WO2012163822A1 - Polyester with styrene copolymers - Google Patents

Polyester with styrene copolymers Download PDF

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WO2012163822A1
WO2012163822A1 PCT/EP2012/059823 EP2012059823W WO2012163822A1 WO 2012163822 A1 WO2012163822 A1 WO 2012163822A1 EP 2012059823 W EP2012059823 W EP 2012059823W WO 2012163822 A1 WO2012163822 A1 WO 2012163822A1
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molding compositions
component
thermoplastic molding
compositions according
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PCT/EP2012/059823
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German (de)
French (fr)
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Martin Weber
Peter Eibeck
Nok-Young Choi
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Basf Se
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • C08L25/12Copolymers of styrene with unsaturated nitriles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Abstract

The invention relates to thermoplastic moulding materials which contain: A) between 2 and 98.5 wt.% of at least one polyester; B) between 0 and 70 wt.% of at least one polycarbonate; C) between 1 and 97.5 wt.% of a copolymerisate consisting of c1) 60 to 95 wt.% of styrene or substituted styrenes of general formula (I) or mixtures thereof, R representing an alkyl group comprising between 1 and 8 C atoms or a hydrogen atom, R1 representing an alkyl group comprising between 1 and 8 C atoms, and n being the value 1, 2 or 3, and c2) 5 to 40 wt.% of at least one unsaturated nitrile; D) between 0.5 and 30 wt.% of a copolymer that consists of d1) 49.5 to 93.5 wt.% structural units derived from one or more vinyl-aromatic monomers, d2) 6 to 50 wt.% structural units derived from one or more vinyl cyanides, d3) 0.5 to 2.4 wt.% structural units derived from one or more dicarboxylic acid hydrides, and d4) 0 to 25 wt.% structural units derived from additional copolymerisable monomers, each of these weight per cents relating to the total weight of the structural units derived from components d1, d2, d3 and d4, and together producing 100 wt.%; E) between 0 and 50 wt.% of a diene-free rubber; and F) between 0 and 60 wt.% of additional additives, the sum of the weight per cents A) to F) equalling 100%.

Description

Polyester with styrene

The invention relates to thermoplastic molding materials containing

A) from 2 to 98.5 wt .-% of at least one polyester

B) 0 to 70 wt .-% of at least one polycarbonate

C) from 1 to 97.5 wt .-% of a copolymer of

Ci) of 60 to 95 wt .-% of styrene or substituted styrenes of the general formula I or mixtures thereof

Figure imgf000003_0001
wherein R is an alkyl group having 1 to 8 carbon atoms or a hydrogen atom and R 1 is alkyl of 1 to 8 carbon atoms and n is 1, 2 or 3 and

C2) 5 to 40 wt .-% of at least one unsaturated nitrile,

D) from 0.5 to 30 wt .-% of a copolymer of di) 49.5 to 93.5 wt .-% which derives from one or more vinyl aromatic monomer structural units, d2) of 6 to 50 wt .-% or from a more vinyl cyanides dissipating structural units,

0.5 to 2.4 wt .-% which derives from one or more dicarboxylic moieties, and

0 to 25 wt .-% which derives from other copolymerizable monomers structural units, wherein the wt .-% are each based on the total weight of the derived from the components di, d2, d3 and d4 structural units and the total is 100 wt .-% , e) 0 to 50 wt .-% of a rubber which contains no diene,

F) 0 to 60 wt .-% other additives, where the sum of the weight percentages A) to F) is 100%.

Furthermore, the invention relates to the use of the thermoplastic molding compositions for producing fibers, films and moldings and also fibers, films and moldings, which are obtainable from the novel thermoplastic molding compositions.

Polymer blends are attracting increasing interest in art because they offer customized combinations of properties. this polymer mixtures of incompatible polymers, the unusual combination of properties have of particular interest. Polymer mixtures based on polyesters and styrene copolymers have long been known (DE 33 36 499, US 4,485,212, EP 135 677). However, because of the incompatibility between polyesters and styrene copolymers these products have inadequate mechanical properties.

Therefore, different approaches have been discussed in the literature to improve the compatibility of the phases, in particular functionalized styrene copolymers (EP 284 086, US 4,902,749, US 5,310,793, Lee P. C., Kuo W.-F., Chang F.-C , polymer 1994, 35, 5641,) and reactive acrylated latcopolymere (EP 573,680, US 4,352,904, E. Hage, sharks W., Keskkula, Paul DR polymer, 1997, 38, 3237 are used). The subject of DE 37 33 829 are glass fiber reinforced molding compositions based on polyesters and styrene copolymers in which styrene-acrylonitrile-maleic anhydride terpolymers be used to improve the compatibility. The improvement in mechanical properties is offset by a significant deterioration in the processing stability.

The US 2010/0152359 A1 describes blends of polyesters, styrene copolymers and graft copolymers, wherein a recycled material is used as polyester. The products in question have improved chemical resistance. Fiber-reinforced products are not mentioned.

Subject of DE 10 2009 055 403 are molding compositions based on polyesters, butadiene-containing Stryolcopolymeren and reactive styrene copolymers as compatibilizers. It is an object of the present invention to provide blends of polyester with SAN and optionally rubbers available which have good mechanical properties, especially toughness, good long-term use stability and a high processing stability, especially at the required for fiber-reinforced molding material mixture temperatures.

Accordingly, the molding compositions defined were found. Preferred embodiments are disclosed in the dependent claims.

As component (A), the molding compositions of the invention from 2 to 98.5, preferably from 20 to 97.5 preferably 20 to 80 wt .-% of at least one thermoplastic

Polyester.

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

Such polyalkylene terephthalates are known per se and described in the literature.

They contain an aromatic ring in the main chain of the aromatic from the

Dicarboxylic acid is derived. The aromatic ring may also be substituted, for example by halogen such as chlorine and bromine, or by Ci-C4-alkyl groups such as methyl, ethyl, 25 i- or n-propyl and n-, i- and t-butyl groups.

These polyalkylene terephthalates may be prepared by reacting aromatic dicarboxylic acids, their esters or other derivatives thereof with aliphatic dihydroxy compounds in esterbildenden be prepared in a known manner.

Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures of these. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids may be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic 35 and cyclohexanedicarboxylic acids.

Among the aliphatic dihydroxy compounds is given to 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 of these.

Particularly preferred polyesters (A) are polyalkylene terephthalates which derive from alkanediols having 2 to 6 carbon atoms, to call. Of these, Polyethylente- be terephthalate, polypropylene terephthalate and polybutylene terephthalate, or mixtures thereof. 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 intrinsic viscosity of the polyester (A) is generally in the range of 50 to 220, as preference from 80 to 160 (measured in a 0.5 wt .-% solution in a phenol / o-dichlorobenzene mixture (weight Verh. 1: 1 at 25 ° C) according to ISO 1628th

Particularly preferred are polyester whose carboxyl end group up to 100 meq / kg, preferably up to 50 meq / kg and especially up to 40 meq / kg of polyester. Such polyesters can be prepared, for example, by the process of DE-A 44 01 055th The carboxyl end group content is usually determined by titration (Z.8. Potentiometry).

Particularly preferred molding materials contain, as component A) a mixture of poly-esters, which are different from PBT, such as polyethylene terephthalate (PET). The proportion of the polyethylene terephthalate is preferably in the mixture up to 50, more preferably 1, 0 to 35 wt .-%, based on 100 wt .-% A).

Furthermore, it is advantageous to use recycled PET materials (also named scrap PET), optionally in micro research with polyalkylene terephthalates such as PBT use.

Recycled materials are generally:

1) known as post industrial recycled materials. This is production wastes during the polycondensation or during processing, such as sprues from injection molding, start up material from injection molding or extrusion or edge trims from extruder sheets or films-founded.

2) post-consumer recycled materials: these are plastic items which are collected by the end user and processes the wetting of the tongue. The quantitatively dominant by far items are blow-molded PET bottles for mineral water, soft drinks and juices.

Both types of recycled material may be used either as ground material or in the form of granules. In the latter case, the crude recycled materials are melted after the separation and purification in an extruder and granulated. This allows the handling and free flow, and metering for further processing steps usually facilitates.

Either pelletized or present as recycled material to be ground can be employed, wherein the edge length should be 10 mm, preferably less than 8 mm. Due to the hydrolytic cleavage of polyesters during processing (due to traces of moisture) it is advisable to pre-dry the recycled material. The residual moisture content after drying is preferably <0.2%, in particular <0.05%. A further group of fully aromatic polyesters may be mentioned, the carboxylic acids from aromatic di- and derived aromatic dihydroxy compounds.

Aromatic dicarboxylic acids are the compounds previously mentioned for the polyalkylene terephthalates. Mixtures of from 5 to 100 mol% of isophthalic acid and from 0 to 95 mol% of terephthalic acid, particularly mixtures of terephthalic acid with about 80% 20% isophthalic acid are preferably used up to approximately equivalent mixtures of these two acids.

The aromatic dihydroxy compounds preferably have the general formula

Figure imgf000007_0001
in which Z represents an alkylene or cycloalkylene group having up to 8 carbon atoms, an arylene group having up to 12 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in which m is 0 to 2 has. can carry as substituents on the phenylene connects fertilize and Ci-C6 alkyl or alkoxy groups and fluorine, chlorine or bromine.

Of parent compounds for these compounds, for example, dihydroxydiphenyl,

Di (hydroxyphenyl) alkane,

Di (hydroxyphenyl) cycloalkane,

Di (hydroxyphenyl) sulfide,

Di (hydroxyphenyl) ether,

ketone di- (hydroxyphenyl),

di- (hydroxyphenyl) sulfoxide,

a, a'-di- (hydroxyphenyl) -dialkylbenzol,

Di (hydroxyphenyl) sulfone, di- (hydroxybenzoyl) benzene, resorcinol and hydroquinone, as well as their nuclear-alkylated or nuclear halogenated derivatives of these. Of these

4,4'-dihydroxydiphenyl,

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

a, a'-di- (4-hydroxyphenyl) -p-diisopropylbenzene,

2,2-di- (3'-methyl-4'-hydroxyphenyl) propane, and

2,2-di- (3'-chloro-4'-hydroxyphenyl) propane, and especially

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

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

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

3,4'-dihydroxybenzophenone,

4,4'-dihydroxydiphenyl sulfone and

2.2- di (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane or mixtures thereof. Of course, to use mixtures of polyalkylene terephthalates and fully aromatic polyesters. These generally comprise from 20 to 98 wt .-% of polyalkylene terephthalate and 2 to 80 wt .-% of the wholly aromatic polyester.

Of course, polyester block as copolyetheresters can be used. Such products are known per se and in the literature, described for example in US-A 3651 014. Also commercially relevant products are available, for example Hytrel® (DuPont).

As component B) include halogen-free polycarbonates can be used according to the invention advertising the in amounts of from 0 to 70, preferably up to 60 wt .-%. Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula

Figure imgf000008_0001
wherein Q is a single bond, d- to Cs-alkylene, a C2-C3 alkylidene, a C3 to C6 cycloalkylidene, a C6- to Ci2-arylene group and -O-, -S- or -SO2- and m is a whole number from 0 to second The diphenols may on the phenylene radicals also have substituents such as Ci - C6 alkyl or Ci - to C6-alkoxy.

Preferred diphenols of the above formula are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -

2methylbutan, 1, 1-bis (4-hydroxyphenyl) -cyclohexane. Particularly preferred are 2,2-bis (4-hydroxyphenyl) -propane and 1, 1-bis (4-hydroxyphenyl) -cyclohexane and 1, 1 -bis- (4- hydroxyphenyl) -3,3,5-trimethylcyclohexane , Both homopolycarbonates and copolycarbonates are suitable as component B, are preferred in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A

The suitable polycarbonates may be branched in a known manner, preferably by incorporation of 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those with three or more than three phenolic OH groups.

Particularly suitable polycarbonates have been found to have relative viscosities η Γθ ι νοη 1, 10 to 1 50, especially from 1 having 25-1, 40th This corresponds to average molecular weights M w (weight-average) from 10,000 to 200,000, preferably 20,000 to 80,000 g / mol.

The diphenols of the general formula are known per se or can be prepared by known methods.

The preparation of the polycarbonates can take place (the so-called pyridine process), for example, by reacting the diphenols with phosgene by the phase boundary method or with phosgene by the homogeneous phase process, wherein the molecular weight to be established is obtained in known manner by an appropriate amount of known chain terminators. (Regarding polydiorganosiloxane-containing polycarbonates see, for example DE-OS 33 34 782).

Suitable chain terminators are, for example, phenol, pt-butylphenol, but also long-chain alkylphenols, such as 4- (1, 3-tetramethyl-butyl) -phenol according to DE-OS 28 42 005 or alkylphenols Monoa- ​​or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents, according to DE-A 3506472, such as p-nonylphenyl, 3,5-di-t-butylphenol, pt-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- (3, 5-dimethylheptyl) -phenol.

A halogen-free polycarbonates for the purposes of the present invention means that the polycarbonates obtained from halogen-free diphenols, halogen-free chain terminators and, optionally halogen-free branching agents, the content of minor ppm amounts of hydrolyzable chlorine, resulting, for example, from the preparation of the polycarbonates with phosgene by the interfacial process, is not to be considered as halogens in the context of the invention. Such polycarbonates containing ppm levels of hydrolyzable chlorine are halogen-free polycarbonates for the purposes of the present invention. Other suitable components A) may be mentioned amorphous polyester, said phosgene acid units, aromatic dicarboxylic acid such as isophthalic acid and / or terephthalic acid has been replaced in the preparation. Further details may be made at this point to EP-A 71 1810.

Further suitable copolycarbonates having cycloalkyl radicals as monomer

EP-A 365 916..

Furthermore, bisphenol A may be replaced by bisphenol TMC. Polycarbonates of this are obtainable from Bayer with the trademark APEC HT®.

As component C), the molding compositions of the invention from 1 to 97.5, preferably from 1 to 80 and especially 1 to 20 wt .-% of a copolymer of

60 to 95, preferably 70 to 85 wt .-% of styrene or substituted styrenes of the general formula I or mixtures thereof

CK

Figure imgf000010_0001
wherein R is an alkyl group having 1 to 8 carbon atoms or a hydrogen atom and R 1 is alkyl of 1 to 8 carbon atoms and n is 1, 2 or 3 and

C2) 5 to 40, preferably 15 to 30 wt .-% of at least one unsaturated nitrile.

Preferred radicals R are methyl, ethyl or hydrogen, and

Preferred radicals R 1 are methyl, ethyl.

Preferred components C1) are styrene or α-methyl styrene or mixtures thereof.

Preferred components C2) are acrylonitrile or methacrylonitrile or mixtures thereof.

The copolymers C are resin-like, thermoplastic and rubber-free. C Particularly preferred copolymers are those of styrene and acrylonitrile, of α-methyl styrene and acrylonitrile or from styrene, α-methyl styrene and acrylonitrile. Also, several of the copoly- mers described are used simultaneously. The Copolimerisate C are known per se and can be prepared by radical polymerization, in particular by emulsion, suspension, solution and bulk polymerization. They have viscosity numbers in the range from 40 to 160, corresponding to average molecular weights Mw (weight average) from 40,000 to 2,000,000.

As component D) The novel molding materials contain from 0.5 to 30, preferably 1 to 20 and especially 1 to 10 wt .-% (based on A to F) of a copolymer of di) 49.5 to 93.5 wt .-% from one or more vinyl aromatic monomers off conductive structural units,

d2) of 6 to 50 wt .-% which derives from one or more vinyl cyanides structural units,

Ö3) from 0.5 to 2.4 wt .-% which derives from one or more dicarboxylic moieties, and

d 4) from 0 to 25 wt .-% which derives from other copolymerizable monomers structural units, wherein the wt .-% in each case on the total weight of itself), and d 4) structural units derived are obtained from the components di), d2), DSS and together 100 wt .-% yield.

Preferred components D

Figure imgf000011_0001

d 2) 6 to 50 wt .-%

d 3) 0.8 to 2.2 wt .-%

d 4) from 0 to 25 wt .-%.

As a component di) are all known to the expert and described in the prior art, for example DE 100 58 302 A1 vinyl aromatic monomers into consideration; Styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, vinyl naphthalene or mixtures thereof are preferably used; particularly preferably styrene is used.

As component 2) are all known to the expert and in the state of the art, described, for example, vinyl cyanides DE 25 40 517 A1 into consideration; Acrylonitrile, methacrylonitrile or mixtures thereof are preferably used; more preferably acrylic acid nitrile is used.

As component DSS) are all known to the expert and described in the prior art dicarboxylic into consideration; Maleic anhydride, methylmaleic anhydride, itaconic anhydride or mixtures thereof are preferably used; particularly preferably maleic anhydride is employed. As component d 4) of the copolymers D) according to the invention can further be used with the components di), d2) and 3) copolymerizable and of these various monomers which are familiar to the expert. Particularly preferably constructed the copolymers D) of styrene-acrylonitrile-maleic anhydride copolymers are described.

The preparation of the copolymers D) is carried out by bulk or solution polymerization, but preferably as a solution in the presence of an organic solvent, examples game, cyclohexane, ethylbenzene, toluene or dimethyl sulfoxide, preferably ethylbenzene.

Both in the solution as well as in the bulk polymerization, the initiation of the polymerization can be effected by addition of chemical polymerization initiators in principle as described for example in DE 100 58 302 A1; preferably the initiation takes place by means of heat but, without addition of a polymerization initiator. The preparation can be carried out in a batch or semi-batch process, however, a continuous process is preferably carried out.

In a particularly preferred embodiment of the method according to the invention the process management is carried out continuously under steady-state conditions; under steady state conditions means that the concentrations of all reactants and composition of the copolymers A) formed remain over the duration of the reaction is practically constant (data on the relationship between monomer and polymer composition as well as the stationary reaction may in particular EP 0001625 A1 and

be taken from DE 25 40 517 A1).

Suitable process parameters such as pressure, temperature, residence times etc., apparatus suitable for carrying out the method as well as suitable amount of current dosages of the monomers, if any of the solvents, if any of the initiators and optionally further polymerization are tion additives known in the art and described in the prior art ,

The work-up of the polymerization and the isolation of the copolymers D), according to known in the art and methods described in the art take place, for example, by separation of low molecular compounds by application of vacuum, or stripping with inert gas.

Preferred components D) have a difference of nitrile content of less than 10 wt .-% to the nitrile content of the component C). One or a mixture of different graft copolymers are used as component E) in the inventive molding compositions in amounts of 0 to 50 wt .-%, based on the sum of components A to F,. Preferred molding compositions according to the invention contained ten of 1 to 40, more preferably from 1 to 20 wt .-% of at least one Pfropfcopolyme- risates E.

The graft polymers E are composed of

40 to 80 wt .-%, preferably 50 to 70 wt .-% of a grafting base comprising an elastomeric polymer based on alkyl acrylates having from 1 to 8 carbon atoms in the alkyl moiety and having a glass transition temperature of below 0 ° C E2) 20 to 60 wt .-%, preferably 30 to 50 wt .-% of a graft layer comprising

E21) 60 to 95 wt .-%, preferably 70 to 85 wt .-% of styrene or substituted styrenes of the formula I E22) 5 to 40 wt .-%, preferably 15 to 30 wt .-% of at least one unsaturated nitrile, preferably acrylonitrile or methacrylonitrile or mixtures thereof.

For the graft egg polymers come into consideration, whose glass transition temperature below 10 ° C, preferably below 0 ° C, more preferably below -20 ° C. These are elastomers based on C1-C8-alkyl esters of acrylic acid, which may contain further comonomers, if appropriate.

Preferred backbones are egg, which are constructed from E11) 69.9 to 99.9 wt .-%, preferably 99 wt .-% of at least one alkyl acrylate having 1 to 8 carbon atoms in the alkyl radical, preferably n-butyl acrylate and / or 2 ethyl hexyl acrylate, in particular n-butyl acrylate as sole alkyl acrylate

E12) 0 to 30 wt .-%, in particular 20 to 30 wt .-% of a further copolymerizable monoethylenically unsaturated monomers such as styrene, acrylonitrile, methyl methacrylate or vinyl methyl ether or mixtures thereof

E13) 0.1 to 5 wt .-%, preferably 1 to 4 wt .-% of a copolymerizable, polyfunctional, preferably bi- or tri-functional, which effects crosslinking monomers.

bi- or polyfunctional crosslinking E13) are monomers which preferably contain two, if necessary also three or more, capable of copolymerization ethylene lenische double bonds which are not conjugated in the 1, 3 positions. Suitable crosslinking monomers are for example divinylbenzene, diallyl maleate, diallyl fumarate, diallyl lylphthalat, triallyl or triallyl. A particularly advantageous Vernetzungsmo- nomeres the acrylate tricyclodecenyl (DE-A 12 60 135, see.) Has proved.

This type of graft is known per se and described in the literature, for example in DE-A 31 49 358th

Of the graft E2, preferred are those in which R E21 styrene or a-methylstyrene or mixtures thereof and acrylonitrile or methacrylonitrile are at E22. As preferred monomer mixtures are styrene and acrylonitrile or α-methylstyrene and acrylonitrile. The grafts are obtainable by copolymerization of the component E21 and E 22nd

The graft egg of the graft polymers E) which is constructed from the components En, where appropriate, E12, and E13 is also referred to as an ASA rubber. The preparation is known per se and, for example, in DE-A 28 26 925, DE-A 31 49 358 and

DE-A 3414 1 18.

The preparation of the graft polymers E can be carried out, for example, by the method described in DE-PS 12 60 135 method. The construction of the graft (graft shell) of the graft polymers can be one or two stages.

In the case of single-stage construction of the graft shell, a mixture of the monomers is E21 and E22 in the desired weight ratio in the range 95: 5 to 50:50, preferably from 90:10 to 65:35 in the presence of the elastomer egg, in a manner known manner (see. for example, DE-OS 28 26 925), preferably in emulsion polymerization.

In case of a two-stage synthesis of the graft shell E2 stage 1 will generally comprise 20 to 70 wt .-%, preferably 25 to 50 wt .-%, based on E2, from. For their preparation, only styrene or substituted styrenes or mixtures thereof (E21) are preferably used.

The 2nd stage of the graft shell generally accounts for from 30 to 80 wt .-%, in particular 50 to 75 wt .-%, each based on E2, from. For their preparation are mixtures of the monomers E21 and E22 nitriles in a weight ratio E21 / E22 of generally 90:10 to 60:40, in particular 80:20 to 70:30 applied.

The conditions of the graft polymerization are preferably chosen so that particle sizes from 50 to 700 nm result (d50 value of the integral mass distribution). Measures are known and are described for example in DE-OS 2,826,925th By the seed latex method, a coarse rubber dispersion can be prepared directly.

To obtain very tough products, it is often advantageous to use a mixture of at least two graft polymers with different particle sizes.

To achieve this, the particles of the rubber are prepared in known manner, for example by agglomeration, so that the latex bimodal (50 to 180 nm and 200 to 700 nm) is established.

In a preferred embodiment, a mixture of two graft polymers having particle diameters (d50 value of the integral mass distribution) of 50 to 180 nm and 200 to 700 nm is used in the weight ratio 70:30 to 30:70. The chemical composition of the two graft polymers is preferably the same although the shell of the coarse-particle graft polymer can be constructed in two stages in particular.

As component E) also ethylene copolymers, ethylene-propylene copolymers, polyester elastomers or thermoplastic polyurethanes can be used.

More generally, these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, isobutene, chloroprene, Vinylace- did styrene, acrylonitrile and acrylic or methacrylic acid ester having 1 to 18 carbon atoms in the alcohol - component.

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

As component F) The novel molding compositions may contain from 0 to 60, especially up to 50% by weight of other additives.

As component F) The novel molding compositions may contain from 0 to 5, preferably 0.05 to 3 and in particular 0.1 to 2 wt .-% of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids having from 10 to 40, preferably 16 to 22 carbon atoms contained with a- liphatischen saturated alcohols or amines having from 2 to 40, preferably 2 to 6 carbon atoms.

The carboxylic acids may 1 - or 2-valued. Examples include pelargonic, palmitic acid called lauric acid, margaric acid, behenic acid and particularly preferably stearic acid, capric acid, acid (a mixture of fatty acids having 30 to 40 carbon atoms). The aliphatic alcohols may be 1 - Trivalent 4 to. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, and glycerol and pentaerythritol are preferred. The aliphatic amines may be 1 - to 3-valent. Examples are stearyl amine, ethylenediamine, propylenediamine, hexamethylenediamine, di amine (6-aminohexyl), wherein ethylene diamine and hexamethylene diamine are particularly preferred. Preferred esters or amides are correspondingly glycerol, glycerol tristearate, ethylenediamine, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.

It can be used in combination with amides, mixtures of different esters or amides or esters, wherein the mixing ratio is arbitrary.

As a fibrous or particulate fillers F) carbon fibers, glass fibers, glass beads, amorphous silica, asbestos, calcium silicate, calcium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, and feldspar may be mentioned that in amounts up to 60 wt .-% , in particular up to 50% are used.

Preferred fibrous fillers carbon fibers, aramid fibers and Kaliumtita- nat fibers may be mentioned, wherein glass fibers are particularly preferred as E-glass. These can be used as rovings or chopped glass in the commercially available forms.

The fibrous fillers may be pretreated to improve compatibility with the thermoplastic with a silane compound superficial.

Suitable silane compounds have the general formula

(X- (CH 2) n) kS i (0-C m H 2m + 1) 4-k where the substituents have the following meanings:

X is NH 2 -, CH-CH-, HO-,

\ /

O 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, as substituent X a glycidyl group. 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 F) for surface coating. Also suitable are needle-shaped mineral fillers.

Acicular mineral fillers are mineral fillers will be understood by strongly developed acicular character in the sense of the invention. An example is acicular wollastonite. 1 to 1: 1: 1 to 35: 1, preferably from 8 to 1 ratio of 8 - The mineral preferably has an L / D (length to diameter). The mineral filler can optionally be pre-treated with the aforementioned silane compounds; but the pretreatment is not essential.

Other fillers are kaolin, calcined kaolin, talc and chalk may be mentioned.

As component F thermoplastic molding compositions of the invention may include conventional processing aids such as stabilizers, agents against thermal decomposition and decomposition by ultraviolet light, lubricants, mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.. Examples of antioxidants and heat stabilizers are known as 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. UV stabilizers which are wt .-%, based on the molding composition, generally used in amounts of up to 2, are various substituted resorcinols, salicylates, benzotriazoles and benzophenones le.

As Umesterungsstabilisatoren be mentioned Irgafos® PEPQ and phosphates (eg Monozinkphos- phat).

Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, and organic pigments such as phthalocyanines, quinacridones, perylenes, and dyes such as nigrosine and anthraquinones may be added as a colorant.

As a nucleating agent sodium phenyl phosphinate, alumina, silica, and preferably talc may be employed.

Other lubricants and mold release agents are usually begins einge- in amounts up to 1 wt .-%. There are preferably long-chain fatty acids (eg stearic acid or behenic acid),

Salts (such as calcium stearate or zinc stearate) or montan waxes (mixtures of straight-th of saturated carboxylic acids having chain lengths of from 28 to 32 carbon atoms), as well as Ca or Na montanate, and low molecular weight polyethylene or polypropylene waxes.

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

The molding compositions may comprise from 0 to 2 wt .-% fluorine-containing Ethylenpolyme- risate. These are polymers of ethylene having a fluorine content from 55 to 76 wt .-%, preferably 70 to 76 wt .-%.

Examples include polytetrafluoroethylene (PTFE), Tetrafluorethylenhexafluorpropylen- copolymers or tetrafluoroethylene copolymers with minor amounts (generally up to 50 wt .-%) copolymerizable ethylenically unsaturated monomers. These are described, for example, by Schildknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952, page 484-494 and by Wall in "Fluoropolymers" (Wiley Interscience, 1972).

These fluorine-containing ethylene polymers are homogeneously distributed in the molding materials, and preferably have a particle size dso (number average) in the range of 0.05 to 1 μηη, in particular from 0.1 to 5 μηη on. These small particle sizes can be particularly forthcoming Trains t by the use of aqueous dispersions of fluorine containing ethylene polymers and their incorporation into a polyester melt.

The thermoplastic molding compositions of the invention can be prepared by processes known per se, in which the starting components in conventional Mischvorrichtun- one gene such as screw extruders, Brabender mixers or Banbury mixers, and then extruded. After extrusion, the extrudate can be cooled and comminuted. As well as individual components are premixed and then the remaining starting materials and / or likewise mixed. The mixing temperatures are generally from 230 to 290 ° C.

According to another preferred method, components C) and D) and optionally E) and / or F) may be mixed with a polyester prepolymer, compounded, and pelletized. The granulate obtained is then condensed in the solid phase under inert gas, continuously or batchwise at a temperature below the melting point of component A) to the desired viscosity.

The thermoplastic molding compositions are distinguished by a good workmanship and good thermal stability combined with good mechanical properties. In particular, the toughness is improved and processing stability at high temperatures.

These are suitable for the production of fibers, films and moldings of any type, in particular for applications as connectors, switches, housings, housing cover, Scheinwerferhin- tergrund (bezel), shower heads, faucets, iron, rotary switches, stove buttons, Friteusen- lids, door handles, ( rear) mirror housings, (tailgate) wipers, payments Lichtwellenleiterummante-. In the E / D area with the inventive polyesters plug, plug parts, connectors, cable harness components, circuit carrier, the circuit carrier components, three-dimensional molded interconnect devices, electrical connecting elements, mechatronic components or optoelectronic devices can be manufactured. In automobile interiors is a use for dashboards, steering column switch, seat parts, head rests, center consoles, gearbox components and door modules, possible in the car-exterior door handles, front headlight components, exterior mirror components, windshield wiper components wiper protective housing, grille, roof rails, roof frames and exterior bodywork parts.

is the use of polyesters for the production of components for domestic appliances for kitchen and household sector, such as fryers, irons, buttons, as well as applications in the garden and leisure sector, eg components possible for irrigation systems or garden equipment.

Examples

Component A:

Polybutylene terephthalate having a viscosity number VN of 130 ml / g and a Carboxylendgrup- pengehalt of 34 meq / kg (Ultradur B 4500, BASF SE) (VN measured in 0.5 wt .-% solution of phenol / o-dichlorobenzene, 1 : 1 blend at 25 ° C).

Component C / 1

SAN weight with a AN-content of 19.% And a viscosity number of 70 ml / g (measured in DMF, 0.5 wt .-% solution).

Component C / 2

SAN weight with a AN-content of 35.% And a viscosity number of 65 ml / g (measured in DMF, 0.5 wt .-% solution).

Component DA / 1

As component D / V1 a styrene-acrylonitrile-maleic anhydride terpolymer was used which had a composition of 75 / 24.6 / 0.4 (wt .-%), viscosity number: 66 ml / g. Component D / 1

As component D / 1 is a styrene-acrylonitrile-maleic anhydride terpolymer was used which had a composition of 74.5 / 24.5 / 1 0 (wt% .-), viscosity number: 66 ml / g.

Component D / 2

As component D / 2, a styrene-acrylonitrile-maleic anhydride terpolymer was used which had a composition of 74.1 / 23.9 / 2.0 (wt .-%), viscosity number: 67 ml / g.

Component DA / 2

As component D / V2 a styrene-acrylonitrile-maleic anhydride terpolymer was used which had a composition of 74 / 23.5 / 2.5 (wt .-%), viscosity number: 68 ml / g.

Preparation of graft copolymer E a) Preparation of polystyrene-core

700 g of water, 3.4 g of the sodium salt of a C12 to C18 paraffin sulfonic acid, 1, 75 g of potassium, 2.5 g of sodium hydrogen carbonate, 1 g sodium pyrophosphate and 50 g of a seed latex, polystyrene (solid content = 38.7%, d50 = 85 nm) were heated to 70 ° C. Subsequently, a mixture of 550 g of styrene, 1 1, 5 g of DCPA and 10 g of divinylbenzene was added over 2 hours.

After completion of the monomer emulsion was kept for one hour at 65 ° C. The polystyrene core had an average particle diameter d 50 of 250 nm. The emulsion had a solids content of 38.5%. b) Preparation of polybutylacrylate shell

To the obtained emulsion, 10 g of sodium salt of a C12 to C18 paraffin were sulfonic acid, 6.5 g of potassium peroxodisulfate, 5 g of sodium bicarbonate and 2 g of sodium pyrophosphate as well as 2490 g of water. At 65 ° C 1730 g of butyl acrylate and 35 g of DCPA was added within 3.5 h and then further stirred for 2 hours at 65 ° C. (D50 = 420 nm solid content = 38.6%). c) Preparation of the polystyrene / acrylonitrile graft shell

6070 g of the emulsion thus obtained were diluted with 2600 g water and 5 g of the sodium salt of a C12 to C18 paraffin sulfonic acid and 4.5 g of potassium peroxodisulfate were added. At 65 ° C a mixture of 790 g of styrene and 260 g of acrylonitrile was added dropwise within 2 h and another 2 h at 65 ° C. (D50 = 500 nm, solid content = 34.8%). The graft polymer E was precipitated by means of calcium chloride solution at 95 ° C from the emulsion, washed with water and dried in warm air stream.

component F

Glass fiber, which was equipped with an epoxy sizing, fiber diameter 10 μηη. Preparation and testing of the molding compositions for mixing the components was used, a twin-screw extruder, the melt temperature was 260 ° C. The melt was passed through a water bath and granulated.

Furthermore, the mechanical properties to manufactured by injection molding samples (. Melt temperature: 250 ° C / Werkzeugtemp 80 ° C) were determined.

The impact strength of the products was determined 179 1 eU on ISO specimens to ISO.

Tensile strength and elongation at break were determined to ISO 527th The thermal resistance of the products was characterized by storage of tensile specimens at 120 ° C / 500h in a circulating air cabinet and subsequent tensile tests. To assess the processing stability of the molding compositions were processed Melt temperature / 80 ° C mold temperature and at 300 ° C. The composition of the styrene copolymers used was determined by quantitative infrared spectroscopy.

The compositions of the molding compositions and the results of the tests are listed in Table 1 below.

Table 1:

No molding compound. V1 V2 V3 4 5 V6 V7

Component [wt .-%]

C / 1 10.7 to 6.7 6.7 6.7 6.7 -

C / 2-10.7 - - - - 6.7

A 58.2 58.2 58.2 58.2 58.2 58.2 58.2

DA / 1 - - 4 - - - -

D1 - - - 4 - - 4

D2 - - - - 4 - -

DA / 2 - - - - - 4 -

E 11.1 11.1 11.1 11.1 11.1 11.1 11.1

F 20 20 20 20 20 20 20 n a [kJ / m 2] 52.9 49.7 53.3 62.6 61.7 53.5 53.7

Tensile strength [N / mm 2] 103 99 104 114 114 110 104

Elongation at break [%] 2.7 2.6 2.7 3.1 3.0 2.9 2.5

Tear strength 100 97 102 113 112 101 100 500 h / 120 ° C [MPa]

a n processing at 42.3 40.4 41.4 58.7 56.7 37.4 45.3 300 ° C / 80 ° C [kJ / m 2]

Claims

claims
1 . Thermoplastic molding compositions containing
2 to 98.5 wt .-% of at least one polyester
0 to 70 wt .-% of at least one polycarbonate
1 to 97.5 wt .-% of a copolymer of
60 to 95 wt .-% of styrene or substituted styrenes of the general formula I or mixtures thereof
Figure imgf000023_0001
wherein R is an alkyl group having 1 to 8 carbon atoms or a hydrogen atom and R 1 is alkyl of 1 to 8 carbon atoms and n is 1, 2 or 3 and
5 to 40 wt .-% of at least one unsaturated nitrile,
D) from 0.5 to 30 wt .-% of a copolymer of
49.5 to 93.5 wt .-% which derives from one or more vinyl aromatic monomer structural units,
6 to 50 wt .-% which derives from one or more vinyl cyanides structural units,
0.5 to 2.4 wt .-% which derives from one or more dicarboxylic moieties, and
0 to 25 wt .-% which derives from other copolymerizable monomers structural units, wherein the wt .-% are each based on the total weight of the derived from the components di, d2, d3 and d4 structural units and the total is 100 wt .-% .
0 to 50 wt .-% of a rubber which contains no diene, F) O to 60 wt .-% other additives, where the sum of the weight percentages A) to F) is 100%.
Thermoplastic molding compositions according to claim 1, containing
10 to 97.5 wt .-%
0 to 60 wt .-%
1 to 97.5 wt .-%
0.5 to 30 wt .-%
1 to 40 wt .-%
0 to 60 wt .-%, wherein the sum of the weight percentages A) to F) is 100%.
Thermoplastic molding compositions according to claims 1 or 2, comprising constructed as component E) is a graft polymer of
Egg) 40 to 80 wt .-% of a grafting base comprising an elastomeric polymer based on alkyl acrylates having from 1 to 8 carbon atoms in the alkyl moiety and having a glass transition temperature of below 10 ° C,
E2) 20 to 60 wt .-% of a graft layer comprising
E21) 60 to 95 wt .-% of styrene or substituted styrenes of the general formula I or mixtures thereof,
E22) 5 to 40 wt .-% of at least one unsaturated nitrile.
Thermoplastic molding compositions according to claims 1 to 3, containing as component D a copolymer of
Figure imgf000024_0001
d 2) 6 to 50 wt .-%
d 3) 0.8 to 2.2 wt .-%
d 4) from 0 to 25 wt .-%
Thermoplastic molding compositions according to claims 1 to 4, wherein component D) is a terpolymer of di) of styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, vinyl naphthalene or a mixture of two or more of these monomers, component c) acrylonitrile, methacrylonitrile or a mixture of these monomers and
Component DSS) maleic anhydride, methylmaleic anhydride, itaconic anhydride or mixture of two or more of these monomers.
6. Thermoplastic molding compositions according to claims 1 to 5, in which the copolymer D) is a styrene-acrylonitrile-maleic anhydride copolymer.
7. Thermoplastic molding compositions according to claims 1 to 6, in which component D) is obtainable by bulk or solution polymerization.
8. Thermoplastic molding compositions according to claims 1 to 7, wherein component D) by thermal polymerization without the addition of a polymerization initiator is prepared.
9. Thermoplastic molding compositions according to claims 1 to 8, wherein the difference of the nitrile content of the components C) and D) is less than 10 wt .-%.
10. Use of the thermoplastic molding compositions according to claims 1 to 9 for producing fibers, films and moldings of any type.
1. 1 Molded bodies of any kind, fibers and foils obtainable from the thermoplastic molding compositions according to claims 1 to 9.
PCT/EP2012/059823 2011-06-01 2012-05-25 Polyester with styrene copolymers WO2012163822A1 (en)

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