-diisopropanolamine,

N-propyl-dibutanolamine,

N-propyl-Dipentanolamin,

N-propyl-dihexanolamine,

Diethanolethylamine, diethanolpropylamine, diethanolmethylamine, Dipropanolmethylamin,

Cyclohexanoldiethanolamin,

Dicyclohexanolethanolamin,

Cyclohexyldiethanolamine, dicyclohexyldiethanolamine,

Dicyclohexanolethylamin,

benzyldiethanolamine,

Dibenzylethanolamin,

Benzyldipropanolamine, tripentanolamine,

Trihexanolamin,

Ethylhexylethanolamin,

octadecyldiethanolamine,

Polyethanolamine,

Preferred trialkanolamines are

Trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, tripentanolamine,

or derivatives derived therefrom.

Preferably R ¹ = CH ₂ -CH ₂ bis (CH ₂ Je, preferably (CH ₂ ) ₂ - (CH ₂ ) ₄ R ² .R ⁵ = c ₂ to C ₆ , preferably C ₂ and C ₃ , eg N, N , N ', N'-tetrahydroxyethylethylenediamine, N, N, N', N'-tetrahydroxyethylbutylenediamine, N, N, N ', N'-tetrahydroxypropylethylenediamine, N, N, N', N'-tetrahydroxyisopropylethylenediamine, N, N, N ', N'-Tetrahydroxypropylbutylenediamine, N, N, N', N'-tetrahydroxyisopropylbutylenediamine. Particularly preferred component B) is obtainable by intermolecular polycondensation of at least one trialkanolamine of the general formula

in which the radicals R ¹ to R ³ independently of one another are identical or different, preferably alkylene, groups having 2 to 10 C atoms, preferably 2 to 6 C atoms.

The starting material used is preferably triethanolamine, tripropanolamine, triisopropanolamine or tributanolamine or mixtures thereof; optionally in combination with dialkanolamines, such as diethanolamine, dipropanolamine, diisopropanolamine, dibutanolamine, N, N'-dihydroxyalkyl-piperidine (alkyl = C1-C8), dicyclohexanolamine, dipentanolamine, dihexanolamine, with dialkanolamines being preferred.

Furthermore, the o.g. Trialkanolamine optionally be used in combination with di- or higher functional polyetherols, in particular based on ethylene oxide and / or propylene oxide.

However, very particular preference is given to using triethanolamine and triisopropanolamine or mixtures thereof as starting material.

The highly functional highly branched or hyperbranched polyetheramines formed by the process according to the invention are terminated with hydroxyl groups after the reaction, ie without further modification. They dissolve well in various solvents.

Examples of such solvents are aromatic and / or (cyclo) aliphatic hydrocarbons and mixtures thereof, halogenated hydrocarbons, ketones, esters and ethers.

Preference is given to aromatic hydrocarbons, (cyclo) aliphatic hydrocarbons, alkanoic acid alkyl esters, ketones, alkoxylated alkanoic acid alkyl esters and mixtures thereof.

Particularly preferred are mono- or polyalkylated benzenes and naphthalenes, ketones, Alkansäurealkylester and alkoxylated Alkansäurealkylester and mixtures thereof. Preferred aromatic hydrocarbon mixtures are those which comprise predominantly aromatic C 7 - to C 20 -hydrocarbons and may have a boiling range of from 10 to 300 ^° C., particular preference is given to toluene, o-, m- or p-xylene, trimethylbenzene isomers, tetramethylbenzene isomers, ethylbenzene , Cumene, tetrahydronaphthalene and mixtures containing such.

Examples include the Solvesso® brands of ExxonMobil Chemical, especially Solvesso® 100 (CAS No. 64742-95-6, predominantly C ₉ and Cio aromatics, boiling range about 154-178 ° C), 150 (boiling range about 182-207 ⁰ C) and 200 (CAS No. 64742-94-5), as well as Shell's Shellsol® grades. Hydrocarbon mixtures on paraffins, cycloparaffins and aromatics are also known under the designations crystal oil (for example crystal oil 30, boiling range about 158-198 ° C. or crystal oil 60: CAS No. 64742-82-1), white spirit (for example likewise CAS No. 64747). 82-1) or solvent naphtha (light: boiling range about 155-180 ⁰ C, heavy: boiling range about 225-300 °), commercially available. The aromatic content of such hydrocarbon mixtures is generally more than 90% by weight, preferably more than 95, more preferably more than 98, and very preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.

The content of aliphatic hydrocarbons is generally less than 5, preferably less than 2.5 and more preferably less than 1 wt .-%.

Halogenated hydrocarbons are, for example, chlorobenzene and dichlorobenzene or isomeric mixtures thereof.

Esters include, for example, n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate.

Ethers are, for example, THF, dioxane and the dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.

Examples of ketones are acetone, 2-butanone, 2-pentanone, 3-pentanone, hexanone, isobutyl methyl ketone, heptanone, cyclopentanone, cyclohexanone or cycloheptanone.

Examples of (cyclo) aliphatic hydrocarbons are decalin, alkylated decalin and isomer mixtures of straight-chain or branched alkanes and / or cycloalkyls. Preference is furthermore given to n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2, 3-methoxyethyl acetate, 2-butanone, isobutyl methyl ketone and mixtures thereof, in particular with the abovementioned aromatic hydrocarbon mixtures.

Such mixtures can be prepared in a volume ratio of 5: 1 to 1: 5, preferably in a volume ratio of 4: 1 to 1: 4, more preferably in a volume ratio of 3: 1 to 1: 3 and most preferably in a volume ratio of 2: 1 to 1: 2 ,

Preferred solvents are butyl acetate, methoxypropyl acetate, isobutyl methyl ketone, 2-butanone, Solvesso® brands and xylene.

Other suitable solvents for the polyetheramines are, for example, water, alcohols, such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, ethylene carbonate or propylene carbonate.

In the context of this invention, a highly functional hyperbranched or hyperbranched polyetheramine is to be understood as meaning a product which, in addition to the ether groups and the amino groups which form the polymer backbone, also has an average of at least three, preferably at least six, more preferably at least ten functional groups Has groups. The functional groups are OH groups. In principle, the number of terminal or pendant functional groups is not limited to the top, but products having a very large number of functional groups may have undesirable properties such as high viscosity or poor solubility. The high-functionality polyetheramine polyols of the present invention generally have not more than 500 terminal or pendant functional groups, preferably not more than 100 terminal or pendant groups.

In the context of this invention, hyperbranched polyetheramines are understood as meaning undyed macromolecules having hydroxyl, ether and amine groups which are structurally as well as molecularly nonuniform. They can be constructed on the one hand, starting from a central molecule analogous to dendrimers, but with uneven chain length of the branches. On the other hand, they can also be constructed linearly with functional side groups or, as a combination of the two extremes, they can have linear and branched molecular parts. For the definition of dendrimeric and hyperbranched polymers see also PJ. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.

The polyetheramines are prepared either in bulk or in solution. Suitable solvents are the solvents already mentioned above. It is a preferred embodiment to carry out the reaction without solvent. The temperature during production should be sufficient for the reaction of the amino alcohol. In general, for the implementation of a temperature of 100 ⁰ C to 350 ⁰ C, preferably 150 to 300, particularly preferably requires 180 to 280 ° C, and especially 200 to 250 ⁰ C.

In a preferred embodiment, the condensation reaction is carried out in bulk. The water or low molecular weight reaction products liberated in the reaction may be removed from the reaction equilibrium to accelerate the reaction, e.g. by distillation, if appropriate under reduced pressure.

Separation of the water or low molecular weight reaction products can also be accomplished by passing a stream of gas substantially inert under the reaction conditions (stripping), e.g. Nitrogen or noble gas, for example helium, neon or argon, be supported.

To accelerate the reaction, it is also possible to add catalysts or catalyst mixtures. Suitable catalysts are compounds which catalyze etherification or transetherification reactions, e.g. Alkali metal hydroxides, alkali metal carbonates, alkali hydrogen carbonates, preferably of sodium, potassium or cesium, acidic compounds such as iron chloride or zinc chloride, formic acid, oxalic acid or

Phosphorus-containing acidic compounds, such as phosphoric acid, polyphosphoric acid, phosphorous acid or hypophosphorous acid.

Preference is given to using phosphoric acid, phosphorous acid or hypophosphorous acid, if appropriate in a form diluted with water.

The addition of the catalyst is generally carried out in an amount of 0.001 to 10, preferably from 0.005 to 7, particularly preferably 0.01 to 5 mol%, based on the amount of alkanolamine or alkanolamine used.

Furthermore, it is also possible to control the intermolecular polycondensation reaction both by adding the appropriate catalyst and by selecting a suitable temperature. Furthermore, the average molecular weight of the polymer can be adjusted via the composition of the starting components and over the residence time.

The polymers prepared at elevated temperature are usually stable at room temperature for a longer period of time, for example for at least 6 weeks, without turbidity, precipitation and / or viscosity increase. There are various possibilities for stopping the intermolecular polycondensation reaction. For example, the temperature can be lowered to a range in which the reaction comes to a standstill and the polycondensation product is storage-stable. This is typically below 60 ⁰ C, preferably below 50 ⁰ C, particularly preferably below 40 ° C and very particularly preferably at room temperature of the case.

Furthermore, one can deactivate the catalyst, for basic catalysts e.g. by adding an acidic component, e.g. a Lewis acid or an organic or inorganic protic acid, in the case of acidic catalysts by addition of a basic component, e.g. a Lewis base or an organic or inorganic base.

Further, it is possible to stop the reaction by dilution with a precooled solvent. This is particularly preferred if it is necessary to adjust the viscosity of the reaction mixture by adding solvent.

The high-functionality highly branched or hyperbranched Polyetherami- ne invention generally have a glass transition temperature of less than 50 ⁰ C, preferably less than 30 and more preferably less than 10 ° C.

The OH number is usually 50 to 1000 mg KOH / g, preferably 100 to 900 mg KOH / g and most preferably 150 to 800 mg KOH / g.

The weight-average molecular weight M _w is usually between 1,000 and 500,000, preferably from 2,000 to 300,000 g / mol, the number average molecular weight M _n between 500 and 50,000, preferably between 1,000 and 40,000 g / mol, measured by gel permeation chromatography with hexafluoroisopropanol as the mobile phase and polymethylmethacrylate (PMMA) as standard.

The preparation of the high-functionality polyetheramines according to the invention is usually carried out in a pressure range from 0.1 mbar to 20 bar, preferably at 1 mbar to 5 bar, in reactors or reactor cascades which are operated batchwise, semicontinuously or continuously.

By the aforementioned adjustment of the reaction conditions and optionally by the choice of the suitable solvent, the products according to the invention can be further processed after preparation without further purification.

If necessary, the reaction mixture may be discolored, for example by treatment with activated charcoal or metal oxides such as alumina, silica, magnesia, zirconia, boria or mixtures thereof, in amounts of For example, 0.1 to 50 wt .-%, preferably 0.5 to 25 wt .-%, particularly preferably 1 to 10 wt .-% at temperatures of for example 10 to 100 ⁰ C, preferably 20 to 80 ⁰ C and particularly preferably Be subjected to 30 to 60 ° C.

Optionally, the reaction mixture may also be filtered to remove any precipitates that may be present.

In a further preferred embodiment, the product is stripped, that is freed from low molecular weight, volatile compounds. For this purpose, after reaching the desired degree of conversion, the catalyst can optionally be deactivated and the low molecular weight volatiles, e.g. Water, the amino alcohols used as starting material or volatile oligomeric or cyclic compounds by distillation, optionally with the introduction of a gas, preferably nitrogen, or noble gases, optionally at reduced pressure, are removed.

The highly functional highly branched polyetheramines formed by the process according to the invention are terminated with hydroxyl groups after the reaction, ie without further modification. They dissolve well in various solvents, e.g. in water, alcohols, such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, terahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate.

As component C), the molding compositions according to the invention may contain from 0 to 60, in particular up to 50% by weight of further additives and processing aids which are different from B) and / or A).

Customary additives C) are, for example, in amounts of up to 40, preferably up to 15,% by weight of 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 e.g. in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg Thieme Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph of CB. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977).

In the following some preferred types of such elastomers are presented. Preferred types of 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 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 also 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 also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, for example 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 adding 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 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 monomers containing epoxy groups and / or methacrylic acid and / or monomers containing acid anhydride groups and the remaining amount of (meth) acrylic acid esters.

Particularly preferred are copolymers of

50 to 98, in particular 55 to 95 wt .-% 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 10 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 emulsifiers and catalysts which can be used are known per se.

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

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 may 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 can be the core, the outer shell or a middle shell (in the case of elastomers with more than two-shelled construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase.

In addition to the rubber phase, one or more hard components (with glass transition temperatures of more than 2O ⁰ C) on the structure of the elastomer, so these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, Acrylsäureestern and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers. In addition, smaller proportions of other comonomers can also be used here. 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

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 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 5 -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

Y OZ 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, so-called graft-linking monomers can also be used, i. Monomers with two or more polymerizable double bonds, which react at different rates during polymerization. Preferably, those compounds are used 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) e.g. polymerized much slower (polymerize). The different polymerization rates bring a certain proportion of unsaturated double bonds in the rubber with it. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the grafting monomers to form chemical bonds, ie. the grafted phase is at least partially linked via chemical bonds to the graft base.

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:

These graft polymers, in particular ABS and / or ASA polymers in amounts of up to 40% by weight, are preferably used for the impact modification of PBT, if appropriate in a mixture with up to 40% by weight of polyethylene terephthalate. Corresponding blend products are available under the trademark Ultradur®S (formerly Ultrablend®S from BASF AG).

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 concomitant use of crosslinking monomers or monomers having reactive groups.

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

The elastomers described can also be prepared by other customary processes, for example 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 abovementioned rubber types.

As fibrous or particulate fillers C) there may be mentioned carbon fibers, glass fibers, glass spheres, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, which are present in quantities of up to 20 Wt .-%, in particular up to 10 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

in which the substituents have the following meanings:

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

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

The silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1, 5 and in particular 0.8 to 1 wt .-% (based on E) for surface coating.

Also suitable are acicular mineral fillers. In the context of the invention, the term "needle-shaped mineral fillers" is understood to mean a mineral filler with a pronounced, needle-like character. An example is acicular wollastonite. Preferably, the mineral has a UD (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1. The mineral filler may optionally be pretreated with the aforementioned silane compounds; however, pretreatment is not essential.

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

As component C), the thermoplastic molding compositions of the invention may contain conventional processing aids such as stabilizers, antioxidants, 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 antioxidants and heat stabilizers sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations up to 1 wt .-%, based on the weight of the thermoplastic molding compositions mentioned.

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

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

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

Also preferred are esters or amides of saturated or unsaturated aliphatic carboxylic acids having 10 to 40, preferably 16 to 22 carbon atoms with aliphatic saturated alcohols or amines containing 2 to 40, preferably 2 to 6 carbon atoms.

The carboxylic acids can be 1- or 2-valent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids having 30 to 40 carbon atoms). The aliphatic alcohols can be 1 - to 4-valent. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.

The aliphatic amines can be monohydric to trihydric. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred. 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.

Other lubricants and mold release agents are usually used in amounts of up to 1% by weight. Preferred are long-chain fatty acids (eg stearic acid or behenic acid), their salts (eg Ca or Zn stearate) or montan waxes (mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 C atoms) and Ca or Na. Montanat and low molecular weight polyethylene or polypropylene waxes.

Examples of plasticizers are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils and N- (n-butyl) benzenesulfonamide.

The novel molding materials may contain from 0 to 2% by weight of fluorine-containing ethylene polymers. These are polymers of ethylene with a fluorine content of 55 to 76 wt .-%, preferably 70 to 76 wt .-%.

Examples of these are polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers. These are e.g. by Schildknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484 to 494 and by Wall in "Fluoropolymers" (Wiley Interscience, 1972).

These fluorine-containing ethylene polymers are homogeneously distributed in the molding compositions and preferably have a particle size d.sub.50 (number average) in the range from 0.05 to 10 .mu.m, in particular from 0.1 to 5 .mu.m. These small particle sizes can be particularly preferably by using aqueous dispersions of achieve fluorine-containing ethylene polymers and their incorporation into a polyester melt.

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 (for example application or tumbling of component B) onto the granules and then to add the remaining starting materials individually and / or likewise mixed. The mixing temperatures are generally from 230 to 290 ^° C. Preferably, component B) can also be added hot feed or directly into the intake of the extruder.

According to a further preferred procedure, the components B) and optionally C) can be mixed with a polyester 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 very good flowability and electrical insulation.

In particular, the processing of the individual components (without clumping or caking) is also possible without problems, even with high filler contents or high molecular weight (see flowability).

The polymer matrix does not degrade significantly during processing, thereby preserving the mechanical properties.

These are suitable for the production of fibers, films and moldings of any kind, in particular for applications in the E / E sector, in particular for plugs, wiring harnesses, switches, housing parts, housing cover, headlight background (Bezel), shower head, fittings, irons, rotary switches, stove knobs , Friteus lid, door handles, (rear) mirror housings, (rear) windscreen wipers, fiber optic sheathing.

Examples

Component A / 1:

Polybutylene terephthalate having a viscosity number of 130 ml / g and a carboxyl end group content of 34 meq / kg (Ultradur® B 4520 from BASF AG) (VZ measured in 0.5% strength by weight solution of phenol / o-dichlorobenzene, 1: 1 mixture at 25 ° C.), containing 0.65% by weight of pentaerythritol tetrastearate (component C / 1), based on 100% by weight of A ).

Component A / 2:

Ecoflex® FBX 7011 (BASF AG):

Aliphatic aromatic copolyester with VZ: 180 ml / g.

Component A / 3:

Polycarbonate based on bisphenol A with a VZ of 59 ml / g according to ISO 1628-4 (Makrolon® 2805 from Bayer AG)

Component A / 4:

PBT like A / 1 but without component C / 1

Component A / 5:

PBT with a VZ of 160 ml / g according to ISO 1628 (Ultradur® B 6550 from BASF AG).

Preparation of component B

In a four-necked flask equipped with stirrer, distillation bridge, gas inlet tube and internal thermometer, 2000 g of triethanolamine (TEA) or triisopropanolamine (TIPA) and 13.5 g of 50% aqueous hypophosphorous acid were added and the mixture was heated to 230 ⁰ C. At about 220 ⁰ C slowly began the formation of condensate. The reaction mixture was stirred at 230 ^° C. for the time indicated in Table 1, the condensate formed in the reaction being removed by means of a moderate stream of nitrogen as stripping gas via the distillation bridge. Towards the end of the stated reaction time, residual condensate was removed at a reduced pressure of 500 mbar. After the time indicated in Table 1, the batch was cooled to 140 ° C and the pressure slowly and gradually reduced to lOOmbar to remove remaining volatiles.

The product mixture was then cooled to room temperature and analyzed.

Analysis of the products according to the invention:

The polyetheramine polyols were analyzed by gel permeation chromatography with a refractometer as detector. The mobile phase was hexafluoroisopropanol (HFIP) was used as the standard for determining the molecular weight polymethyl methacrylate (PMMA) was used.

The OH number was determined in accordance with DIN 53240, Part 2.

Table 1: Starting materials and end products

Component C / 2:

Glass fibers with an average thickness of 10 microns.

Component C / 3:

Paraloid® BLX 3670 from Rohm and Haas

(Core of butadiene / styrene, shell of methyl methacrylate)

Component C / 4:

Irgofos® 168 from Ciba Spez. GmbH

Production of molding compounds

The components A) to C) were mixed on a twin-screw extruder at 250 to 260 ⁰ C and extruded in a water bath. After granulation and drying, specimens were sprayed and tested on an injection molding machine.

The MVR was determined according to ISO 1 133, at 250 ° C / 2.16 kg load,

the VZ according to ISO 1628-1, 5;

Charpy Impact notched according to ISO 179-2 / 1 eA at 23 ° C; unnotched at -30 ⁰ C according to ISO 179-2 / 1 eU

Tensile properties according to ISO 527-2.

Modulus of elasticity according to ISO 527-2

The results of the measurements and the compositions of the molding compositions are shown in Tables 2 to 4.

Table 2

Table 3

Claims

claims

1. Thermoplastic molding compositions containing

A) 10 to 99% by weight of at least one thermoplastic polyester,

B) 0.01 to 30% by weight of at least one highly branched or hyperbranched polyetheramine,

C) 0 to 60% by weight of other additives,

wherein the sum of the weight percentages of components A) to C) is 100%.

2. Thermoplastic molding compositions according to claim 1, wherein the component B) has a glass transition temperature of less than 50 ⁰ C.

3. Thermoplastic molding compositions according to claims 1 or 2, wherein component B) has an OH number of 100 to 900 mg KOH / g.

4. Thermoplastic molding compositions according to claims 1 to 3, wherein component B) is a highly functional polyetheramine.

5. Thermoplastic molding compositions according to claims 1 to 4, wherein the component B) has on average at least 3 further functional OH groups, in addition to the ether and the amino groups which form the polymer backbone.

6. Thermoplastic molding compositions according to claims 1 to 5, wherein component B) is obtainable by reacting at least one trialkanolamine with optionally dialkanolamines or optionally with di- or higher functional polyetherols.

7. Thermoplastic molding compositions according to claims 1 to 6, in which component B) is obtainable by intermolecular polycondensation of at least one trialkanolamine of the general formula

in which the radicals R to R independently of one another are identical or different alkylene groups having 2 to 10 C atoms.

8. Thermoplastic molding compositions according to claims 1 to 7, in which component A) is composed of a mixture of an aromatic polyester and a polyester based on aliphatic and aromatic dicarboxylic acids and an aliphatic dihydroxy compound.

9. Use of highly branched or hyperbranched polyetheramines B) to improve the flowability of polyesters A).

10. Use of the thermoplastic molding compositions according to claims 1 to 8 for the production of fibers, films and moldings of any kind.

1 1. Fibers, films and moldings, obtainable from the thermoplastic moldings according to claims 1 to 8.