Title of Invention	"HOMOGENEOUS PROCESS FOR THE HYDROGENATION OF DICARBOXYLIC ACIDS AND/OR ANHYDRIDES THEREOF"
Abstract	A homogeneous process for the hydrogenation of dicarboxylic acids and/or anhydrides in the presence of a catalyst comprising: (a) ruthenium, rhodium, iron, osmium or palladium; and (b) an organic phosphine of the kind such as herein described; wherein the hydrogenation is carried out in the presence of at least 1% by weight water and wherein the reaction is carried out at a pressure of from 500 psig to 2000 psig and a temperature of from 200°C to 300°C such that from 1 mol to 10 mol of hydrogen are used to strip 1 mole of product from the reactor.

Title of Invention

"HOMOGENEOUS PROCESS FOR THE HYDROGENATION OF DICARBOXYLIC ACIDS AND/OR ANHYDRIDES THEREOF"

Abstract

A homogeneous process for the hydrogenation of dicarboxylic acids and/or anhydrides in the presence of a catalyst comprising: (a) ruthenium, rhodium, iron, osmium or palladium; and (b) an organic phosphine of the kind such as herein described; wherein the hydrogenation is carried out in the presence of at least 1% by weight water and wherein the reaction is carried out at a pressure of from 500 psig to 2000 psig and a temperature of from 200°C to 300°C such that from 1 mol to 10 mol of hydrogen are used to strip 1 mole of product from the reactor.

Full Text	Moulding compositions based on a thermoplastic polyester with improved flowabilitv This invention relates to moulding compositions based on a thermoplastic polyester and on at least one copolymer composed of at least one a-olefin with at least one methacrylic ester or acrylic ester of an aliphatic alcohol having from 1 to 4 carbon atoms, the MFI (Melt Flow Index) of the copolymer being not less than 50g/10min, to a process for preparation of these moulding compositions, and also the use of these moulding compositions for production of mouldings for the electrical, electronics, telecommunications, motor vehicle or computer industry, in sports, in the household, in medicine or for the entertainment industry. Highly flowable thermoplastic compositions are of interest for a wide variety of injection moulding applications. By way of example, thin-walled components in the electrical, electronics and motor vehicle industry require low viscosities from the thermoplastics composition in order to permit material to be charged to the mould with minimum injection pressures and, respectively, clamping forces in the appropriate injection moulding machines. This also applies to simultaneous charging of material to two or more injection moulding components by way of a shared runner system in what are known as multicavity tooling systems. Shorter cycle times can moreover often be achieved using low-viscosity thermoplastic compositions. Good flowabilities are also specifically very important for highly filled thermoplastic compositions, e.g. with glassfibre and/or mineral contents above 40% by weight. However, although the thermoplastic compositions have high flowability, the actual components produced therefrom are subjected to stringent mechanical requirements, and the lowering of viscosity cannot therefore be permitted to cause any significant impairment of mechanical properties. Indeed, because of the structure of the components to be produced, the requirements placed upon mechanical properties such as impact resistance or outer fibre strain, are increasingly often more stringent than for standard thermoplastics. There are a number of ways of obtaining highly flowable, low-viscosity thermoplastic moulding compositions. One way uses low-viscosity polymer resins with very low molecular weight as base polymers for the thermoplastic moulding compositions. However, the use of low-molecular-weight polymer resins is often associated with sacrifices in mechanical properties, in particular toughness. Preparation of a low-viscosity polymer resin in an existing polymerization plant moreover often requires complicated intervention attended by capital expenditure. Another way uses what are known as flow aids, also termed flow agents or flow assistants or internal lubricants, which can be added as an additive to the polymer resin. These flow aids are known from the literature, e.g. in Kunststoffe 2000, 90 (9), p. 116-118, and by way of example can be fatty acid esters of polyols, or amides derived from fatty acids and from amines. However, these fatty acid esters, such as pentaerythritol tetrastearate or ethylene glycol dimontanoate, have only limited miscibility with polar thermoplastics, such as polyamides, polyalkylene terephthalates or polycarbonates. Their concentration increases at the surface of the moulding and they are therefore also used as mould-release aids. Particularly at relatively high concentrations, they can also migrate out of these mouldings to the surface on heat-ageing and become concentrated at the surface. By way of example, in coated mouldings this can lead to problems with regard to adhesion to paint or to metal. As an alternative to the surface-active flow aids, it is possible to use internal flow aids which are compatible with the polymer resins. Examples of those suitable for this purpose are low-molecular-weight compounds or branched, highly branched or dendritic polymers whose polarity is similar to that of the polymer resin. These highly branched or dendritic systems are known from the literature and their basis can by way of example be branched polyesters, polyamides, polyesteramides, polyethers or polyamines, as described in Kunststoffe 2001, 91 (10), pp. 179-190, or in Advances in Polymer Science 1999, 143 (Branched Polymers II), pp. 1-34. EP 0 682 057 Al describes the use of the nitrogen-containing first-generation 4-cascade dendrimer: l,4-diaminobutane[4]propylamine (N,N'-tetrabis(3-ammopropyl)-l,4-butanediarnine) DAB(PA)4 to lower viscosity in nylon-6, nylon-6,6 and polybutylene terephthalate. While use of DAB(PA)4 to lower viscosity in polyamides has practically no effect on the impact resistance of the resultant moulding compositions (difference WO-A 98 27159 describes an improvement in toughness of glassfibre-reinforced polyesters or polycarbonates via use of two copolymers composed of ethene and of acrylates, one copolymer also bearing a reactive epoxy or oxirane function. Flow improvement in the moulding compositions is an object of the invention, but the comparison system described composed of polyester and of the copolymer composed of ethene and methylacrylate has higher melt viscosity than the pure polyester system. JP 01247454 describes mixtures which have low-temperature toughness, of polyesters with a copolymer composed of ethene and of an unreactive alkyl acrylate whose MFI is 5.8 g / 10 min (at 190°C, 2.16 kg) and with a copolymer composed of ethene and of an acrylate having an additional reactive group. The subject of that application is not flow improvement in moulding compositions. EP-A 1 191 067 (= US 6 759 480) describes the impact modification of thermoplastics, inter alia of polyamide and polybutylene terephthalate via a mixture composed of a copolymer composed of ethene with an unreactive alkyl acrylate, and also of a copolymer composed of ethene with an acrylate having an additional reactive group. There is no discussion of the flowability of the moulding composition. EP-A 0 838 501 (= US 6 020 414) describes mixtures having low-temperature toughness of reinforcing materials and polyesters with a copolymer composed of ethene and of an unreactive alkyl acrylate, and also with a copolymer composed of ethene and of an acrylate having an additional reactive group. The best embodiment in that application is achieved with a copolymer composed of ethene and methyl acrylate. The subject of that application is not flow improvement in moulding compositions. WO-A 2 001 038 437 (AU 4 610 801 A) describes mixtures composed of polyester with a core-shell rubber and with two different copolymers composed of ethene and of acrylates with and without additional reactive groups. The toughness of the moulding compositions can be improved, and the flowability even of the binary mixtures composed of polyester and of one of the other constituents mentioned is, according to Table 4 and Table 9, not better for the mixtures used than for the pure polyesters. The copolymer used composed of ethene and 2-ethylhexyl acrylate has an MFI value (MFI = Melt Flow Index) of 2 g/10 min (at 190°C, 2.16 kg). The object of the present invention then consisted in lowering the viscosity of polycondensate compositions based on thermoplastic polyesters by treating the polymer melt with additives, without any resultant need to accept the losses that occur when using low-viscosity linear polymer resins or when using additives disclosed in the literature in properties such as impact resistance, tensile strain at break and hydrolysis resistance. In terms of stiffness and ultimate tensile strength, the compositions based on thermoplastic polyesters should if at all possible not differ significantly from the polycondensate compositions based on thermoplastic polyesters and not treated with additives, in order to permit problem-free replacement of the materials for plastics structures based on thermoplastic polyesters. Achievement of the object is provided by thermoplastic moulding compositions comprising A) from 99 to 10 parts by weight, preferably from 98 to 30 parts by weight, particularly preferably from 97 to 60 parts by weight, of at least one thermoplastic polyester, preferably of a polyalkylene terephthalate and B) from 1 to 20 parts by weight, preferably from 2 to 15 parts by weight, particularly preferably from 3 to 9 parts by weight, of at least one copolymer composed of at least one olefm, preferably one a-olefin and of at least one methacrylic ester or acrylic ester of an aliphatic alcohol having from 1 to 4 carbon atoms, the MFI (Melt Flow Index) of the copolymer B) being not less than 50 g/10 min, and preferably being from 80 to 900g/10min, which are therefore provided by the present invention. For the purposes of the present invention, measurement or determination of the MFI (Melt Flow Index) always took place at 190°C with atest load of 2.16 kg. Surprisingly, it has been found that mixtures of thermoplastic polyesters and of a copolymer of a-olefins with methacrylic esters or with acrylic esters of aliphatic alcohols having from 1 to 4 carbon atoms whose MFI is not less than 50 g/10 min lead to the desired lowering of the melt viscosity of the inventive moulding compositions prepared therefrom, and that these inventive moulding compositions, when compared with moulding compositions without copolymer, exhibit no sacrifices, but rather indeed marked improvements, in properties such as impact resistance, outer fibre strain, hydrolysis resistance, density, surface quality and shrinkage. The moulding compositions have excellent suitability for use in thin-wall technology. According to the invention, the thermoplastic moulding compositions comprise, as component A), at least one thermoplastic polyester, preferably semiaromatic polyesters. The thermoplastic, preferably semiaromatic, polyesters to be used according to the invention as component A) have been selected from the group of the polyalkylene terephthalates, preferably selected from the group of the polyethylene terephthalates, of the polytrimethylene terephthalates and of the polybutylene terephthalates, particularly preferably of the polybutylene terephthalates and polyethylene terephthalates, very particularly preferably of polybutylene terephthalate. Semiaromatic polyesters are materials whose molecules contain not only aromatic moieties but also aliphatic moieties. For the purposes of the invention, polyalkylene terephthalates are reaction products derived from aromatic dicarboxylic acids or from their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols or are mixtures of these reaction products. Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or from its reactive derivatives) and from aliphatic or cycloaliphatic diols having from 2 to 10 carbon atoms, by known methods (Kunststoff-Handbuch [Plastics Handbook], Vol. VIII, pp. 695 et seq., Karl-Hanser-Verlag, Munich 1973). Preferred polyalkylene terephthalates contain at least 80 mol%, preferably 90 mol%, based on the dicarboxylic acid, of terephthalic acid radicals and at least 80 mol%, preferably at least 90 mol%, based on the diol component, of ethylene glycol radicals and/or 1,3-propanediol radicals and/or 1,4-butanediol radicals. The preferred polyalkylene terephthalates can contain, alongside terephthalic acid radicals, up to 20 mol% of radicals of other aromatic dicarboxylic acids having from 8 to 14 carbon atoms or radicals of aliphatic dicarboxylic acids having from 4 to 12 carbon atoms, e.g. radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, cyclohexanedicarboxylic acid. The preferred polyalkylene terephthalates can contain, alongside ethylene radicals and, respectively, 1,3-propanediol radicals and, respectively, 1,4-butanediol radicals, up to 20 mol% of other aliphatic diols having from 3 to 12 carbon atoms or of cycloaliphatic diols having from 6 to 21 carbon atoms, e.g. radicals of 1,3-propanediol, 2-ethyl- 1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6- hexanediol, cyclohexane-l,4-dimethanol, 3-methyl-2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4- trimethyl-l,3-pentanediol and 2,2,4-trimethyl-l,6-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl- 1,3-propanediol, 2,5-hexanediol, l,4-di(p-hydroxyethoxy)benzene, 2,2-bis(4- hydroxycyclohexyl)propane, 2,4-dmydroxy-l,l,3,3-tetramethylcyclobutane, 2,2-bis(3-p- hydroxyethoxyphenyl)propane and 2,2-bis(4-hydroxypropoxyphenyl)propane (DE-A 24 07 674 (= US 4 035 958), DE-A 24 07 776, DE-A 27 15 932 (= US 4 176 224)). The polyalkylene terephthalates can be branched via incorporation of relatively small amounts of tri-or tetrahydric alcohols or of tri- or tetrabasic carboxylic acid, as described by way of example in DE-A 19 00 270 (= US-A 3 692 744). Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol. It is preferable not to use more than 1 mol% of the branching agent, based on the acid component. Particular preference is given to polyalkylene terephthalates prepared solely from terephthalic acid and from its reactive derivatives (e.g. dialkyl esters thereof) and ethylene glycol and/or 1,3-propanediol and/or 1,4-butanediol (polyethylene terephthalate and polybutylene terephthalate), and mixtures of these polyalkylene terephthalates. Other preferred polyalkylene terephthalates are copolyesters prepared from at least two of the abovementioned acid components and/or from at least two of the abovementioned alcohol components, particularly preferred copolyesters being poly(ethylene glycol/l,4-butanediol) terephthalates. The intrinsic viscosity of the polyalkylene terephthalates is generally from about 0.3 cm3/g to 1.5 cm3/g, preferably from 0.4 cm3/g to 1.3 cm3/g, particularly preferably from 0.5 cm3/g to 1.0 cm3/g, in each case measured in phenol/o-dichlorobenzene (1:1 parts by weight) at 25°C. The thermoplastic polyesters to be used according to the invention can also be used in a mixture with other polyesters and/or with other polymers. Conventional additives, e.g. mould-release agents, stabilizers and/or flow aids can be admixed in the melt with the polyesters to be used according to the invention, or can be applied to their surface. The inventive compositions comprise, as component B), copolymers, preferably random copolymers composed of at least one olefin, preferably an a-olefin and of at least one methacrylic ester or acrylic ester of an aliphatic alcohol having from 1 to 4 carbon atoms, the MFI of the copolymer B) being not less than 50 g/10 min, and preferably being from 80 to 900 g/10 min. hi one preferred embodiment, less than 4% by weight, particularly preferably less than 1.5% by weight and very particularly preferably 0% by weight of the copolymer B) is composed of monomer units which contain further reactive functional groups (selected from the group consisting of epoxides, oxetanes, anhydrides, imides, aziridines, furans, acids, amines, oxazolines). Suitable olefins, preferably a-olefins as constituent of the copolymers B) preferably have from 2 to 10 carbon atoms and can be unsubstituted or have substitution by one or more aliphatic, cycloaliphatic or aromatic groups. Preferred olefins have been selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-l-pentene. Particularly preferred olefins are ethene and propene, and ethene is very particularly preferred. Mixtures of the olefins described are also suitable. hi another preferred embodiment, the further reactive functional groups (selected from the group consisting of epoxides, oxetanes, anhydrides, imides, aziridines, furans, acids, amines, oxazolines) of the copolymer B) are introduced exclusively by way of the olefins into the copolymer B). The content of the olefin in the copolymer B) is from 50 to 95% by weight, preferably from 61 to 93% by weight. The copolymer B) is further defined via the second constituent alongside the olefin. A suitable second constituent is alkyl esters of acrylic acid or methacrylic acid whose alkyl group is formed by from 1 to 4 carbon atoms. By way of example, the alkyl group of the methacrylic or acrylic ester can have been selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl. The alkyl group of the methacrylic or acrylic ester very particularly preferably has 4 carbon atoms and comprises the n-butyl, sec-butyl, isobutyl or tert-butyl. Particular preference is given to n-butyl acrylate. The alkyl group of the methacrylic or acrylic ester has preferably been selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl. According to the invention, particular preference is given to copolymers B) in which the olefin is copolymerized with butyl acrylate, in particular n-butyl acrylate. Mixtures of the acrylic or methacrylic esters described are likewise suitable. It is preferable here to use more than 50% by weight, particularly preferably more than 90% by weight and very particularly preferably 100% by weight, of butyl acrylate, based on the total amount of acrylic and methacrylic ester in copolymer B). In another preferred embodiment, the further reactive functional groups (selected from the group consisting of epoxides, oxetanes, anhydrides, imides, aziridines, furans, acids, amines, oxazolines) of the copolymer B) are introduced exclusively by way of acrylic or methacrylic ester into the copolymer B). The content of the acrylic or methacrylic esters in the copolymer B) is preferably from 5 to 50% by weight, particularly preferably from 7 to 39% by weight. A feature of suitable copolymers B) is not only their constitution but also their low molecular weight. Accordingly, copolymers B) suitable for the inventive moulding compositions are only those whose MFI value, measured at 190°C and with a load of 2.16 kg, is at least 50 g/10 min, preferably from 80to900g/10min. Examples of suitable copolymers of component B) can have been selected from the group of the materials supplied by Atofina (Arkema since October 2004) with the trade mark Lotryl®, this usually being used as hot-melt adhesive. In one preferred embodiment, the inventive thermoplastic moulding compositions can comprise, in addition to components A) and B), one or more components from the series C), D), E), F) or G). In one preferred embodiment of this type, the thermoplastic moulding compositions can also comprise, in addition to components A) and B), C) from 0.001 to 70 parts by weight, preferably from 5 to 50 parts by weight, particularly preferably from 9 to 47 parts by weight, of a filler and/or reinforcing material. However, the material can also comprise a mixture composed of two or more different fillers and/or reinforcing materials, for example based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar, barium sulphate, glass beads and/or fibrous fillers and/or reinforcing materials based on carbon fibres and/or glassfibres. It is preferable to use mineral particulate fillers based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar, barium sulphate and/or glassfibres. According to the invention, it is particularly preferable to use mineral particulate fillers based on talc, wollastonite, kaolin and/or glassfibres. Particularly for applications which demand isotropy in dimensional stability and demand high thermal dimensional stability, for example in motor vehicle applications for exterior bodywork parts, it is preferable to use mineral fillers, in particular talc, wollastonite or kaolin. A further particular preference is also the use of acicular mineral fillers as component C). According to the invention, acicular mineral fillers are a mineral filler with pronounced acicular character. An example which may be mentioned is acicular wollastonites. The length : diameter ratio of the material is preferably from 2:1 to 35:1, particularly preferably from 3:1 to 19:1, most preferably from 4:1 to 12:1. The average particle size of the inventive acicular minerals is preferably smaller than 20 jam, particularly preferably smaller than 15 urn, with particular preference smaller than 10 urn, determined using a CILAS GRANULOMETER. As previously described above, the filler and/or reinforcing material may, if appropriate, have been surface-modified, for example using a coupling agent or coupling agent system, e.g. based on silane. However, the pretreatment is not essential. In particular when glassfibres are used, polymer dispersions, film-formers, branching agents and/or glassfibre processing aids can also be used in addition to silanes. The glassfibres to be used with particular preference according to the invention whose fibre diameter is generally from 7 to 18 um, preferably from 9 to 15 um, are added in the form of continuous-filament fibres or in the form of chopped or ground glassfibres. The fibres can have been equipped with a suitable size system and with a coupling agent or coupling agent system, e.g. based on silane. Familiar coupling agents based on silane for pretreatment are silane compounds having by way of example the general formula (I) (I) (X-(CH2)q)k-Si-(0-CrH2r+1)4-k where the substituents are as follows: X: NH2-,HO-, H2c^^c—, rl q: a whole number from 2 to 10, preferably from 3 to 4, r: a whole number from 1 to 5, preferably from 1 to 2, k: a whole number from 1 to 3, preferably 1, Preferred coupling agents are silane compounds from the group of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane, and also the corresponding silanes which contain a glycidyl group as substituent X. The amounts generally used of the silane compounds for surface coating of the fillers are from 0.05 to 2% by weight, preferably from 0.25 to 1.5% by weight and in particular from 0.5 to 1% by weight, based on the mineral filler. The consequence of processing to give the moulding composition or moulding is that the d97 or d50 value of the particulate fillers in the moulding composition or in the moulding can be smaller than that of the fillers initially used. A consequence of the processing to give the moulding composition or moulding is that the length distributions of the glassfibres in the moulding composition or in the moulding can be shorter than those of the material initially used. In an alternative preferred embodiment, the thermoplastic moulding compositions can also comprise, in addition to components A) and B) and/or C) D) from 0.001 to 50 parts by weight, preferably from 9 to 35 parts by weight, of at least one flame retardant. Flame retardants that can be used in component D) are commercially available organic halogen compounds with synergists or are commercially available organic nitrogen compounds or are organic/inorganic phosphorus compounds individually or in a mixture. It is also possible to use mineral flame retardant additives such as magnesium hydroxide or Ca Mg carbonate hydrates (e.g. DE-A 4 236 122 (= CA 2 109 024 Al)). It is also possible to use salts of aliphatic or of aromatic sulphonic acids. Examples which may be mentioned of halogen-containing, in particular brominated and chlorinated compounds are: ethylene-l,2-bistetrabromophthalimide, epoxidized tetrabromobisphenol A resin, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, pentabromopolyacrylate, brominated polystyrene and decabromodiphenyl ether. Examples of suitable organophosphorus compounds are the phosphorus compounds according to WO-A 98/17720 (= US 6 538 024), e.g. triphenyl phosphate (TPP), resorcinol bis(diphenyl phosphate) (RDP) and the oligomers derived therefrom, and also bisphenol A bis(diphenyl phosphate) (BDP) and the oligomers derived therefrom, and organic and inorganic phosphonic acid derivatives and salts thereof, organic and inorganic phosphim'c acid derivatives and salts thereof, in particular metal dialkylphosphinates, e.g. aluminium tris[dialkylphosphinates] or zinc bis[dialkylphosphinates] and moreover red phosphorus, phosphites, hypophosphites, phospine oxides, phosphazenes, melamine pyrophosphate and mixtures of these. Nitrogen compounds which can be used are those from the group of the allantoin derivatives, cyanuric acid derivatives, dicyandiamide derivatives, glycoluril derivatives, guanidine derivatives, ammonium derivatives and melamine derivatives, preferably allantoin, benzoguanamine, glycoluril, melamine, condensates of melamine, e.g. melem, melam or melom and, respectively, higher-condensation-level compounds of this type and adducts of melamine with acids, e.g. with cyanuric acid (melamine cyanurate), phosphoric acid (melamine phosphate) or with condensed phosphoric acids (e.g. melamine polyphosphate). Examples of suitable synergists are antimony compounds, in particular antimony trioxide, sodium antimonate and antimony pentoxide, zinc compounds, e.g. zinc borate, zinc oxide, zinc phosphate and zinc sulphide, tin compounds, e.g. tin stannate and tin borate, and also magnesium compounds, e.g. magnesium oxide, magnesium carbonate and magnesium borate. The materials known as carbonizers can also be added to the flame retardant, examples being phenol-formaldehyde resins, polycarbonates, polyphenyl ethers, polyimides, polysulphones, polyether sulphones, polyphenylene sulphides and polyether ketones, antidrip agents, such as tetrafluoro-ethylene polymers. In another alternative preferred embodiment, the thermoplastic moulding compositions can also comprise, in addition to components A) and B) and/or C) and/or D) E) from 0.001 to 80 parts by weight, preferably from 2 to 40 parts by weight, particularly preferably from 4 to 19 parts by weight, of at least one elastomer modifier. The elastomer modifiers to be used as component E) comprise one or more graft polymers of E.I from 5 to 95% by weight, preferably from 30 to 90% by weight, of at least one vinyl monomer E.2 from 95 to 5% by weight, preferably from 70 to 10% by weight, of one or more graft bases with glass transition temperatures The median particle size (d50 value) of the graft base E.2 is generally from 0.05 to 10 um, preferably from 0.1 to 5 urn, particularly preferably from 0.2 to 1 (am. Monomers E. 1 are preferably mixtures composed of E. 1.1 from 50 to 99% by weight of vinylaromatics and/or ring-substituted vinylaromatics (such as styrene, a-methyl styrene, p-methyl styrene, p-chlorostyrene) and/or (Ci-Cg)-alkyl methacrylates (e.g. methyl methacrylate, ethyl methacrylate) and E.I.2 from 1 to 50% by weight of vinyl cyanides (unsaturated nitriles, such as acrylonitrile and methacrylonitrile) and/or (Ci-C8)-alkyl (meth)acrylate (e.g. methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and/or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (e.g. maleic anhydride and N-phenylmaleimide). Preferred monomers E.I.I have been selected from at least one of the monomers styrene, a-methylstyrene and methyl methacrylate, and preferred monomers E.I.2 have been selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate. Particularly preferred monomers are E. 1.1 styrene and E. 1.2 acrylonitrile. Examples of suitable graft bases E.2 for the graft polymers to be used in the elastomer modifiers E) are diene rubbers, EP(D)M rubbers, i.e. rubbers based on ethylene/propylene and, if appropriate, diene, acrylate rubbers, polyurethane rubbers, silicone rubbers, chloroprene rubbers and ethylene-vinyl acetate rubbers. Preferred graft bases E.2 are diene rubbers (e.g. based on butadiene, isoprene, etc.) or mixtures of diene rubbers, or are copolymers of diene rubbers or of their mixtures with further copolymerizable monomers (e.g. according to E. 1.1 and E. 1.2), with the proviso that the glass transition temperature of component E.2 is Pure polybutadiene rubber is particularly preferred as graft base E.2. Examples of particularly preferred polymers E) are ABS polymers (emulsion, bulk and suspension ABS), as described by way of example in DE-A 2 035 390 (= US-A 3 644 574) or in DE-A 2248242 (=GB-A 1 409 275) or in Ullmann, Enzyklopadie der Technischen Chemie [Encyclopaedia of Industrial Chemistry], Vol. 19 (1980), pp. 280 et seq. The gel content of the graft base E.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene). The elastomer modifiers or graft copolymers E) are prepared via free-radical polymerization, e.g. via emulsion, suspensions, solution or bulk polymerization, preferably via emulsion or bulk nnlvmftnVatinn polymerization. Other particularly suitable graft rubbers are ABS polymers which are prepared via redox initiation using an initiator system composed of organic hydroperoxide and ascorbic acid according to US-A 4937285. Because it is known that the graft monomers are not necessarily entirely grafted onto the graft base during the grafting reaction, products which are obtained via (co)polymerization of the graft monomers in the presence of the graft base and are produced concomitantly during the work-up are also graft polymers E according to the invention. Suitable acrylate rubbers are based on graft bases E.2 which are preferably polymers composed of alkyl acrylates, if appropriate with up to 40% by weight, based on E.2, of other polymerizable, ethylenically unsaturated monomers. Among the preferred polymerizable acrylic esters are Q-Cs-alkyl esters, such as methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably halo-Ci-Cg-alkyl esters, such as chloroethyl acrylate, and also mixtures of these monomers. For crosslinking, monomers having more than one polymerizable double bond can be copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having from 3 to 8 carbon atoms and of unsaturated monohydric alcohols having from 3 to 12 carbon atoms, or of saturated polyols having from 2 to 4 OH groups and from 2 to 20 carbon atoms, e.g. ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, e.g. trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, such as di- and trivinylbenzenes; and also triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least 3 ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes. The amount of the crosslinking monomers is preferably from 0.02 to 5% by weight, in particular from 0.05 to 2% by weight, based on the graft base E.2. In the case of cyclic crosslinking monomers having at least 3 ethylenically unsaturated groups, it is advantageous to restrict the amount to below 1% by weight of the graft base E.2. Examples of preferred "other" polymerizable, ethylenically unsaturated monomers which can serve alongside the acrylic esters, if appropriate, for preparation of the graft base E.2 are acrylonitrile, styrene, a-methylstyrene, acrylamides, vinyl d-Ce-alkyl ethers, methyl methacrylate, butadiene. Acrylate rubbers preferred as graft base E.2 are emulsion polymers whose gel content is at least 60% by weight. Further suitable graft bases according to E.2 are silicone rubbers having sites active for grafting purposes, as described in DE-A 3 704 657 (= US 4 859 740), DE-A 3 704 655 (= US 4 861 831), DE-A 3 631 540 (= US 4 806 593) and DE-A 3 631 539 (= US 4 812 515). Alongside elastomer modifiers based on graft polymers, it is also possible to use, as component E), elastomer modifiers not based on graft polymers but having glass transition temperatures In another alternative preferred embodiment, the thermoplastic moulding compositions can also comprise, in addition to components A) and B), and/or C) and/or D) and/or E) F) from 0.001 to 80 parts by weight, preferably from 10 to 70 parts by weight, particularly preferably from 20 to 60 parts by weight, of a polycarbonate. Preferred polycarbonates are those homopolycarbonates and copolycarbonates based on bisphenols of the general formula (II), HO-Z-OH (II) in which Z is a divalent organic radical having from 6 to 30 carbon atoms and containing one or more aromatic groups. Bisphenols of the formula (III) are preferred (Figure Remove) in which A is a single bond, Cl-C5-alkylene, C2-C5-alkylidene, C5-C6-cycloalkylidene, -0-, -SO-, -CO-, -S-, -S02-, or is C6-C12-arylene, onto which further aromatic rings, if appropriate containing heteroatoms, may have been condensed, or A is a radical of the formula (IV) or (V) (Figure Remove) in which X is in each case Ci-C^-alkyl, preferably methyl or halogen, preferably chlorine and/or bromine, n is in each case, independently of the others, 0, 1 or 2, p is 1 or 0, R7 and R8, individually selectable for each Y, and independently of each other, are hydrogen or Ci-C6-alkyl, preferably hydrogen, methyl or ethyl, Y is carbon and m is a whole number from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom Y, R7 and R8 are simultaneously alkyl. Examples of bisphenols according to the general formula (II) are bisphenols belonging to the following groups: dihydroxybiphenyls, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, indanebisphenols, bis(hydroxyphenyl) sulphides, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulphones, bis(hydroxyphenyl) sulphoxides and ct,a'-bis(hydroxyphenyl)diisopropylbenzenes. Other examples of bisphenols according to the general formula (II) are derivatives of the bisphenols mentioned, e.g. obtainable via alkylation or halogenation on the aromatic rings of the bisphenols mentioned. Examples of bisphenols according to the general formula (II) are in particular the following compounds: hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl) sulphide, bis(4-hydroxyphenyl) sulphone, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3,5-dimethyl-4- hydroxyphenyl) sulphone, l,l-bis(3,5-dimethyl-4-hydroxyphenyl)-p/m-diisopropylbenzene, 1,1 -bis(4-hydroxyphenyl)-l -phenylethane, 1,1 -bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1 -bis(4-hydroxyphenyl)-3 -methylcyclohexane, 1,1 -bis(4-hydroxyphenyl)-3,3 -dimethylcyclohexane, 1,1 -bis(4-hydroxyphenyl)-4-methylcyclohexane, 1,1 -bis(4-hydroxyphenyl)cyclohexane, 1,1 -bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis-(4-hydroxyphenyl)propane (i.e. bisphenol A), 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, a,a'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, a,a'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (i.e. bisphenol M), a,a'-bis(4-hydroxyphenyl)-p-diisopropylbenzene and indanebisphenol. Polycarbonates to be used with particular preference according to the invention as component F) are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane. The bisphenols according to the general formula (II) and described can be prepared by known processes, e.g. from the corresponding phenols and ketones. The bisphenols mentioned and processes for their production are described by way of example in the monograph H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, pp. 77-98, Interscience Publishers, New York, London, Sydney, 1964. l,l-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and its preparation is described by way of example in US-A 4 982 014. Indanebisphenols can by way of example be prepared from isopropenylphenol or from its derivatives or from dimers of isopropenylphenol or of its derivatives in the presence of a Friedel-Craft catalyst in organic solvents. Polycarbonates can be prepared by known processes. Examples of suitable processes for preparation of polycarbonates are preparation from bisphenols using phosgene by the interfacial process or from bisphenols using phosgene by the homogeneous-phase process known as the pyridine process, or from bisphenols using carbonic esters by the melt transesterification process. These preparation processes are described by way of example in H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, pp. 31-76, Interscience Publishers, New York, London, Sydney, 1964. In the preparation of polycarbonate, it is preferable to use raw materials and auxiliaries with a very low level of contaminants. In particular in preparation by the melt transesterification process, the intention is that the bisphenols used and the carbonic acid derivatives used have minimal content of alkali metal ions and alkaline earth metal ions. These pure raw materials are obtainable by way of example by recrystallizing, washing or distilling the carbonic acid derivatives, e.g. carbonic esters, and the bisphenols. The weight-average molar mass (M,_w), which by way of example can be determined by an ultracentrifuge method or by scattered-light measurement, is preferably from 10 000 to 200 000 g/mol for the polycarbonates suitable according to the invention. Their weight-average molar mass is particularly preferably from 12 000 to 80 000 g/mol, with particular preference from 20 000 to 35 000 g/mol. By way of example, it is possible to adjust the average molar mass of the inventive polycarbonates in a known manner via an appropriate amount of chain terminators. The chain terminators may be used individually or in the form of a mixture of various chain terminators. Suitable chain terminators are either monophenols or else monocarboxylic acids. Examples of suitable monophenols are phenol, p-chlorophenol, p-tert-butylphenol, cumylphenol or 2,4,6-tribromophenol, and also long-chain alkylphenols, e.g. 4-(l,l,3,3-tetramethylbutyl)phenol or monoalkylphenols and, respectively, dialkylphenols having a total of from 8 to 20 carbon atoms in the alkyl substituents, e.g. 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2-(3,5-dimethylheptyl)phenol or 4-(3,5-dimethylheptyl)phenol. Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halobenzoic acids. Preferred chain terminators are phenol, p-tert-butylphenol, 4-(l,l,3,3-tetramethylbutyl)phenol and cumylphenol. The amount of chain terminators is preferably from 0.25 to 10 mol%, based on the entirety of the bisphenols used in each case. The polycarbonates used according to the invention may have branching in a known manner, and specifically preferably via incorporation of branching agents whose functionality is three or higher. Examples of suitable branching agents are those having three or more than three phenolic groups or those having three or more than three carboxylic acid groups. Examples of suitable branching agents are phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 1 !3,5-tri(4-hydroxyphenyl)benzene, 1,1,1 -tris(4-hydroxyphenyl)ethane, tri(4-hydroxyphenyl)phenylmethane, 2,2-bis [4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, 2,6-bis(2-hydroxy-5 '-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, hexa(4-(4-hydroxyphenylisopropyl)phenyl)terephthalic ester, tetra(4-hydroxyphenyl)methane, tetra(4-(4-hydroxyphenylisopropyl)phenoxy)methane and l,4-bis(4',4"-dihydroxytriphenylmethyl)benzene, and also 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride, 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole, trimesyl trichloride and a,a',a"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene. Preferred branching agents are l,l,l-tris(4-hydroxyphenyl)ethane and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole. The amount of any branching agents to be used is preferably from 0.05 mol% to 2 mol%, based on the molar amount of bisphenols used. By way of example, if the polycarbonate is prepared by the interfacial process, the branching agents can be used as an initial charge with the bisphenols and the chain terminators in the aqueous alkaline phase, or can be added dissolved in an organic solvent together with the carbonic acid derivatives. In the case of the transesterification process, the branching agents are preferably metered in together with the dihydroxyaromatics or bisphenols. Preferred catalysts to be used during the preparation of polycarbonate by the melt transesterification process are the phosphonium salts and ammonium salts known from the literature. Copolycarbonates can also be used. For the purposes of the invention, copolycarbonates are in particular polydiorganosiloxane-polycarbonate block copolymers whose weight-average molar mass (M,_w) is preferably from 10000 to 200000 g/mol, particularly preferably from 20000 to 80 000 g/mol (determined via gel chromatography after prior calibration via light-scattering measurement or ultracentrifuge method). The content of aromatic carbonate structural units in the polydiorganosiloxane-polycarbonate block copolymers is preferably from 75 to 97.5 parts by weight, particularly preferably from 85 to 97 parts by weight. The content of polydiorganosiloxane structural units in the polydiorganosiloxane-polycarbonate block copolymers is preferably from 25 to 2.5 parts by weight, particularly preferably from 15 to 3 parts by weight. The polydiorgano-siloxane-polycarbonate block copolymers can by way of example be prepared starting from polydiorganosiloxanes which contain a,ra-bishydroxyaryloxy end groups, their average degree of polymerization preferably being Pn - from 5 to 100, particularly preferably Pn = from 20 to 80. The polydiorganosiloxane-polycarbonate block polymers can also be a mixture composed of polydiorganosiloxane-polycarbonate block copolymers with conventional polysiloxane-free, thermoplastic polycarbonates, the total content of polydiorganosiloxane structural units in this mixture preferably being from 2.5 to 25 parts by weight. These polydiorganosiloxane-polycarbonate block copolymers are characterized in that their polymer chain contains on the one hand aromatic carbonate structural units (VI) and on the other hand contains polydiorganosiloxanes (VII) containing aryloxy end groups, O —O-Ar-O-C-O-Ar-O- R9 -O-Ar-O—(Si-0)j—O-Ar-O-R10 in which Ar is identical or different difunctional aromatic radicals and R9 and R10 are identical or different and are linear alkyl, branched alkyl, alkenyl, halogenated linear alkyl, halogenated branched alkyl, aryl or halogenated aryl, preferably methyl, and 1 is the average degree of polymerization which is preferably from 5 to 100, particularly preferably from 20 to 80. Alkyl in the above formula (VII) is preferably Ci-C2o-alkyl, and alkenyl in the above formula (VII) is preferably C2-C6-alkenyl; aryl in the above formulae (VI) or (VII) is preferably Ce-Cu-aryl. Halogenated in the above formulae means partially or completely chlorinated, brominated or fluorinated. Examples of alkyl radicals, alkenyl radicals, aryl radicals, halogenated alkyl radicals and halogenated aryl radicals are methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, chloromethyl, perfluorobutyl, perfluorooctyl and chlorophenyl. These polydiorganosiloxane-polycarbonate block copolymers and their preparation are prior art and are described by way of example in US-A 3 189 662. By way of example, preferred polydiorganosiloxane-polycarbonate block copolymers can be prepared by reacting polydiorganosiloxanes containing a,co-bishydroxyaryloxy end groups together with other bisphenols, if appropriate with concomitant use of branching agents in the conventional amounts, e.g. by the interfacial process (as described by way of example hi H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, pp. 31-76, Interscience Publishers, New York, London, Sydney, 1964). The polydiorganosiloxanes containing a,co-bishydroxyaryloxy end groups and used as starting materials for this synthesis, and their preparation, are prior art and are described by way of example in US-A 3419 634. Conventional additives, e.g. mould-release agents, stabilizers and/or flow agents can be admixed in the melt with the polycarbonates or applied to their surface. By this stage, prior to compounding with the other components of the inventive moulding compositions, the polycarbonates to be used preferably comprise mould-release agents. hi another alternative preferred embodiment, the thermoplastic moulding compositions can also comprise, in addition to components A) and B), and/or C) and/or D) and/or E) and/or F) G) from 0.001 to 10 parts by weight, preferably from 0.05 to 5 parts by weight, particularly preferably from 0.1 to 3.5 parts by weight, of other conventional additives. Examples of conventional additives of component G) are stabilizers (e.g. UV stabilizers, heat stabilizers, gamma-ray stabilizers), antistatic agents, flow aids, mould-release agents, further fire-protection additives, emulsifiers, nucleating agents, plasticizers, lubricants, dyes, pigments and additives for increasing electrical conductivity. The additives mentioned and further suitable additives are described by way of example in Gachter, Muller, Kunststoff-Additive [Plastics Additives], 3rd Edition, Hanser-Verlag, Munich, Vienna, 1989 and in Plastics Additives Handbook, 5th Edition, Hanser-Verlag, Munich, 2001. The additives may be used alone or in a mixture, or in the form of masterbatches. Examples of stabilizers which can be used are organophosphorus compounds, phosphites, sterically hindered phenols, hydroquinones, aromatic secondary amines, e.g. diphenylamines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, and also various substituted representatives of these groups and mixtures thereof. Examples of pigments that can be used are titanium dioxide, zinc sulphide, ultramarine blue, iron oxide, carbon black, phthalocyanines, quinacridones, perylenes, nigrosin and anthraquinones. Examples of nucleating agents which can be used are sodium phenylphosphinate or calcium phenylphosphinate, aluminium oxide, silicon dioxide, and also preferably talc. Examples of lubricants and mould-release agents which can be used are ester waxes, pentaerytritol tetrastearate (PETS), long-chain fatty acids (e.g. stearic acid or behenic acid), salts thereof (e.g. Ca stearate or Zn stearate), and also amide derivatives (e.g. ethylenebisstearylamide) or montan waxes (mixtures composed of straight-chain, saturated carboxylic acids having chain lengths of from 28 to 32 carbon atoms). Examples of plasticizers which can be used are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N-(n-butyl)benzenesulphonamide. The component G) used can also be polyolefins, preferably polyethylene and/or polypropylene. Low-molecular-weight polyethylene waxes and low-molecular-weight polypropylene waxes are particularly preferred. Additives which can be added to increase electrical conductivity are carbon blacks, conductivity blacks, carbon fibrils, nanoscale graphite fibres and nanoscale carbon fibres, graphite, conductive polymers, metal fibres, and also other conventional additives for increasing electrical conductivity. Nanoscale fibres which can preferably be used are those known as "single-wall carbon nanotubes" or "multiwall carbon nanotubes" (e.g. from Hyperion Catalysis). According to the invention, the following combinations of the components are preferred AB; A,B,C; A,B,D; A,B,E; A,B,F; A,B,G; A,B,C,D; A,B,C,E; A,B,C,F; A,B,C,G; A,B,D,E; A,B,D,F; A,B,D,G; A,B,E,F; A,B,E,G; A,B,F,G; A,B,C,D,E; A,B,C,D,F; A,B,C,D,G; A,B,C,E,F; A,B,C,E,G; A,B,C,F,G; A,B,E,F,G; A,B,D,E,F; A,B,D,E,G; A,B,D,F,G; A,B,C,D,E,F: A,B,C,D,E,G: A,B,D,E,F,G; A,B,C,E,F,G; A,B,C,D,F,G; A,B,C,D,E,F,G. However, the present invention also provides a process for preparation of the inventive thermoplastic moulding compositions. This takes place by known processes via mixing of the components. The mixing of the components takes place via mixing of the appropriate proportions by weight of the components. The mixing of the components preferably takes place at temperatures of from 220 to 330°C via combining, mixing, kneading, extruding or rolling of the components together. It can be advantageous to premix individual components. It can moreover be advantageous to produce mouldings or semifinished products directly from a physical mixture (dry blend) prepared at room temperature (preferably from 0 to 40°C) and composed of premixed components and/or of individual components. The invention further provides the mouldings to be produced from the inventive moulding compositions comprising A) from 99 to 10 parts by weight, preferably from 98 to 30 parts by weight, particularly preferably from 97 to 60 parts by weight, of at least one thermoplastic polyester, preferably of a polyalkylene terephthalate and B) from 1 to 20 parts by weight, preferably from 2 to 15 parts by weight, particularly preferably from 3 to 9 parts by weight, of at least one copolymer composed of at least one olefin, preferably cc-olefin and of at least one methacrylic ester or acrylic ester of an aliphatic alcohol having from 1 to 4 carbon atoms, the MFI (measured at 190°C for 2.16 kg; DIN EN ISO 1133) of the copolymer B) being not less than 50 g/10 min, and preferably being from 80 to 900 g/10 min. The following surprising advantages are exhibited by the inventive moulding compositions in comparison with a moulding composition corresponding to the prior art: markedly improved flowability, in particular at shear rates relevant for thermoplastics processing; improved toughness; improved outer fibre strain, in particular after hydrolysis; lower density; reduced shrinkage; improved hydrolysis resistance; improved surface quality of the mouldings. The inventive moulding compositions can be processed by conventional processes, for example via injection moulding or extrusion, to give mouldings or semifinished products. Examples of semifinished products are foils and sheets. Processing by injection moulding is particularly preferred. The mouldings or semifinished products to be produced according to the invention from the thermoplastic moulding compositions can be small or large parts and by way of example can be used in the motor vehicle, electrical, electronics, telecommunications, information technology, or computer industry, in the household, in sports, in medicine, or in the entertainment industry. In particular, the inventive moulding compositions can be used for applications which require high melt flowability. An example of these applications is what is known as thin-wall technology, in which the wall thicknesses of mouldings to be produced from the moulding compositions are less than 2.5 mm, preferably less than 2.0 mm, particularly preferably less than 1.5 mm and most preferably less than 1.0 mm. Another example of these applications is cycle time reduction, for example via a reduction in processing temperature. Another application example is the processing of the moulding compositions by way of what are known as multitooling systems, in which material is charged by way of a runner system to at least 4 moulds, preferably at least 8 moulds, particularly preferably at least 12 moulds, most preferably at least 16 moulds, in an injection moulding procedure. Examples: Component A: Linear polybutylene terephthalate (Pocan® B 1300, commercially available product from Lanxess Deutschland GmbH, Leverkusen, Germany) with intrinsic viscosity of about 0.93 cm3/g (measured in phenol: 1,2-dichlorobenzene = 1:1 at 25°C) Component B: Copolymer composed of ethene and n-butyl acrylate with ethene content of 70-74% by weight and with an MFI of 175 (Lotryl® 28 BA 175 from Atofina Deutschland, Dusseldorf) (Arkema GmbH since October 2004) [CAS No. 25750-84-9] Component C: Glassfibre sized with silane-containing compounds and with a diameter of 10 jam (CS 7967, commercially available product from Lanxess N.V., Antwerp, Belgium) Component G: The following components familiar for use in thermoplastic polyesters were used as further additives: Nucleating agent: Amounts of from 0.01 to 0.59% by weight of talc [CAS No. 14807-96-6]. Heat stabilizer: Amounts of from 0.01 to 0.59% by weight of conventional stabilizers based on phenyl phosphites. Mould-release agent: Amounts of from 0.1 to 0.68% by weight of commercially available fatty acid esters. The nature and amount of each of the further additives (component G) used are the same for the comparative example and inventive example, specifically using G = 0.7%. The compositions based on PBT were compounded in a ZSK 32 (Werner and Pfleiderer) twin-screw extruder at melt temperatures of from 270 to 275 °C to give moulding compositions, and the melt was discharged into a water bath and then pelletized. The test specimens for the tests listed in the table were injection moulded in an Arburg 320-210-500 injection moulding machine at a melt temperature of about 260°C and at a mould temperature of about 80°C: - 80 x 10 x 4 mm3 test specimens (to ISO 178) - 60 x 60 x 2 mm3 plaques for shrinkage measurement to ISO 294-4 The injection pressure is the internal mould pressure applied in the vicinity of the gate in order to fill the mould cavity. In the curve of pressure as a function of time it is a characteristic inflection point between the mould-filling and compaction phase, and can be determined by way of process data capture. It was determined for the comparative example and for the inventive example during the injection moulding of flat specimens (80 x 10 x 4 mm3). With the exception of the viscosity measurements, all of the tests were carried out on the abovementioned test specimens. Flexural test to determine flexural modulus, flexural strength and outer fibre strain to DIN / EN / ISO 178. Impact resistance: IZOD method to ISO 180 1U at room temperature and at -30°C. Shrinkage: To determine shrinkage properties, standardized sheets of dimension 60 mm x 60 mm x 2 mm (ISO 294-4) are injection moulded. Longitudinal and transverse shrinkage is determined both in terms of moulding shrinkage and in terms of after-shrinkage, via subsequent measurement. Moulding shrinkage and after-shrinkage together give the total shrinkage. Density was determined by the flotation method on test specimens to DIN EN ISO 1183-1. Melt viscosity was determined to DIN 54811 / ISO 11443 at the stated shear rate and temperature, using Viscorobo 94.00 equipment from Gottfert after drying of the pellets at 120°C for 4 hours in a vacuum dryer. Hydrolysis: To measure hydrolysis resistance, test specimens produced from the inventive moulding compositions were stored at 100°C and 100% humidity in a steam sterilizer. After 5 and after 10 days of hydrolysis, impact resistance was measured and the flexural test was carried out. Surface: Test specimens of dimension 60 mm x 60 mm x 2 mm were used for surface appraisal and visual surface assessment. Decisive criteria for judgement were gloss, smoothness, colour and uniform surface structure. Table Comparison Inventive example Component A [%] 69.3 64.3 Component B r%i _ 5.0 Component C [%] 30.0 30.0 Component G r%i 0.7 0.7 Injection pressure [bar] 207 179 Melt viscosity (260°C, 1000 s"1) [Pas] 208 153 Melt viscosity (260°C, 1500 s'1) [Pas] 176 125 Melt viscosity (280°C, 1000 sl) [Pasl 127 107 Melt viscosity (280°C, 1500 s'1) [Pas] 109 89 Izod impact resistance (ISO 180/1U, RT) [kJ/m2] 55 58 Izod impact resistance (ISO 180/1U, RT) after 5 days of hydrolysis [kJ/m2] 25 37 Izod impact resistance (ISO 180/1U, RT) after 10 days of hydrolysis [kJ/m2] 15 28 Izod impact resistance (ISO 180/1U, -30°C) [kJ/m2! 56 70 Total shrinkage (1 h/150°C) longitudinal transverse [%] 0.48 1.30 0.45 1.09 Flexural test: Flexural strength Outer fibre strain for flexural strength Flexural modulus [MPa] [%] [MPal 217 3.4 9016 196 3.4 8316 Flexural test after 5 days of hydrolysis: Flexural strength Outer fibre strain for flexural strength Flexural modulus [MPa] [%] [MPa] 158 2.2 8676 169 2.6 8055 Flexural test after 10 days of hydrolysis: Flexural strength Outer fibre strain for flexural strength Flexural modulus [MPa] [%] [MPa] 121 1.7 8374 138 2.0 8005 Density [g/cm3! 1.53 1.49 Surface quality good very good WE CLAIM; 1. A homogeneous process for the hydrogenation of dicarboxylic acids and/or anhydrides in the presence of a catalyst comprising: (a) ruthenium, rhodium, iron, osmium or palladium; and (b) an organic phosphine of the kind such as herein described; wherein the hydrogenation is carried out in the presence of at least 1% by weight water and wherein the reaction is carried out at a pressure of from 500 psig to 2000 psig and a temperature of from 200°C to 300°C such that from 1 mol to 10 mol of hydrogen are used to strip 1 mole of product from the reactor. 2. The process as claimed in claim 1 wherein the process is a continuous process comprising the steps of: (a) feeding the dicarboxylic acid and/or anhydride to the hydrogenation reactor; (b) hydrogenating the dicarboxylic acid and/or anhydride; (c) recovering the product in an hydrogen stream; (d) separating the product from the hydrogen stream; (e) recycling the hydrogen stream to the reactor; (f) separating any removed catalyst and recycling the catalyst to the reactor, and (g) recovering the product. 3. The process as claimed in claim 1 or 2 wherein the dicarboxylic acid and/or anhydride is a C4 dicarboxylic acid or anhydride such that the process is a process for the production of butanediol, tetrahydrofuran and/or -butyrolactone. 4. The process as claimed in claim 3, wherein any  -butyrolactone produced in the hydrogenation reaction is recycled to the hydrogenation reactor. 5. The process as claimed in claim 3 or 4 wherein the C4 dicarboxylic acid or anhydride is fumaric acid, maleic anhydride, maleic acid, succinic acid or succinic anhydride. 6. The process as claimed in any one of claims 1 to 5 wherein the water is present as the solvent for the reaction. 7. The process as claimed in any one of Claims 1 to 5 wherein one or both of the reactants or the product are the solvent for the catalyst. 8. The process as claimed in claim 7 wherein a solvent is used and the water is present as an additive in the solvent. 9. The process as claimed in any one of claims 1 to 5 wherein the water is produced in situ as a by-product of the hydrogenation reaction. 10. The process as claimed in any one of claims 1 to 9 wherein the reaction takes place in more than one reactor and the reactors are operated in series. 11. The process as claimed in any one of claims 1 to 9 wherein the reaction is carried out at a pressure of 900 psig. 12. The process as claimed in any one of claims 1 to 10 wherein the reaction is carried out at a temperature of 240°C to 250°C. 13. The process as claimed in any one of claims 1 to 12 the catalyst is a ruthenium/phosphine catalyst. 14. The process as claimed in any one of claims 1 to 13 wherein, the ruthenium is present in an amount of from 0.0001 to 5 mol as ruthenium per liter of reaction solution. 15. The process as claimed in any one of claims 1 to 14 wherein the phosphine is tridentate phosphine. 16. The process as claimed in any one of claims 1 to 14 wherein the phosphine is selected from trialkylphosphines, dialkylphosplines, monoalkylphosphines, triarylphosphines, diarylphosphine, monoarylphosphines, diarylmonoalkyl phosphines and dialkylmonoaryl phosphines. 17. The process as claimed in claim 16, wherein the phosphine is selected from tris-1,1,1 -(diphenylphosphinomethyl)methane, tris-1,1,1 -(diphenylphosphinomethyl)- ethane. tris-1.1.1- (diphenylphosphinomethyl)propane, tris-1,1,1- (diphenylphosphinomethyl)butane, tris-1,1,1- (diphenylphosphinomethyl)2,2dimethylpropane, tris-l,3,5-(diphenylphosphino- methyl)cyclohexane, tris-1,1,1 - (dicyclohexylphosphinomethyl)ethane, tris-1,1,1 - (dimethylphosphinomethyl)ethane, tris-1,1,1 - (diethylphosphinomethyl)ethane, 1,5,9- triethyl-1,5-9- triphosphacyclododecane, 1,5,9-triphenyl- 1,5-9- triphosphacyclododecane, bis(2-diphylephosphinoethyl)phenylphosphine, bis- 1,2-(diphenyl phosphino)ethane, bis-1 ,3-(diphenyl phosphino)propane, bis-l,4-(diphenyl phosphino)butane, bis-l,2-(dimethyl phosphino)ethane, bis-1,3-(diethyl phosphino)propane, bis-l,4-(dicyclohexyl phosphino)butane, tricyclohexylphosphine, trioctyl phosphine, trimethyl phosphine, tripyridyl phosphine, triphenylphosphine. 18. A process as claimed in claim 16, wherein the phosphine is selected from tris-1,1,1-(diarylphosphinomethyl)alkane aid tris-1,1,1 -(dialkylphosphinomethyl)alkane. 19. The process as claimed in any one of claims 1 to 18 wherein, the phosphine is present in an amount of from 0.0001 to 5 mol as phosphine per liter of reaction solution. 20. The process as claimed in any one of claims 1 to 19 wherein the catalyst is regenerated in the presence of water and hydrogen.

Full Text

Moulding compositions based on a thermoplastic polyester with improved flowabilitv
This invention relates to moulding compositions based on a thermoplastic polyester and on at least one copolymer composed of at least one a-olefin with at least one methacrylic ester or acrylic ester of an aliphatic alcohol having from 1 to 4 carbon atoms, the MFI (Melt Flow Index) of the copolymer being not less than 50g/10min, to a process for preparation of these moulding compositions, and also the use of these moulding compositions for production of mouldings for the electrical, electronics, telecommunications, motor vehicle or computer industry, in sports, in the household, in medicine or for the entertainment industry.
Highly flowable thermoplastic compositions are of interest for a wide variety of injection moulding applications. By way of example, thin-walled components in the electrical, electronics and motor vehicle industry require low viscosities from the thermoplastics composition in order to permit material to be charged to the mould with minimum injection pressures and, respectively, clamping forces in the appropriate injection moulding machines. This also applies to simultaneous charging of material to two or more injection moulding components by way of a shared runner system in what are known as multicavity tooling systems. Shorter cycle times can moreover often be achieved using low-viscosity thermoplastic compositions. Good flowabilities are also specifically very important for highly filled thermoplastic compositions, e.g. with glassfibre and/or mineral contents above 40% by weight.
However, although the thermoplastic compositions have high flowability, the actual components produced therefrom are subjected to stringent mechanical requirements, and the lowering of viscosity cannot therefore be permitted to cause any significant impairment of mechanical properties. Indeed, because of the structure of the components to be produced, the requirements placed upon mechanical properties such as impact resistance or outer fibre strain, are increasingly often more stringent than for standard thermoplastics.
There are a number of ways of obtaining highly flowable, low-viscosity thermoplastic moulding compositions.
One way uses low-viscosity polymer resins with very low molecular weight as base polymers for the thermoplastic moulding compositions. However, the use of low-molecular-weight polymer resins is often associated with sacrifices in mechanical properties, in particular toughness. Preparation of a low-viscosity polymer resin in an existing polymerization plant moreover often requires complicated intervention attended by capital expenditure.
Another way uses what are known as flow aids, also termed flow agents or flow assistants or

internal lubricants, which can be added as an additive to the polymer resin.
These flow aids are known from the literature, e.g. in Kunststoffe 2000, 90 (9), p. 116-118, and by way of example can be fatty acid esters of polyols, or amides derived from fatty acids and from amines. However, these fatty acid esters, such as pentaerythritol tetrastearate or ethylene glycol dimontanoate, have only limited miscibility with polar thermoplastics, such as polyamides, polyalkylene terephthalates or polycarbonates. Their concentration increases at the surface of the moulding and they are therefore also used as mould-release aids. Particularly at relatively high concentrations, they can also migrate out of these mouldings to the surface on heat-ageing and become concentrated at the surface. By way of example, in coated mouldings this can lead to problems with regard to adhesion to paint or to metal.
As an alternative to the surface-active flow aids, it is possible to use internal flow aids which are compatible with the polymer resins. Examples of those suitable for this purpose are low-molecular-weight compounds or branched, highly branched or dendritic polymers whose polarity is similar to that of the polymer resin. These highly branched or dendritic systems are known from the literature and their basis can by way of example be branched polyesters, polyamides, polyesteramides, polyethers or polyamines, as described in Kunststoffe 2001, 91 (10), pp. 179-190, or in Advances in Polymer Science 1999, 143 (Branched Polymers II), pp. 1-34.
EP 0 682 057 Al describes the use of the nitrogen-containing first-generation 4-cascade dendrimer: l,4-diaminobutane[4]propylamine (N,N'-tetrabis(3-ammopropyl)-l,4-butanediarnine) DAB(PA)4 to lower viscosity in nylon-6, nylon-6,6 and polybutylene terephthalate. While use of DAB(PA)4 to lower viscosity in polyamides has practically no effect on the impact resistance of the resultant moulding compositions (difference WO-A 98 27159 describes an improvement in toughness of glassfibre-reinforced polyesters or polycarbonates via use of two copolymers composed of ethene and of acrylates, one copolymer also bearing a reactive epoxy or oxirane function. Flow improvement in the moulding compositions is an object of the invention, but the comparison system described composed of polyester and of the copolymer composed of ethene and methylacrylate has higher melt viscosity than the pure polyester system.
JP 01247454 describes mixtures which have low-temperature toughness, of polyesters with a copolymer composed of ethene and of an unreactive alkyl acrylate whose MFI is 5.8 g / 10 min (at 190°C, 2.16 kg) and with a copolymer composed of ethene and of an acrylate having an additional

reactive group. The subject of that application is not flow improvement in moulding compositions.
EP-A 1 191 067 (= US 6 759 480) describes the impact modification of thermoplastics, inter alia of polyamide and polybutylene terephthalate via a mixture composed of a copolymer composed of ethene with an unreactive alkyl acrylate, and also of a copolymer composed of ethene with an acrylate having an additional reactive group. There is no discussion of the flowability of the moulding composition.
EP-A 0 838 501 (= US 6 020 414) describes mixtures having low-temperature toughness of reinforcing materials and polyesters with a copolymer composed of ethene and of an unreactive alkyl acrylate, and also with a copolymer composed of ethene and of an acrylate having an additional reactive group. The best embodiment in that application is achieved with a copolymer composed of ethene and methyl acrylate. The subject of that application is not flow improvement in moulding compositions.
WO-A 2 001 038 437 (AU 4 610 801 A) describes mixtures composed of polyester with a core-shell rubber and with two different copolymers composed of ethene and of acrylates with and without additional reactive groups. The toughness of the moulding compositions can be improved, and the flowability even of the binary mixtures composed of polyester and of one of the other constituents mentioned is, according to Table 4 and Table 9, not better for the mixtures used than for the pure polyesters. The copolymer used composed of ethene and 2-ethylhexyl acrylate has an MFI value (MFI = Melt Flow Index) of 2 g/10 min (at 190°C, 2.16 kg).
The object of the present invention then consisted in lowering the viscosity of polycondensate compositions based on thermoplastic polyesters by treating the polymer melt with additives, without any resultant need to accept the losses that occur when using low-viscosity linear polymer resins or when using additives disclosed in the literature in properties such as impact resistance, tensile strain at break and hydrolysis resistance. In terms of stiffness and ultimate tensile strength, the compositions based on thermoplastic polyesters should if at all possible not differ significantly from the polycondensate compositions based on thermoplastic polyesters and not treated with additives, in order to permit problem-free replacement of the materials for plastics structures based on thermoplastic polyesters.
Achievement of the object is provided by thermoplastic moulding compositions comprising
A) from 99 to 10 parts by weight, preferably from 98 to 30 parts by weight, particularly preferably from 97 to 60 parts by weight, of at least one thermoplastic polyester, preferably of a polyalkylene terephthalate and

B) from 1 to 20 parts by weight, preferably from 2 to 15 parts by weight, particularly preferably from 3 to 9 parts by weight, of at least one copolymer composed of at least one olefm, preferably one a-olefin and of at least one methacrylic ester or acrylic ester of an aliphatic alcohol having from 1 to 4 carbon atoms, the MFI (Melt Flow Index) of the copolymer B) being not less than 50 g/10 min, and preferably being from 80 to 900g/10min,
which are therefore provided by the present invention.
For the purposes of the present invention, measurement or determination of the MFI (Melt Flow Index) always took place at 190°C with atest load of 2.16 kg.
Surprisingly, it has been found that mixtures of thermoplastic polyesters and of a copolymer of a-olefins with methacrylic esters or with acrylic esters of aliphatic alcohols having from 1 to 4 carbon atoms whose MFI is not less than 50 g/10 min lead to the desired lowering of the melt viscosity of the inventive moulding compositions prepared therefrom, and that these inventive moulding compositions, when compared with moulding compositions without copolymer, exhibit no sacrifices, but rather indeed marked improvements, in properties such as impact resistance, outer fibre strain, hydrolysis resistance, density, surface quality and shrinkage. The moulding compositions have excellent suitability for use in thin-wall technology.
According to the invention, the thermoplastic moulding compositions comprise, as component A), at least one thermoplastic polyester, preferably semiaromatic polyesters.
The thermoplastic, preferably semiaromatic, polyesters to be used according to the invention as component A) have been selected from the group of the polyalkylene terephthalates, preferably selected from the group of the polyethylene terephthalates, of the polytrimethylene terephthalates and of the polybutylene terephthalates, particularly preferably of the polybutylene terephthalates and polyethylene terephthalates, very particularly preferably of polybutylene terephthalate.
Semiaromatic polyesters are materials whose molecules contain not only aromatic moieties but also aliphatic moieties.
For the purposes of the invention, polyalkylene terephthalates are reaction products derived from aromatic dicarboxylic acids or from their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols or are mixtures of these reaction products.
Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or from its reactive derivatives) and from aliphatic or cycloaliphatic diols having from 2 to 10 carbon atoms, by known

methods (Kunststoff-Handbuch [Plastics Handbook], Vol. VIII, pp. 695 et seq., Karl-Hanser-Verlag, Munich 1973).
Preferred polyalkylene terephthalates contain at least 80 mol%, preferably 90 mol%, based on the dicarboxylic acid, of terephthalic acid radicals and at least 80 mol%, preferably at least 90 mol%, based on the diol component, of ethylene glycol radicals and/or 1,3-propanediol radicals and/or 1,4-butanediol radicals.
The preferred polyalkylene terephthalates can contain, alongside terephthalic acid radicals, up to 20 mol% of radicals of other aromatic dicarboxylic acids having from 8 to 14 carbon atoms or radicals of aliphatic dicarboxylic acids having from 4 to 12 carbon atoms, e.g. radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, cyclohexanedicarboxylic acid.
The preferred polyalkylene terephthalates can contain, alongside ethylene radicals and, respectively,
1,3-propanediol radicals and, respectively, 1,4-butanediol radicals, up to 20 mol% of other aliphatic
diols having from 3 to 12 carbon atoms or of cycloaliphatic diols having from 6 to 21 carbon atoms,
e.g. radicals of 1,3-propanediol, 2-ethyl- 1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-
hexanediol, cyclohexane-l,4-dimethanol, 3-methyl-2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-
trimethyl-l,3-pentanediol and 2,2,4-trimethyl-l,6-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-
1,3-propanediol, 2,5-hexanediol, l,4-di(p-hydroxyethoxy)benzene, 2,2-bis(4-
hydroxycyclohexyl)propane, 2,4-dmydroxy-l,l,3,3-tetramethylcyclobutane, 2,2-bis(3-p-
hydroxyethoxyphenyl)propane and 2,2-bis(4-hydroxypropoxyphenyl)propane (DE-A 24 07 674 (= US 4 035 958), DE-A 24 07 776, DE-A 27 15 932 (= US 4 176 224)).
The polyalkylene terephthalates can be branched via incorporation of relatively small amounts of tri-or tetrahydric alcohols or of tri- or tetrabasic carboxylic acid, as described by way of example in DE-A 19 00 270 (= US-A 3 692 744). Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.
It is preferable not to use more than 1 mol% of the branching agent, based on the acid component.
Particular preference is given to polyalkylene terephthalates prepared solely from terephthalic acid and from its reactive derivatives (e.g. dialkyl esters thereof) and ethylene glycol and/or 1,3-propanediol and/or 1,4-butanediol (polyethylene terephthalate and polybutylene terephthalate), and mixtures of these polyalkylene terephthalates.
Other preferred polyalkylene terephthalates are copolyesters prepared from at least two of the

abovementioned acid components and/or from at least two of the abovementioned alcohol components, particularly preferred copolyesters being poly(ethylene glycol/l,4-butanediol) terephthalates.
The intrinsic viscosity of the polyalkylene terephthalates is generally from about 0.3 cm3/g to 1.5 cm3/g, preferably from 0.4 cm3/g to 1.3 cm3/g, particularly preferably from 0.5 cm3/g to 1.0 cm3/g, in each case measured in phenol/o-dichlorobenzene (1:1 parts by weight) at 25°C.
The thermoplastic polyesters to be used according to the invention can also be used in a mixture with other polyesters and/or with other polymers.
Conventional additives, e.g. mould-release agents, stabilizers and/or flow aids can be admixed in the melt with the polyesters to be used according to the invention, or can be applied to their surface.
The inventive compositions comprise, as component B), copolymers, preferably random copolymers composed of at least one olefin, preferably an a-olefin and of at least one methacrylic ester or acrylic ester of an aliphatic alcohol having from 1 to 4 carbon atoms, the MFI of the copolymer B) being not less than 50 g/10 min, and preferably being from 80 to 900 g/10 min. hi one preferred embodiment, less than 4% by weight, particularly preferably less than 1.5% by weight and very particularly preferably 0% by weight of the copolymer B) is composed of monomer units which contain further reactive functional groups (selected from the group consisting of epoxides, oxetanes, anhydrides, imides, aziridines, furans, acids, amines, oxazolines).
Suitable olefins, preferably a-olefins as constituent of the copolymers B) preferably have from 2 to 10 carbon atoms and can be unsubstituted or have substitution by one or more aliphatic, cycloaliphatic or aromatic groups.
Preferred olefins have been selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-l-pentene. Particularly preferred olefins are ethene and propene, and ethene is very particularly preferred.
Mixtures of the olefins described are also suitable.
hi another preferred embodiment, the further reactive functional groups (selected from the group consisting of epoxides, oxetanes, anhydrides, imides, aziridines, furans, acids, amines, oxazolines) of the copolymer B) are introduced exclusively by way of the olefins into the copolymer B).
The content of the olefin in the copolymer B) is from 50 to 95% by weight, preferably from 61 to 93% by weight.

The copolymer B) is further defined via the second constituent alongside the olefin. A suitable second constituent is alkyl esters of acrylic acid or methacrylic acid whose alkyl group is formed by from 1 to 4 carbon atoms.
By way of example, the alkyl group of the methacrylic or acrylic ester can have been selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl. The alkyl group of the methacrylic or acrylic ester very particularly preferably has 4 carbon atoms and comprises the n-butyl, sec-butyl, isobutyl or tert-butyl. Particular preference is given to n-butyl acrylate.
The alkyl group of the methacrylic or acrylic ester has preferably been selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl.
According to the invention, particular preference is given to copolymers B) in which the olefin is copolymerized with butyl acrylate, in particular n-butyl acrylate.
Mixtures of the acrylic or methacrylic esters described are likewise suitable. It is preferable here to use more than 50% by weight, particularly preferably more than 90% by weight and very particularly preferably 100% by weight, of butyl acrylate, based on the total amount of acrylic and methacrylic ester in copolymer B).
In another preferred embodiment, the further reactive functional groups (selected from the group consisting of epoxides, oxetanes, anhydrides, imides, aziridines, furans, acids, amines, oxazolines) of the copolymer B) are introduced exclusively by way of acrylic or methacrylic ester into the copolymer B).
The content of the acrylic or methacrylic esters in the copolymer B) is preferably from 5 to 50% by weight, particularly preferably from 7 to 39% by weight.
A feature of suitable copolymers B) is not only their constitution but also their low molecular weight. Accordingly, copolymers B) suitable for the inventive moulding compositions are only those whose MFI value, measured at 190°C and with a load of 2.16 kg, is at least 50 g/10 min, preferably from 80to900g/10min.
Examples of suitable copolymers of component B) can have been selected from the group of the materials supplied by Atofina (Arkema since October 2004) with the trade mark Lotryl®, this usually being used as hot-melt adhesive.
In one preferred embodiment, the inventive thermoplastic moulding compositions can comprise, in

addition to components A) and B), one or more components from the series C), D), E), F) or G).
In one preferred embodiment of this type, the thermoplastic moulding compositions can also comprise, in addition to components A) and B),
C) from 0.001 to 70 parts by weight, preferably from 5 to 50 parts by weight, particularly preferably from 9 to 47 parts by weight, of a filler and/or reinforcing material.
However, the material can also comprise a mixture composed of two or more different fillers and/or reinforcing materials, for example based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar, barium sulphate, glass beads and/or fibrous fillers and/or reinforcing materials based on carbon fibres and/or glassfibres. It is preferable to use mineral particulate fillers based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar, barium sulphate and/or glassfibres. According to the invention, it is particularly preferable to use mineral particulate fillers based on talc, wollastonite, kaolin and/or glassfibres.
Particularly for applications which demand isotropy in dimensional stability and demand high thermal dimensional stability, for example in motor vehicle applications for exterior bodywork parts, it is preferable to use mineral fillers, in particular talc, wollastonite or kaolin.
A further particular preference is also the use of acicular mineral fillers as component C). According to the invention, acicular mineral fillers are a mineral filler with pronounced acicular character. An example which may be mentioned is acicular wollastonites. The length : diameter ratio of the material is preferably from 2:1 to 35:1, particularly preferably from 3:1 to 19:1, most preferably from 4:1 to 12:1. The average particle size of the inventive acicular minerals is preferably smaller than 20 jam, particularly preferably smaller than 15 urn, with particular preference smaller than 10 urn, determined using a CILAS GRANULOMETER.
As previously described above, the filler and/or reinforcing material may, if appropriate, have been surface-modified, for example using a coupling agent or coupling agent system, e.g. based on silane. However, the pretreatment is not essential. In particular when glassfibres are used, polymer dispersions, film-formers, branching agents and/or glassfibre processing aids can also be used in addition to silanes.
The glassfibres to be used with particular preference according to the invention whose fibre diameter is generally from 7 to 18 um, preferably from 9 to 15 um, are added in the form of continuous-filament fibres or in the form of chopped or ground glassfibres. The fibres can have been equipped

with a suitable size system and with a coupling agent or coupling agent system, e.g. based on silane.
Familiar coupling agents based on silane for pretreatment are silane compounds having by way of example the general formula (I)
(I) (X-(CH2)q)k-Si-(0-CrH2r+1)4-k where the substituents are as follows:
X: NH2-,HO-, H2c^^c—,
rl
q: a whole number from 2 to 10, preferably from 3 to 4,
r: a whole number from 1 to 5, preferably from 1 to 2,
k: a whole number from 1 to 3, preferably 1,
Preferred coupling agents are silane compounds from the group of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane, and also the corresponding silanes which contain a glycidyl group as substituent X.
The amounts generally used of the silane compounds for surface coating of the fillers are from 0.05 to 2% by weight, preferably from 0.25 to 1.5% by weight and in particular from 0.5 to 1% by weight, based on the mineral filler.
The consequence of processing to give the moulding composition or moulding is that the d97 or d50 value of the particulate fillers in the moulding composition or in the moulding can be smaller than that of the fillers initially used. A consequence of the processing to give the moulding composition or moulding is that the length distributions of the glassfibres in the moulding composition or in the moulding can be shorter than those of the material initially used.
In an alternative preferred embodiment, the thermoplastic moulding compositions can also comprise, in addition to components A) and B) and/or C)
D) from 0.001 to 50 parts by weight, preferably from 9 to 35 parts by weight, of at least one flame retardant.
Flame retardants that can be used in component D) are commercially available organic halogen compounds with synergists or are commercially available organic nitrogen compounds or are organic/inorganic phosphorus compounds individually or in a mixture. It is also possible to use

mineral flame retardant additives such as magnesium hydroxide or Ca Mg carbonate hydrates (e.g. DE-A 4 236 122 (= CA 2 109 024 Al)). It is also possible to use salts of aliphatic or of aromatic sulphonic acids. Examples which may be mentioned of halogen-containing, in particular brominated and chlorinated compounds are: ethylene-l,2-bistetrabromophthalimide, epoxidized tetrabromobisphenol A resin, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, pentabromopolyacrylate, brominated polystyrene and decabromodiphenyl ether. Examples of suitable organophosphorus compounds are the phosphorus compounds according to WO-A 98/17720 (= US 6 538 024), e.g. triphenyl phosphate (TPP), resorcinol bis(diphenyl phosphate) (RDP) and the oligomers derived therefrom, and also bisphenol A bis(diphenyl phosphate) (BDP) and the oligomers derived therefrom, and organic and inorganic phosphonic acid derivatives and salts thereof, organic and inorganic phosphim'c acid derivatives and salts thereof, in particular metal dialkylphosphinates, e.g. aluminium tris[dialkylphosphinates] or zinc bis[dialkylphosphinates] and moreover red phosphorus, phosphites, hypophosphites, phospine oxides, phosphazenes, melamine pyrophosphate and mixtures of these. Nitrogen compounds which can be used are those from the group of the allantoin derivatives, cyanuric acid derivatives, dicyandiamide derivatives, glycoluril derivatives, guanidine derivatives, ammonium derivatives and melamine derivatives, preferably allantoin, benzoguanamine, glycoluril, melamine, condensates of melamine, e.g. melem, melam or melom and, respectively, higher-condensation-level compounds of this type and adducts of melamine with acids, e.g. with cyanuric acid (melamine cyanurate), phosphoric acid (melamine phosphate) or with condensed phosphoric acids (e.g. melamine polyphosphate). Examples of suitable synergists are antimony compounds, in particular antimony trioxide, sodium antimonate and antimony pentoxide, zinc compounds, e.g. zinc borate, zinc oxide, zinc phosphate and zinc sulphide, tin compounds, e.g. tin stannate and tin borate, and also magnesium compounds, e.g. magnesium oxide, magnesium carbonate and magnesium borate. The materials known as carbonizers can also be added to the flame retardant, examples being phenol-formaldehyde resins, polycarbonates, polyphenyl ethers, polyimides, polysulphones, polyether sulphones, polyphenylene sulphides and polyether ketones, antidrip agents, such as tetrafluoro-ethylene polymers.
In another alternative preferred embodiment, the thermoplastic moulding compositions can also comprise, in addition to components A) and B) and/or C) and/or D)
E) from 0.001 to 80 parts by weight, preferably from 2 to 40 parts by weight, particularly preferably from 4 to 19 parts by weight, of at least one elastomer modifier.
The elastomer modifiers to be used as component E) comprise one or more graft polymers of

E.I from 5 to 95% by weight, preferably from 30 to 90% by weight, of at least one vinyl monomer
E.2 from 95 to 5% by weight, preferably from 70 to 10% by weight, of one or more graft bases with glass transition temperatures The median particle size (d50 value) of the graft base E.2 is generally from 0.05 to 10 um, preferably from 0.1 to 5 urn, particularly preferably from 0.2 to 1 (am.
Monomers E. 1 are preferably mixtures composed of
E. 1.1 from 50 to 99% by weight of vinylaromatics and/or ring-substituted vinylaromatics (such as styrene, a-methyl styrene, p-methyl styrene, p-chlorostyrene) and/or (Ci-Cg)-alkyl methacrylates (e.g. methyl methacrylate, ethyl methacrylate) and
E.I.2 from 1 to 50% by weight of vinyl cyanides (unsaturated nitriles, such as acrylonitrile and methacrylonitrile) and/or (Ci-C8)-alkyl (meth)acrylate (e.g. methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and/or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (e.g. maleic anhydride and N-phenylmaleimide).
Preferred monomers E.I.I have been selected from at least one of the monomers styrene, a-methylstyrene and methyl methacrylate, and preferred monomers E.I.2 have been selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
Particularly preferred monomers are E. 1.1 styrene and E. 1.2 acrylonitrile.
Examples of suitable graft bases E.2 for the graft polymers to be used in the elastomer modifiers E) are diene rubbers, EP(D)M rubbers, i.e. rubbers based on ethylene/propylene and, if appropriate, diene, acrylate rubbers, polyurethane rubbers, silicone rubbers, chloroprene rubbers and ethylene-vinyl acetate rubbers.
Preferred graft bases E.2 are diene rubbers (e.g. based on butadiene, isoprene, etc.) or mixtures of diene rubbers, or are copolymers of diene rubbers or of their mixtures with further copolymerizable monomers (e.g. according to E. 1.1 and E. 1.2), with the proviso that the glass transition temperature of component E.2 is Pure polybutadiene rubber is particularly preferred as graft base E.2.
Examples of particularly preferred polymers E) are ABS polymers (emulsion, bulk and suspension

ABS), as described by way of example in DE-A 2 035 390 (= US-A 3 644 574) or in DE-A 2248242 (=GB-A 1 409 275) or in Ullmann, Enzyklopadie der Technischen Chemie [Encyclopaedia of Industrial Chemistry], Vol. 19 (1980), pp. 280 et seq. The gel content of the graft base E.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).
The elastomer modifiers or graft copolymers E) are prepared via free-radical polymerization, e.g. via emulsion, suspensions, solution or bulk polymerization, preferably via emulsion or bulk
nnlvmftnVatinn
polymerization.
Other particularly suitable graft rubbers are ABS polymers which are prepared via redox initiation using an initiator system composed of organic hydroperoxide and ascorbic acid according to US-A 4937285.
Because it is known that the graft monomers are not necessarily entirely grafted onto the graft base during the grafting reaction, products which are obtained via (co)polymerization of the graft monomers in the presence of the graft base and are produced concomitantly during the work-up are also graft polymers E according to the invention.
Suitable acrylate rubbers are based on graft bases E.2 which are preferably polymers composed of alkyl acrylates, if appropriate with up to 40% by weight, based on E.2, of other polymerizable, ethylenically unsaturated monomers. Among the preferred polymerizable acrylic esters are Q-Cs-alkyl esters, such as methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably halo-Ci-Cg-alkyl esters, such as chloroethyl acrylate, and also mixtures of these monomers.
For crosslinking, monomers having more than one polymerizable double bond can be copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having from 3 to 8 carbon atoms and of unsaturated monohydric alcohols having from 3 to 12 carbon atoms, or of saturated polyols having from 2 to 4 OH groups and from 2 to 20 carbon atoms, e.g. ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, e.g. trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, such as di- and trivinylbenzenes; and also triallyl phosphate and diallyl phthalate.
Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least 3 ethylenically unsaturated groups.
Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes. The amount of the crosslinking monomers is preferably from 0.02 to 5% by weight, in particular from 0.05 to 2% by weight, based

on the graft base E.2.
In the case of cyclic crosslinking monomers having at least 3 ethylenically unsaturated groups, it is advantageous to restrict the amount to below 1% by weight of the graft base E.2.
Examples of preferred "other" polymerizable, ethylenically unsaturated monomers which can serve alongside the acrylic esters, if appropriate, for preparation of the graft base E.2 are acrylonitrile, styrene, a-methylstyrene, acrylamides, vinyl d-Ce-alkyl ethers, methyl methacrylate, butadiene. Acrylate rubbers preferred as graft base E.2 are emulsion polymers whose gel content is at least 60% by weight.
Further suitable graft bases according to E.2 are silicone rubbers having sites active for grafting purposes, as described in DE-A 3 704 657 (= US 4 859 740), DE-A 3 704 655 (= US 4 861 831), DE-A 3 631 540 (= US 4 806 593) and DE-A 3 631 539 (= US 4 812 515).
Alongside elastomer modifiers based on graft polymers, it is also possible to use, as component E), elastomer modifiers not based on graft polymers but having glass transition temperatures In another alternative preferred embodiment, the thermoplastic moulding compositions can also comprise, in addition to components A) and B), and/or C) and/or D) and/or E)
F) from 0.001 to 80 parts by weight, preferably from 10 to 70 parts by weight, particularly preferably from 20 to 60 parts by weight, of a polycarbonate.
Preferred polycarbonates are those homopolycarbonates and copolycarbonates based on bisphenols of the general formula (II),
HO-Z-OH (II)
in which Z is a divalent organic radical having from 6 to 30 carbon atoms and containing one or more aromatic groups.
Bisphenols of the formula (III) are preferred
(Figure Remove)

in which
A is a single bond, Cl-C5-alkylene, C2-C5-alkylidene, C5-C6-cycloalkylidene, -0-, -SO-, -CO-, -S-, -S02-, or is C6-C12-arylene, onto which further aromatic rings, if appropriate containing heteroatoms, may have been condensed,
or A is a radical of the formula (IV) or (V)
(Figure Remove)

in which
X is in each case Ci-C^-alkyl, preferably methyl or halogen, preferably chlorine and/or bromine,
n is in each case, independently of the others, 0, 1 or 2,
p is 1 or 0,
R7 and R8, individually selectable for each Y, and independently of each other, are hydrogen or Ci-C6-alkyl, preferably hydrogen, methyl or ethyl,
Y is carbon and

m is a whole number from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom Y, R7 and R8 are simultaneously alkyl.
Examples of bisphenols according to the general formula (II) are bisphenols belonging to the following groups: dihydroxybiphenyls, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, indanebisphenols, bis(hydroxyphenyl) sulphides, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulphones, bis(hydroxyphenyl) sulphoxides and ct,a'-bis(hydroxyphenyl)diisopropylbenzenes.
Other examples of bisphenols according to the general formula (II) are derivatives of the bisphenols mentioned, e.g. obtainable via alkylation or halogenation on the aromatic rings of the bisphenols mentioned.
Examples of bisphenols according to the general formula (II) are in particular the following
compounds: hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl) sulphide,
bis(4-hydroxyphenyl) sulphone, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3,5-dimethyl-4-
hydroxyphenyl) sulphone, l,l-bis(3,5-dimethyl-4-hydroxyphenyl)-p/m-diisopropylbenzene,
1,1 -bis(4-hydroxyphenyl)-l -phenylethane, 1,1 -bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane,
1,1 -bis(4-hydroxyphenyl)-3 -methylcyclohexane, 1,1 -bis(4-hydroxyphenyl)-3,3 -dimethylcyclohexane, 1,1 -bis(4-hydroxyphenyl)-4-methylcyclohexane, 1,1 -bis(4-hydroxyphenyl)cyclohexane, 1,1 -bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis-(4-hydroxyphenyl)propane (i.e. bisphenol A), 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, a,a'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, a,a'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (i.e. bisphenol M), a,a'-bis(4-hydroxyphenyl)-p-diisopropylbenzene and indanebisphenol.
Polycarbonates to be used with particular preference according to the invention as component F) are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
The bisphenols according to the general formula (II) and described can be prepared by known processes, e.g. from the corresponding phenols and ketones.
The bisphenols mentioned and processes for their production are described by way of example in the monograph H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9,

pp. 77-98, Interscience Publishers, New York, London, Sydney, 1964.
l,l-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and its preparation is described by way of example in US-A 4 982 014.
Indanebisphenols can by way of example be prepared from isopropenylphenol or from its derivatives or from dimers of isopropenylphenol or of its derivatives in the presence of a Friedel-Craft catalyst in organic solvents.
Polycarbonates can be prepared by known processes. Examples of suitable processes for preparation of polycarbonates are preparation from bisphenols using phosgene by the interfacial process or from bisphenols using phosgene by the homogeneous-phase process known as the pyridine process, or from bisphenols using carbonic esters by the melt transesterification process. These preparation processes are described by way of example in H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, pp. 31-76, Interscience Publishers, New York, London, Sydney, 1964.
In the preparation of polycarbonate, it is preferable to use raw materials and auxiliaries with a very low level of contaminants. In particular in preparation by the melt transesterification process, the intention is that the bisphenols used and the carbonic acid derivatives used have minimal content of alkali metal ions and alkaline earth metal ions. These pure raw materials are obtainable by way of example by recrystallizing, washing or distilling the carbonic acid derivatives, e.g. carbonic esters, and the bisphenols.
The weight-average molar mass (M,_w), which by way of example can be determined by an ultracentrifuge method or by scattered-light measurement, is preferably from 10 000 to 200 000 g/mol for the polycarbonates suitable according to the invention. Their weight-average molar mass is particularly preferably from 12 000 to 80 000 g/mol, with particular preference from 20 000 to 35 000 g/mol.
By way of example, it is possible to adjust the average molar mass of the inventive polycarbonates in a known manner via an appropriate amount of chain terminators. The chain terminators may be used individually or in the form of a mixture of various chain terminators.
Suitable chain terminators are either monophenols or else monocarboxylic acids. Examples of suitable monophenols are phenol, p-chlorophenol, p-tert-butylphenol, cumylphenol or 2,4,6-tribromophenol, and also long-chain alkylphenols, e.g. 4-(l,l,3,3-tetramethylbutyl)phenol or monoalkylphenols and, respectively, dialkylphenols having a total of from 8 to 20 carbon atoms in

the alkyl substituents, e.g. 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2-(3,5-dimethylheptyl)phenol or 4-(3,5-dimethylheptyl)phenol. Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halobenzoic acids.
Preferred chain terminators are phenol, p-tert-butylphenol, 4-(l,l,3,3-tetramethylbutyl)phenol and cumylphenol.
The amount of chain terminators is preferably from 0.25 to 10 mol%, based on the entirety of the bisphenols used in each case.
The polycarbonates used according to the invention may have branching in a known manner, and specifically preferably via incorporation of branching agents whose functionality is three or higher. Examples of suitable branching agents are those having three or more than three phenolic groups or those having three or more than three carboxylic acid groups.
Examples of suitable branching agents are phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 1 !3,5-tri(4-hydroxyphenyl)benzene, 1,1,1 -tris(4-hydroxyphenyl)ethane, tri(4-hydroxyphenyl)phenylmethane, 2,2-bis [4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, 2,6-bis(2-hydroxy-5 '-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, hexa(4-(4-hydroxyphenylisopropyl)phenyl)terephthalic ester, tetra(4-hydroxyphenyl)methane, tetra(4-(4-hydroxyphenylisopropyl)phenoxy)methane and l,4-bis(4',4"-dihydroxytriphenylmethyl)benzene, and also 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride, 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole, trimesyl trichloride and a,a',a"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene.
Preferred branching agents are l,l,l-tris(4-hydroxyphenyl)ethane and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.
The amount of any branching agents to be used is preferably from 0.05 mol% to 2 mol%, based on the molar amount of bisphenols used.
By way of example, if the polycarbonate is prepared by the interfacial process, the branching agents can be used as an initial charge with the bisphenols and the chain terminators in the aqueous alkaline phase, or can be added dissolved in an organic solvent together with the carbonic acid derivatives. In the case of the transesterification process, the branching agents are preferably metered in together with the dihydroxyaromatics or bisphenols.
Preferred catalysts to be used during the preparation of polycarbonate by the melt transesterification

process are the phosphonium salts and ammonium salts known from the literature.
Copolycarbonates can also be used. For the purposes of the invention, copolycarbonates are in particular polydiorganosiloxane-polycarbonate block copolymers whose weight-average molar mass (M,_w) is preferably from 10000 to 200000 g/mol, particularly preferably from 20000 to 80 000 g/mol (determined via gel chromatography after prior calibration via light-scattering measurement or ultracentrifuge method). The content of aromatic carbonate structural units in the polydiorganosiloxane-polycarbonate block copolymers is preferably from 75 to 97.5 parts by weight, particularly preferably from 85 to 97 parts by weight. The content of polydiorganosiloxane structural units in the polydiorganosiloxane-polycarbonate block copolymers is preferably from 25 to 2.5 parts by weight, particularly preferably from 15 to 3 parts by weight. The polydiorgano-siloxane-polycarbonate block copolymers can by way of example be prepared starting from polydiorganosiloxanes which contain a,ra-bishydroxyaryloxy end groups, their average degree of polymerization preferably being Pn - from 5 to 100, particularly preferably Pn = from 20 to 80.
The polydiorganosiloxane-polycarbonate block polymers can also be a mixture composed of polydiorganosiloxane-polycarbonate block copolymers with conventional polysiloxane-free, thermoplastic polycarbonates, the total content of polydiorganosiloxane structural units in this mixture preferably being from 2.5 to 25 parts by weight.
These polydiorganosiloxane-polycarbonate block copolymers are characterized in that their polymer chain contains on the one hand aromatic carbonate structural units (VI) and on the other hand contains polydiorganosiloxanes (VII) containing aryloxy end groups,
O
—O-Ar-O-C-O-Ar-O-
R9
-O-Ar-O—(Si-0)j—O-Ar-O-R10
in which
Ar is identical or different difunctional aromatic radicals and
R9 and R10 are identical or different and are linear alkyl, branched alkyl, alkenyl, halogenated linear alkyl, halogenated branched alkyl, aryl or halogenated aryl, preferably methyl, and

1 is the average degree of polymerization which is preferably from 5 to 100, particularly
preferably from 20 to 80.
Alkyl in the above formula (VII) is preferably Ci-C2o-alkyl, and alkenyl in the above formula (VII) is preferably C2-C6-alkenyl; aryl in the above formulae (VI) or (VII) is preferably Ce-Cu-aryl. Halogenated in the above formulae means partially or completely chlorinated, brominated or fluorinated.
Examples of alkyl radicals, alkenyl radicals, aryl radicals, halogenated alkyl radicals and halogenated aryl radicals are methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, chloromethyl, perfluorobutyl, perfluorooctyl and chlorophenyl.
These polydiorganosiloxane-polycarbonate block copolymers and their preparation are prior art and are described by way of example in US-A 3 189 662.
By way of example, preferred polydiorganosiloxane-polycarbonate block copolymers can be prepared by reacting polydiorganosiloxanes containing a,co-bishydroxyaryloxy end groups together with other bisphenols, if appropriate with concomitant use of branching agents in the conventional amounts, e.g. by the interfacial process (as described by way of example hi H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, pp. 31-76, Interscience Publishers, New York, London, Sydney, 1964). The polydiorganosiloxanes containing a,co-bishydroxyaryloxy end groups and used as starting materials for this synthesis, and their preparation, are prior art and are described by way of example in US-A 3419 634.
Conventional additives, e.g. mould-release agents, stabilizers and/or flow agents can be admixed in the melt with the polycarbonates or applied to their surface. By this stage, prior to compounding with the other components of the inventive moulding compositions, the polycarbonates to be used preferably comprise mould-release agents.
hi another alternative preferred embodiment, the thermoplastic moulding compositions can also comprise, in addition to components A) and B), and/or C) and/or D) and/or E) and/or F)
G) from 0.001 to 10 parts by weight, preferably from 0.05 to 5 parts by weight, particularly preferably from 0.1 to 3.5 parts by weight, of other conventional additives.
Examples of conventional additives of component G) are stabilizers (e.g. UV stabilizers, heat stabilizers, gamma-ray stabilizers), antistatic agents, flow aids, mould-release agents, further fire-protection additives, emulsifiers, nucleating agents, plasticizers, lubricants, dyes, pigments and additives for increasing electrical conductivity. The additives mentioned and further suitable

additives are described by way of example in Gachter, Muller, Kunststoff-Additive [Plastics Additives], 3rd Edition, Hanser-Verlag, Munich, Vienna, 1989 and in Plastics Additives Handbook, 5th Edition, Hanser-Verlag, Munich, 2001. The additives may be used alone or in a mixture, or in the form of masterbatches.
Examples of stabilizers which can be used are organophosphorus compounds, phosphites, sterically hindered phenols, hydroquinones, aromatic secondary amines, e.g. diphenylamines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, and also various substituted representatives of these groups and mixtures thereof.
Examples of pigments that can be used are titanium dioxide, zinc sulphide, ultramarine blue, iron oxide, carbon black, phthalocyanines, quinacridones, perylenes, nigrosin and anthraquinones.
Examples of nucleating agents which can be used are sodium phenylphosphinate or calcium phenylphosphinate, aluminium oxide, silicon dioxide, and also preferably talc.
Examples of lubricants and mould-release agents which can be used are ester waxes, pentaerytritol tetrastearate (PETS), long-chain fatty acids (e.g. stearic acid or behenic acid), salts thereof (e.g. Ca stearate or Zn stearate), and also amide derivatives (e.g. ethylenebisstearylamide) or montan waxes (mixtures composed of straight-chain, saturated carboxylic acids having chain lengths of from 28 to 32 carbon atoms). Examples of plasticizers which can be used are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N-(n-butyl)benzenesulphonamide.
The component G) used can also be polyolefins, preferably polyethylene and/or polypropylene. Low-molecular-weight polyethylene waxes and low-molecular-weight polypropylene waxes are particularly preferred.
Additives which can be added to increase electrical conductivity are carbon blacks, conductivity blacks, carbon fibrils, nanoscale graphite fibres and nanoscale carbon fibres, graphite, conductive polymers, metal fibres, and also other conventional additives for increasing electrical conductivity. Nanoscale fibres which can preferably be used are those known as "single-wall carbon nanotubes" or "multiwall carbon nanotubes" (e.g. from Hyperion Catalysis).
According to the invention, the following combinations of the components are preferred
AB; A,B,C; A,B,D; A,B,E; A,B,F; A,B,G; A,B,C,D; A,B,C,E; A,B,C,F; A,B,C,G; A,B,D,E; A,B,D,F; A,B,D,G; A,B,E,F; A,B,E,G; A,B,F,G; A,B,C,D,E; A,B,C,D,F; A,B,C,D,G; A,B,C,E,F; A,B,C,E,G; A,B,C,F,G; A,B,E,F,G; A,B,D,E,F; A,B,D,E,G; A,B,D,F,G; A,B,C,D,E,F: A,B,C,D,E,G:

A,B,D,E,F,G; A,B,C,E,F,G; A,B,C,D,F,G; A,B,C,D,E,F,G.
However, the present invention also provides a process for preparation of the inventive thermoplastic moulding compositions. This takes place by known processes via mixing of the components. The mixing of the components takes place via mixing of the appropriate proportions by weight of the components. The mixing of the components preferably takes place at temperatures of from 220 to 330°C via combining, mixing, kneading, extruding or rolling of the components together. It can be advantageous to premix individual components. It can moreover be advantageous to produce mouldings or semifinished products directly from a physical mixture (dry blend) prepared at room temperature (preferably from 0 to 40°C) and composed of premixed components and/or of individual components.
The invention further provides the mouldings to be produced from the inventive moulding compositions comprising
A) from 99 to 10 parts by weight, preferably from 98 to 30 parts by weight, particularly
preferably from 97 to 60 parts by weight, of at least one thermoplastic polyester, preferably
of a polyalkylene terephthalate and
B) from 1 to 20 parts by weight, preferably from 2 to 15 parts by weight, particularly
preferably from 3 to 9 parts by weight, of at least one copolymer composed of at least one
olefin, preferably cc-olefin and of at least one methacrylic ester or acrylic ester of an
aliphatic alcohol having from 1 to 4 carbon atoms, the MFI (measured at 190°C for 2.16 kg;
DIN EN ISO 1133) of the copolymer B) being not less than 50 g/10 min, and preferably
being from 80 to 900 g/10 min.
The following surprising advantages are exhibited by the inventive moulding compositions in comparison with a moulding composition corresponding to the prior art:
markedly improved flowability, in particular at shear rates relevant for thermoplastics processing;
improved toughness;
improved outer fibre strain, in particular after hydrolysis;
lower density;
reduced shrinkage;

improved hydrolysis resistance; improved surface quality of the mouldings.
The inventive moulding compositions can be processed by conventional processes, for example via injection moulding or extrusion, to give mouldings or semifinished products. Examples of semifinished products are foils and sheets. Processing by injection moulding is particularly preferred.
The mouldings or semifinished products to be produced according to the invention from the thermoplastic moulding compositions can be small or large parts and by way of example can be used in the motor vehicle, electrical, electronics, telecommunications, information technology, or computer industry, in the household, in sports, in medicine, or in the entertainment industry. In particular, the inventive moulding compositions can be used for applications which require high melt flowability. An example of these applications is what is known as thin-wall technology, in which the wall thicknesses of mouldings to be produced from the moulding compositions are less than 2.5 mm, preferably less than 2.0 mm, particularly preferably less than 1.5 mm and most preferably less than 1.0 mm. Another example of these applications is cycle time reduction, for example via a reduction in processing temperature. Another application example is the processing of the moulding compositions by way of what are known as multitooling systems, in which material is charged by way of a runner system to at least 4 moulds, preferably at least 8 moulds, particularly preferably at least 12 moulds, most preferably at least 16 moulds, in an injection moulding procedure.

Examples:
Component A: Linear polybutylene terephthalate (Pocan® B 1300, commercially available product from Lanxess Deutschland GmbH, Leverkusen, Germany) with intrinsic viscosity of about 0.93 cm3/g (measured in phenol: 1,2-dichlorobenzene = 1:1 at 25°C)
Component B: Copolymer composed of ethene and n-butyl acrylate with ethene content of 70-74% by weight and with an MFI of 175 (Lotryl® 28 BA 175 from Atofina Deutschland, Dusseldorf) (Arkema GmbH since October 2004) [CAS No. 25750-84-9]
Component C: Glassfibre sized with silane-containing compounds and with a diameter of 10 jam (CS 7967, commercially available product from Lanxess N.V., Antwerp, Belgium)
Component G:
The following components familiar for use in thermoplastic polyesters were used as further additives:
Nucleating agent: Amounts of from 0.01 to 0.59% by weight of talc [CAS No. 14807-96-6].
Heat stabilizer: Amounts of from 0.01 to 0.59% by weight of conventional stabilizers based on phenyl phosphites.
Mould-release agent: Amounts of from 0.1 to 0.68% by weight of commercially available fatty acid esters.
The nature and amount of each of the further additives (component G) used are the same for the comparative example and inventive example, specifically using G = 0.7%.
The compositions based on PBT were compounded in a ZSK 32 (Werner and Pfleiderer) twin-screw extruder at melt temperatures of from 270 to 275 °C to give moulding compositions, and the melt was discharged into a water bath and then pelletized.
The test specimens for the tests listed in the table were injection moulded in an Arburg 320-210-500 injection moulding machine at a melt temperature of about 260°C and at a mould temperature of about 80°C:
- 80 x 10 x 4 mm3 test specimens (to ISO 178)
- 60 x 60 x 2 mm3 plaques for shrinkage measurement to ISO 294-4
The injection pressure is the internal mould pressure applied in the vicinity of the gate in order to fill

the mould cavity. In the curve of pressure as a function of time it is a characteristic inflection point between the mould-filling and compaction phase, and can be determined by way of process data capture. It was determined for the comparative example and for the inventive example during the injection moulding of flat specimens (80 x 10 x 4 mm3).
With the exception of the viscosity measurements, all of the tests were carried out on the abovementioned test specimens.
Flexural test to determine flexural modulus, flexural strength and outer fibre strain to DIN / EN / ISO 178.
Impact resistance: IZOD method to ISO 180 1U at room temperature and at -30°C.
Shrinkage: To determine shrinkage properties, standardized sheets of dimension 60 mm x 60 mm x 2 mm (ISO 294-4) are injection moulded. Longitudinal and transverse shrinkage is determined both in terms of moulding shrinkage and in terms of after-shrinkage, via subsequent measurement. Moulding shrinkage and after-shrinkage together give the total shrinkage.
Density was determined by the flotation method on test specimens to DIN EN ISO 1183-1.
Melt viscosity was determined to DIN 54811 / ISO 11443 at the stated shear rate and temperature, using Viscorobo 94.00 equipment from Gottfert after drying of the pellets at 120°C for 4 hours in a vacuum dryer.
Hydrolysis:
To measure hydrolysis resistance, test specimens produced from the inventive moulding compositions were stored at 100°C and 100% humidity in a steam sterilizer. After 5 and after 10 days of hydrolysis, impact resistance was measured and the flexural test was carried out.
Surface: Test specimens of dimension 60 mm x 60 mm x 2 mm were used for surface appraisal and visual surface assessment. Decisive criteria for judgement were gloss, smoothness, colour and uniform surface structure.

Table

Comparison Inventive example
Component A [%] 69.3 64.3
Component B r%i _ 5.0
Component C [%] 30.0 30.0
Component G r%i 0.7 0.7
Injection pressure [bar] 207 179
Melt viscosity (260°C, 1000 s"1) [Pas] 208 153
Melt viscosity (260°C, 1500 s'1) [Pas] 176 125
Melt viscosity (280°C, 1000 sl) [Pasl 127 107
Melt viscosity (280°C, 1500 s'1) [Pas] 109 89
Izod impact resistance (ISO 180/1U, RT) [kJ/m2] 55 58
Izod impact resistance (ISO 180/1U, RT) after 5 days of hydrolysis [kJ/m2] 25 37
Izod impact resistance (ISO 180/1U, RT) after 10 days of hydrolysis [kJ/m2] 15 28
Izod impact resistance (ISO 180/1U, -30°C) [kJ/m2! 56 70
Total shrinkage (1 h/150°C) longitudinal transverse [%] 0.48 1.30 0.45 1.09
Flexural test: Flexural strength Outer fibre strain for flexural strength Flexural modulus [MPa]
[%] [MPal 217 3.4 9016 196 3.4 8316
Flexural test after 5 days of hydrolysis: Flexural strength Outer fibre strain for flexural strength Flexural modulus [MPa]
[%] [MPa] 158 2.2 8676 169 2.6 8055
Flexural test after 10 days of hydrolysis: Flexural strength Outer fibre strain for flexural strength Flexural modulus [MPa]
[%] [MPa] 121 1.7 8374 138 2.0 8005
Density [g/cm3! 1.53 1.49
Surface quality good very good

WE CLAIM;
1. A homogeneous process for the hydrogenation of dicarboxylic acids and/or
anhydrides in the presence of a catalyst comprising:
(a) ruthenium, rhodium, iron, osmium or palladium; and
(b) an organic phosphine of the kind such as herein described;
wherein the hydrogenation is carried out in the presence of at least 1% by weight water and wherein the reaction is carried out at a pressure of from 500 psig to 2000 psig and a temperature of from 200°C to 300°C such that from 1 mol to 10 mol of hydrogen are used to strip 1 mole of product from the reactor.
2. The process as claimed in claim 1 wherein the process is a continuous process
comprising the steps of:
(a) feeding the dicarboxylic acid and/or anhydride to the hydrogenation reactor;
(b) hydrogenating the dicarboxylic acid and/or anhydride;
(c) recovering the product in an hydrogen stream;
(d) separating the product from the hydrogen stream;
(e) recycling the hydrogen stream to the reactor;
(f) separating any removed catalyst and recycling the catalyst to the reactor, and
(g) recovering the product.

3. The process as claimed in claim 1 or 2 wherein the dicarboxylic acid and/or anhydride is a C4 dicarboxylic acid or anhydride such that the process is a process for the production of butanediol, tetrahydrofuran and/or -butyrolactone.
4. The process as claimed in claim 3, wherein any  -butyrolactone produced in the hydrogenation reaction is recycled to the hydrogenation reactor.
5. The process as claimed in claim 3 or 4 wherein the C4 dicarboxylic acid or anhydride is fumaric acid, maleic anhydride, maleic acid, succinic acid or succinic anhydride.
6. The process as claimed in any one of claims 1 to 5 wherein the water is present as the solvent for the reaction.

7. The process as claimed in any one of Claims 1 to 5 wherein one or both of the reactants or the product are the solvent for the catalyst.
8. The process as claimed in claim 7 wherein a solvent is used and the water is present as an additive in the solvent.
9. The process as claimed in any one of claims 1 to 5 wherein the water is produced in situ as a by-product of the hydrogenation reaction.
10. The process as claimed in any one of claims 1 to 9 wherein the reaction takes place in more than one reactor and the reactors are operated in series.
11. The process as claimed in any one of claims 1 to 9 wherein the reaction is carried out at a pressure of 900 psig.
12. The process as claimed in any one of claims 1 to 10 wherein the reaction is carried out at a temperature of 240°C to 250°C.
13. The process as claimed in any one of claims 1 to 12 the catalyst is a ruthenium/phosphine catalyst.
14. The process as claimed in any one of claims 1 to 13 wherein, the ruthenium is present in an amount of from 0.0001 to 5 mol as ruthenium per liter of reaction solution.
15. The process as claimed in any one of claims 1 to 14 wherein the phosphine is tridentate phosphine.
16. The process as claimed in any one of claims 1 to 14 wherein the phosphine is selected from trialkylphosphines, dialkylphosplines, monoalkylphosphines, triarylphosphines, diarylphosphine, monoarylphosphines, diarylmonoalkyl phosphines and dialkylmonoaryl phosphines.
17. The process as claimed in claim 16, wherein the phosphine is selected from tris-1,1,1 -(diphenylphosphinomethyl)methane, tris-1,1,1 -(diphenylphosphinomethyl)-
ethane. tris-1.1.1- (diphenylphosphinomethyl)propane, tris-1,1,1-

(diphenylphosphinomethyl)butane, tris-1,1,1-
(diphenylphosphinomethyl)2,2dimethylpropane, tris-l,3,5-(diphenylphosphino-
methyl)cyclohexane, tris-1,1,1 - (dicyclohexylphosphinomethyl)ethane, tris-1,1,1 -
(dimethylphosphinomethyl)ethane, tris-1,1,1 - (diethylphosphinomethyl)ethane, 1,5,9-
triethyl-1,5-9- triphosphacyclododecane, 1,5,9-triphenyl- 1,5-9-
triphosphacyclododecane, bis(2-diphylephosphinoethyl)phenylphosphine, bis- 1,2-(diphenyl phosphino)ethane, bis-1 ,3-(diphenyl phosphino)propane, bis-l,4-(diphenyl phosphino)butane, bis-l,2-(dimethyl phosphino)ethane, bis-1,3-(diethyl phosphino)propane, bis-l,4-(dicyclohexyl phosphino)butane, tricyclohexylphosphine, trioctyl phosphine, trimethyl phosphine, tripyridyl phosphine, triphenylphosphine.
18. A process as claimed in claim 16, wherein the phosphine is selected from tris-1,1,1-(diarylphosphinomethyl)alkane aid tris-1,1,1 -(dialkylphosphinomethyl)alkane.
19. The process as claimed in any one of claims 1 to 18 wherein, the phosphine is present in an amount of from 0.0001 to 5 mol as phosphine per liter of reaction solution.
20. The process as claimed in any one of claims 1 to 19 wherein the catalyst is regenerated in the presence of water and hydrogen.

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Patent Number

271301

Indian Patent Application Number

2118/DELNP/2006

PG Journal Number

08/2016

Publication Date

19-Feb-2016

Grant Date

15-Feb-2016

Date of Filing

19-Apr-2006

Name of Patentee

DAVY PROCESS TECHNOLOGY LIMITED

Applicant Address

20 EASTBOURNE TERRACE, LONDON, W2 6LE, ENGLAND

Inventors:

#	Inventor's Name	Inventor's Address
1	MICHAEL ANTHONY WOOD	28 FIR TREE CLOSE, HILTON, YARM, TS15 9JZ, GREAT BRITAIN
2	SIMON PETER CRABTREE	4 DURHAM ROAD, DURHAM, DHI 5AL, GREAT BRITAIN.
3	DEREK VINCENT TYERS	THE BARN, COWESBY, THIRSK, NORTH YORKSHIRE Y07 2JL, GREAT BRITAIN.

PCT International Classification Number

C07C 29/149

PCT International Application Number

PCT/GB2004/004397

PCT International Filing date

2004-10-15

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	0325526.2	2003-10-31	Germany