TW201333103A - Process for the preparation and stabilisation of impact-modified polycarbonate compositions using dilute solutions of acidic compounds - Google Patents

Abstract

The present invention relates to a process for the preparation of stabilised impact-modified polycarbonate compositions using dilute aqueous acidic solutions, and to the compositions so prepared themselves.

Description

Method for producing and stabilizing impact-modified polycarbonate compositions using a dilute solution of an acid compound

The present invention relates to a process for producing and stabilizing an impact-modified polycarbonate composition using a dilute solution of an acid compound, and to the composition itself prepared therefrom.

According to the kneading method of the present invention, the preparation of the impact-modified polycarbonate composition can have the advantages of combining hydrolytic stability and high processing stability, and the above advantages can be affected by different media. It is known to measure streaks, degradation of polycarbonate molecular weight, natural color and gloss stability, as well as low-temperature notched impact strength, elongation at break and stress crack resistance. In each case, the composition is at a high process temperature. It is prepared and considered.

In the process of polymer, the term "mixing" refers to the preparation of a finished plastic molding composition, and selectively from a variety of polymer materials and selectively added polymer additives, such as fillers. And reinforcing materials, adhesion promoters, lubricants, stabilizers, etc. "Kneading" mainly occurs in kneaders or extruders and includes feeding, melting, dispersing, mixing, degassing, and establishing pressure. Force and other process operations. Curing of the compound is generally carried out after mixing, and is affected by cooling and granulation.

The emulsion polymer used as an impact modifier in the polycarbonate composition is generally worked up in an acidic medium for the purpose of neutralizing a polymerization aid having a basic action, for example, emulsification. Agent. This is necessary to ensure adequate thermal stability of the composition, as it is well known that basic molecules tend to cause thermal degradation of the polycarbonate at process temperatures.

It is often necessary to stabilize the polycarbonate composition by adding an acidic additive such that it contains an emulsified graft polymer as an impact modifier. Especially when the emulsified graft polymer has been used it is in a medium which is alkaline or acidic.

Although the compositions conventionally known in the prior art generally have good processing stability, in the case of application (for example, at temperatures <100 ° C and high humidity), hydrolytic cleavage of polycarbonate is also exhibited. Ideal stability and poor natural color (yellow).

EP-A 900 827 describes an impact modified polycarbonate composition which has improved thermal stability and an emulsifying polymer comprising an alkaline component substantially free of any degraded polycarbonate. According to this application, such a polycarbonate composition which is impact modified with an emulsion polymer derived from the alkaline impurities in its preparation exhibits undesirable processing stability.

Patent EP-A 576 950 A1 and WO-A 2007/065579 describe a composition comprising a polycarbonate and an acrylonitrile-butadiene-styrene (ABS) polymer, wherein the composition contains basic impurities and is polyfunctional. The organic carboxylic acid is stable. The complete molecular weight of the polycarbonate component at high process temperatures The amount has good thermal stability, but the surface of the molded article prepared by injection molding tends to form defects (streaks).

US 2006/0287422 describes a thermoplastic composition comprising a polycarbonate, an impact modifier, a selective vinyl copolymer thereof, a mineral filler and an acid or acid salt, wherein the composition has improved mechanical properties and reduces thermal degradation. Propensity. This application also discloses that the preferred acid as the phosphorus-based compound has a general structural formula of H _m P _t O _n , and particularly may also be phosphoric acid. This application also discloses that the compositions of the present invention can be prepared according to the processes described in the prior art.

An impact modified polycarbonate composition having improved properties of combined hydrolysis and process stability is described in WO-A 2010/063381, the composition of which comprises a polycarbonate, an emulsified graft polymer containing a basic impurity And an acidic phosphorus compound having at least one P-OH functional group. As the acidic phosphorus compound, it has been described as a specific cyclic organic phosphite compound and an inorganic or organic phosphorus compound such as phosphoric acid or a phosphate.

Patent EP 22 57 590 discloses an improved property incorporating natural color, hydrolytic stability and process stability, comprising a polycarbonate and a rubber modified graft polymer prepared therefrom containing a residue of a fatty acid salt emulsion Where the pH of the grafted polymer in the aqueous phase dispersion is greater than 7, and an acidic additive. Hydroxy-functional mono- and polycarboxylic acids and phosphoric acid are disclosed as acidic additives in this application.

For example, when an acidic compound such as citric acid or phosphoric acid is added according to the prior art, the use of an acidic substance in a polycarbonate composition prepared according to the process described in the prior art tends to have disadvantages such as The streaks on the surface of the composition prepared by this composition or the apparent molecular weight degradation and insufficient Satisfactory mechanical properties.

None of the persons mentioned in the present invention describe a process for the preparation of a stable polycarbonate composition according to the present invention.

Accordingly, it is an object of the present invention to provide a method for making a stabilized impact modified polycarbonate composition without the aforementioned disadvantages.

Surprisingly, it has been found that the impact modified polymer composition prepared according to the process of the present invention has a desired property profile including: A in each case, based on the composition A+B+ 10 to 98 parts by weight, preferably 30 to 90 parts by weight, more preferably 50 to 80 parts by weight, particularly preferably 55 to 65 parts by weight, at least one selected from the group consisting of C + D + E a polymer of a group consisting of a family of polycarbonates, aromatic polyester carbonates, and aromatic polyesters, and mixtures thereof, in each case, based on a total of 0.5% of the components A+B+C+D+E 50.0 parts by weight, preferably 1 to 30 parts by weight, more preferably 1.5 to 20.0 parts by weight, particularly preferably 1.5 to 5.0 parts by weight of at least one powdered rubber-modified vinyl (co)polymer, In each case, based on 0 to 80 parts by weight, based on the total of the components A+B+C+D+E, preferably 10 to 60 parts by weight, more preferably 15 to 50 parts by weight, particularly preferably 20 to 40 parts by weight of at least one selected from the group consisting of rubber-modified vinyl (co)polymers in the form of granules and rubber-free vinyl (co)polymers. D is, in each case, 0.002 to 0.200 parts by weight, based on the total of the components A+B+C+D+E, preferably 0.005 to 0.100 parts by weight, more preferably 0.005 to 0.050 parts by weight, particularly preferably It is 0.007 to 0.020 parts by weight of at least one Brönsted acid, and E is, in each case, 0.1 to 40.0 parts by weight based on the total of the components A+B+C+D+E, preferably 0.2 to 25.0 parts by weight, more preferably 0.3 to 10.0 parts by weight, particularly preferably 0.5 to 3.0 parts by weight of an additive excluding a commonly added acid, wherein the parts by weight used in the present invention are all composed The sum of the components A+B+C+D+E is normalized as 100, wherein, in the method according to the invention, (i) in the first method step, the concentration is prepared to be 0.3 to 30 wt.%, Preferably, it is from 0.5 to 15 wt.%, more preferably from 0.5 to 8 wt.%, particularly preferably from 1 to 6 wt.% of the solution of the acidic compound D, and (ii) in the second method step, a solution of the acidic compound D and a wholly or partial amount of the graft polymer powder according to the component B, and optionally one or more polycarbonate-ABS groups in part or in whole The powder component of the material is physically blended, and (iii) the prepared mixture is melted, mixed, and dispersed in each other in the mixing unit together with the additional residue component AE of the composition (which is selectively mixed first). Wherein the solvent added to the composition with the acidic compound solution is again removed by applying a low pressure to the degassing zone of the mixing unit, and then the prepared polymer melt is solid by cold and granulation. Chemical.

In a preferred embodiment, in step (ii), in addition to the stabilizer component D, the additional additive according to component E is also mixed with component B.

In a particularly preferred embodiment, in step (ii), in addition to component D and the optional additional stabilizer according to component E, no other polymer component is mixed with component B in the composition.

In a further preferred embodiment, in step (ii), component B and the acidic compound solution from process step (i) are first mixed prior to the addition of additional powdered components.

Wherein the amount of the component B is more than 10 parts by weight, it is preferred to use only a part amount of B in the step (ii), and a particularly preferred partial amount is 1.5 to 5.0 parts by weight, which is calculated based on the total amount of all the components. .

As the solvent in the step (i), an organic solvent and an inorganic solvent can be used, and an inorganic solvent is preferred.

In a particularly preferred embodiment, the solvent in step (i) is water.

In a further preferred embodiment, the solution of the component D used in the mixture prepared in the step (ii) is not more than 30 parts by weight (calculated based on the total amount of the components B and D in the mixture), in particular It is preferably not more than 20 parts by weight, particularly preferably 10 to 20 parts by weight. In a preferred embodiment, the mixture produced in step (ii) is combined with the total amount of components A to E or the remaining portion thereof after step (ii), together with thermal energy in the mixing unit. / or a supply of mechanical energy to be heated to 200 ° C to 350 ° C, preferably from 220 ° C to 320 ° C, particularly preferably from 240 ° C to 300 ° C, followed by melting, mixing, dispersing in each other, and subsequently Degassing is performed in the degassing zone of the mixing unit.

- wherein the mixing unit has a melting zone and a mixing zone or a combined melting and mixing zone,

- wherein in step (ii), the amount of all or a selected portion of the resulting mixture and the composition of the components A to D in each case can be metered into the region of the mixing unit (hereinafter referred to as entry) The zone, upstream of the melt zone or otherwise entering the downstream zone of the melt zone, directly enters the premixed melt of the composition of the composition, which is metered into the entry zone of the mixing zone.

- wherein the absolute pressure p _{abs of the} degassing zone established in the mixing unit does not exceed 800 mbar, preferably does not exceed 500 mbar, particularly preferably does not exceed 200 mbar,

- the average residence time in which the composition melt is contacted with the solvent introduced into the process by the mixture prepared in the process step (ii) is preferably limited to a maximum of 90 seconds, particularly preferably a maximum of 60 seconds, particularly The optimum maximum is 30 seconds and the resulting melt is again cooled to solidify as it leaves the mixing unit.

In the context of the present invention, "powder" or "powdered" means a mixture of ingredients or components which are present in a solid state, and wherein the particles have a particle size of less than 2 mm, preferably less than 1 mm, especially less than 0.5 mm.

In the context of the present invention, "granular" means a mixture of components or components which are present in a solid state and which have a particle size of at least 2 mm and generally no more than 10 mm. The granulated particles may be of any desired shape, such as a lenticular shape, a spherical shape or a cylindrical shape.

Ingredient A

Aromatic polycarbonates according to the invention which are suitable according to the invention are known in the literature or can be prepared by processes known in the literature (for the preparation of aromatic polycarbonates, for example, see Schnell, "Chemistry and Physics of Polycarbonates" ", Interscience Publishers, 1964 and DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396; Aromatic polyester carbonates are visible in DE-A 3 077 934).

For example, the reaction of bisphenol with a carbonic acid halide (preferably phosgene) and/or an aromatic dicarboxylic acid dihalide (preferably a benzenedicarboxylic acid dihalide) is based on an interface method, The preparation of the aromatic polycarbonate can be carried out selectively using a chain terminator such as a monophenol and optionally a branching agent having three or more functional groups such as trisphenol or tetraphenol. For example, it is also feasible to prepare a reaction by a melt polymerization method of bisphenol and diphenyl carbonate.

The bisphenol used in the preparation of the aromatic polycarbonate and/or the aromatic polyester carbonate is preferably those having the formula (I) Wherein A is a single bond, C ₁ - to C ₅ -alkylene, C ₂ - to C ₅ -alkylene, C ₅ - to C ₆ -cycloalkylene, -O-, -SO-, -CO -, -S-, -SO ₂ -, C ₆ - to C ₁₂ - extended aryl, and further selectively fused to an aromatic ring containing a hetero atom, or a group of formula (II) or (III) B may in each case be a C ₁ - to C ₁₂ -alkyl group, preferably a methyl group, a halogen, preferably chlorine and /bromine. Each of x may be independent of the others, and is 0, 1 or 2, p is 1 or 0, and R ⁵ and R ^{6 may} each independently be selected from each of X ¹ and each of each other independently of hydrogen, C ₁ - to C ₆ -alkyl, preferably hydrogen, methyl or ethyl, X ¹ is carbon and m is an integer from 4 to 7, preferably 4 or 5, provided that at least one atom is X ¹ , R ⁵ and R ^{6 are} simultaneously an alkyl group.

Preferred diphenols may be hydroquinone, resorcinol, dihydroxydiphenol, bis-(hydroxyphenyl)-C ₁ -C ₅ -alkane, bis-(hydroxyphenyl)-C ₅ -C ₆ cycloalkane, bis-(hydroxyphenyl)ether, bis-(hydroxyphenyl)anthracene, bis-(hydroxyphenyl)ketone, bis(hydroxyphenyl)anthracene, and α,α-bis-(hydroxyphenyl) )-Diisopropyl-benzene and its brominated and/or chlorinated derivatives on the ring.

Particularly preferred diphenols may be 4,4'-dihydroxybiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4 -hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylphosphonium and its di- and tetra-chlorinated or brominated derivatives, for example 2,2-bis(3-chloro-4-hydroxyphenyl)-propane, 2, 2-bis-(3,5-dichloro-4-hydroxyphenyl)propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane. Particularly preferred may be 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A).

Diphenols may be used in their own or in any mixture. The diphenol may be a diphenol which is conventionally known in the literature or obtainable according to methods well known in the literature.

According to DE-A2842005, suitable chain terminators for the preparation of thermoplastic aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, or Long-chain alkyl phenols such as 4-[2-(2,4,4-trimethylpentyl)]-phenol, 4-(1,3-tetramethylbutyl)-phenol or monoalkylphenol or a monoalkylphenol or a dialkylphenol having a total of 8 to 20 carbon atoms on its alkyl substituent, such as 3,5-di-t-butylphenol, p-isooctylphenol, p- Third octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol. The amount of the general chain terminator is from 0.5 mol% to 10 mol%, which is calculated based on the total number of moles of diphenol in a particular case.

The thermoplastic aromatic polycarbonate has an average weight average molecular weight (M _w , as measured by, for example, GPC, ultracentrifuge or scattered light) of 10,000 to 200,000 g/mol, preferably 15,000 to 80,000 g/mol, Particularly preferred is 24,000 to 32,000 g/mol.

The thermoplastic aromatic polycarbonate may be branched by a conventional method, preferably by incorporating 0.05 to 2.0 mol% (depending on the total amount of diphenol used) Or more than three functional groups of compounds, for example, those having three or more phenolic groups.

Both homopolycarbonates and copolycarbonates are suitable. The polycarbonate used to prepare the component A according to the invention may be used in an amount of from 1 to 25 wt.%, preferably from 2.5 to 25 wt.%, of a polydiorganofluorene having a hydroxyaryloxy terminal functional group. Alkane, which is calculated based on the total amount of diphenol used. These are known (US 3 419 634) and can be prepared according to methods known in the literature. The preparation of copolycarbonates containing polydiorganotoxioxanes is described in DE-A 3 334 782.

A preferred polycarbonate other than bisphenol A homopolycarbonate may be a bisphenol A copolycarbonate having up to 15 mol% (calculated based on the total amount of diphenol used). These are preferred or particularly preferred, especially 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-propane.

The aromatic dicarboxylic acid dihalide used for the preparation of the aromatic polyester carbonate may preferably be isophthalic acid, terephthalic acid, diphenyl ether 4,4'-dicarboxylic acid, and naphthalene-2. 6-Dicarboxylic acid diacid dichloride.

Particularly preferred is a mixture of phthalic acid and terephthalic acid dichloride in a ratio of 1:20 to 20:1.

In the preparation of the polyester carbonate, a carbonic acid halide (preferably phosgene) is additionally used as a derivative of a difunctional acid.

A chain terminator suitable for the preparation of an aromatic polyester carbonate, in addition to the monophenols already mentioned above, may also be a chlorocarbonate and a ruthenium chloride of an aromatic monocarboxylic acid, the selectivity of which may be from C ₁ - to Substituted with a C ₂₂ -alkyl or halogen atom, it may also be an aliphatic C ₂ - to C ₂₂ -monocarbon fluorene chloride.

The amount of chain terminator in each case is from 0.1 to 10 mol%, based on the molar number of the diphenol in the case of the phenolic chain terminator, and in the case of the monocarboxylic hydrazine chain terminator. Molar number of dicarboxylic acid dicarboxylic acid.

The aromatic polyester carbonate may also contain an aromatic hydroxycarboxylic acid incorporated therein.

The aromatic polyester carbonates can be linear and branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934).

For example, those which can be used as a branching agent are carboxy fluorene chlorides having three or more functional groups, such as tris(R) chloride, 1,3,3,3,3,3,3,3,3, 3',4,4'-benzophenone-tetracarboxylic acid tetradecyl chloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrahydrochloride or 1,2,4,5-benzenetetracarboxylic acid tetrahydrochloride , in an amount of 0.01 to 1.0 mol% (calculated based on dioxonium dicarboxylate used), or a phenol having three or more functional groups, such as phloroglucinol, 4,6-dimethyl- 2,4,6-tris-(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4,6-tris-(4-hydroxyphenyl)-heptane, 1 , 3,5-tris-(4-hydroxyphenyl)-benzene, 1,1,1-tris-(4-hydroxyphenyl)-ethane, tris-(4-hydroxyphenyl)-phenylmethane, 2,2-bis[4,4-bis(4-hydroxy-phenyl)-cyclohexyl]-propane, 2,4-bis(4-hydroxyphenyl-isopropyl)-phenol, tetra-(4- Hydroxyphenyl)-methane, 2,6-bis(2-hydroxy-5-methyl-benzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-di Hydroxyphenyl)-propane, tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxy)-methane, 1,4-bis[4,4'-dihydroxytriphenyl)-methyl The base is -benzene, and the amount thereof is from 0.01 to 1.0 mol% (calculated based on the bisphenol used). The phenolic branching agent can be placed in the reaction tank with the diphenol; the hydrazine chloride branching agent can be added together with the dioxonium chloride.

The content of the carbonate unit structure in the thermoplastic aromatic polyester carbonate can be varied as desired. A preferred carbonate group content of up to 100 mol%, particularly up to 80 mol%, particularly preferably up to 50 mol%, which is an ester The sum of the base and carbonate groups is calculated. The esters and carbonates contained in the aromatic polyester carbonate can be present as a polycondensation product in the form of a block or an arbitrary arrangement.

The relative solution viscosity (η _rel ) in the aromatic polycarbonate and the polyester carbonate ranges from 1.18 to 1.4, preferably from 1.20 to 1.32 (measured by taking 0.5 g of polycarbonate or polyester carbonate). The ester was tested in 100 ml of dichloromethane solution at 25 ° C).

In a preferred embodiment, the aromatic polyester which is a component A according to the present invention is an aromatic dicarboxylic acid or a reactive derivative thereof, such as a dimethyl ester or an acid anhydride, and an aliphatic or cycloaliphatic group. Or a reaction product of an aromatic aliphatic diol, and a mixture of such reaction products.

Particularly preferred aromatic esters contain at least 80 wt.% of terephthalic acid groups, preferably at least 90 wt.%, calculated as the dicarboxylic acid component, and at least 80 wt.% The ethylene glycol and/or 1,4-butanediol group preferably contains at least 90 mol%, which is calculated as the diol component.

When a terephthalic acid group is also contained, the preferred aromatic polyester can contain up to 20 mol%, preferably up to 10 mol% of other aromatic or cycloaliphatic having 8 to 14 carbon atoms. a carboxylic acid or an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, such as phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid a group of succinic acid, adipic acid, sebacic acid, sebacic acid, cyclohexane diacetic acid.

When the ethylene glycol and/or 1,4-butanediol group is also contained, the preferred aromatic polyester can contain up to 20 mol%, preferably up to 10 mol%, and other from 3 to 12 carbon atoms. An aliphatic diol or a cyclic fat having 6 to 21 carbon atoms Group diols, such as 1,3-propanediol, 2-ethyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexane-1, 4-Dimethanol, 3-ethyl-2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2 -ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2,5-hexanediol, 1,4-bis-(β-hydroxyethoxy)-benzene , 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(4-β -Hydroxyethoxy-phenyl)-propane and 2,2-bis-(4-hydroxy-propoxyphenyl)-propane (DE-A 2 407 674, 2407776, 2,715, 932).

Aromatic polyesters can be branched by incorporation of relatively small amounts of tri- or tetra- or alcohols or tri- or tetra-carboxylic acids, as described in DE-A 1 900 270 and US-PS 3 692 744. Examples of preferred branching agents are 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, trimethylolethane and trimethylolpropane and pentaerythritol.

Particularly preferred aromatic polyesters can be prepared entirely from terephthalic acid and reactive derivatives thereof (such as its dialkyl esters) as well as ethylene glycol and/or 1,4-butanediol, and such polymerizations A mixture of alkyl terephthalates.

The mixture of polyalkylene terephthalate contains from 1 to 50 wt.%, preferably from 1 to 30 wt.% of polyethylene terephthalate, and from 50 to 99 wt.%, preferably It is 70 to 99 wt.% of polybutylene terephthalate.

The preferred aromatic polyesters generally have a limiting viscosity of from 0.4 to 1.5 dl/g, preferably from 0.5 to 1.2 dl/g, in a phenol/o-dichlorobenzene solution (1:1). The parts by weight were measured at 25 ° C on a Ubbelohde viscometer.

Aromatic polyesters can be prepared using conventional methods (see, for example, Kunststoff-Handbuch, Volume VIII, p. 695 ff, Carl-Hanser-Verlag, Munich 1973).

Ingredient A can be in the form of a powder and/or a granule.

Ingredient B

Component B is a powdered graft polymer or a mixture of a plurality of powdered graft polymers. Preferred graft polymers for component B include one or more of the following graft polymers B.1 is at least one vinyl monomer of 5 to 95 wt.%, preferably 20 to 90 wt.%, particularly 25 to 50 wt.% based on the component B. B.2 is at least one or more rubber-based graft bases of 95 to 5 wt.% graft base, preferably 80 to 10 wt.%, particularly 75 to 50 wt.% (based on component B) Above, the glass transition temperature of the graft base is preferably <10 ° C, more preferably < 0 ° C, and particularly preferably < -20 ° C.

The glass transition temperature is measured by differential scanning calorimetry (DSC) at a heating rate of 10 K/min according to DIN EN 61006, and _Tg is defined as the midpoint temperature (tangent method).

The graft base B.2 generally has an average particle size (d ₅₀ value) of from 0.05 to 10 μm, preferably from 0.1 to 2 μm, particularly preferably from 0.15 to 0.6 μm.

The average particle size d ₅₀ is 50 wt.% of the particles in each case above and below the diameter. It can be measured by ultra-high speed centrifugation (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796).

The monomer B.1 is preferably a mixture of B.1.1 based on 50 to 99 parts by weight of B.1, preferably 60 to 80 parts by weight, particularly 70 to 80 parts by weight of a vinyl aromatic. a compound and/or a cyclic substituted vinyl aromatic compound (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and/or methacrylic acid (C ₁ -C ₈ - an alkyl ester such as methyl methacrylate, ethyl methacrylate, and B.1.2 based on 1 to 50 parts by weight of B.1, preferably 20 to 40 parts by weight, particularly 20 to 30 parts by weight of vinyl cyanide (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and/or (C ₁ -C ₈ )-alkyl (meth)acrylates, such as methyl methacrylate, acrylic acid N-butyl ester, tributyl acrylate, and/or derivatives of unsaturated carboxylic acids such as anhydrides and quinone imines, such as maleic anhydride and N-phenylmaleimide.

Preferably, the B.1.1 single system is selected from at least one monomer of styrene, α-methylstyrene, and methyl methacrylate, and preferably the B.1.2 single system is selected from the group consisting of acrylonitrile and maleic anhydride. And at least one monomer of methyl methacrylate. Particularly preferred monomers are B.1.1 styrene and B.1.2 acrylonitrile.

The graft base B.2 suitable for grafting polymer B is, for example, a diene rubber, an EP(D)M rubber, that is to say such based on ethylene/propylene, and optionally based on a diene, an acrylate, a polyamine Acid esters, polyoxyn oxide, chloroprene and ethylene/vinyl acetate rubber, and polyoxyn/acrylate composite rubber.

The preferred graft base B.2 is a diene rubber, for example based on butadiene and isoprene, or a mixture of diene rubbers or a copolymer of diene rubber or a copolymer containing further copolymerizable monomers. Mixture (as in B.1.1 and B.1.2).

Particularly preferred is a pure polybutadiene rubber.

Particularly preferred polymers B are, for example, ABS or MBS polymers (emulsifiers, masses and suspended ABS), for example in DE-OS 2 035 390 (=US-PS 3 644 574) or in DE-OS 2 248 242 (=GB-PS 1 409 275) Or as described in Ullmanns, Enzyklopädie der Technischen Chemie, Vol. 19 (1980), p. 280 ff.

The grafted copolymer B can be prepared by free radical polymerization, such as, for example, emulsification, suspension, solution or bulk polymerization, preferably by emulsion polymerization.

A particularly suitable graft polymer B has a core-shell structure.

The gel content of the graft base B.2 is at least 30 wt.%, preferably at least 40 wt.% (measured in toluene) in the case of preparing the graft polymer by emulsion polymerization.

The gel content of the graft base B.2 or the graft polymer B is measured at 25 ° C in a solvent which is not dissolved in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I und II, Georg Thieme-Verlag, Stuttgart 1977).

A particularly suitable graft rubber is also an ABS polymer which is prepared by a redox reaction starting from an initiator system of organic hydrogen peroxide and ascorbic acid according to US Pat. No. 4,937,285.

As is known, in the grafting reaction, the grafting monomer is not necessarily completely grafted onto the grafting substrate, and the grafting polymer B can also be understood according to the invention by the presence of grafting monomers. The graft monomer is obtained by (co)polymerization, and the product can be obtained as a result of working up. Such products may or may not contain (co)polymers of grafting monomers, that is to say the (co)polymers are not chemically bonded to the rubber.

Suitable acrylic rubbers according to B.2 are preferably polymers of alkyl acrylates having a selectivity up to 40 wt.% of other polymerizable, ethylenically unsaturated monomers based on B.2. Preferred polymerizable acrylates include C ₁ - to C ₈ -alkyl esters such as methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably Halo-C ₁ -C ₈ -alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.

For crosslinking, monomers having more than one polymerizable double bond can be copolymerized. Preferred examples of the crosslinking monomer are unsaturated monocarboxylic acid esters having 3 to 8 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms, or 2 to 4 OH groups and 2 to a saturated polyol of 20 carbon atoms, such as ethylene glycol dimethacrylate, allyl methacrylate; a polyunsaturated heterocyclic compound such as trivinyl cyanate and cyanuric cyanurate The ester; the polyfunctional vinyl compound is like di- and trivinylbenzene; it can also be triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least three ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomer triallyl cyanurate, triallyl isocyanurate, tripropylene decyl hexahydro-s-three , triallyl benzene. The amount of the crosslinking monomer is preferably from 0.02 to 5 wt.%, particularly from 0.05 to 2 wt.%, based on the graft base B.2. In the case of a cyclic crosslinking monomer having at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1 wt.% based on the graft base B.2.

Preferred "other" polymerizable, ethylenically unsaturated monomers which are optionally used in the preparation of the graft base B.2 in addition to the propyl esters are, for example, acrylonitrile, styrene, alpha-methylstyrene, Acrylamide, vinyl C ₁ -C ₆ -alkyl ether, methyl methacrylate, butadiene. The acrylate rubber preferably used as the graft base B.2 is an emulsified polymer having a gel content of at least 60 wt.%.

Further suitable graft bases according to B.2 have a grafting reaction position, as described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539. Polyoxyethylene rubber.

Ingredient C

The rubber-free vinyl (co)polymer according to the component C.1 is preferably at least one derived from a vinyl aromatic compound, a vinyl cyanide (unsaturated nitrile), or a (meth)acrylic acid (C ₁ to C _8). a rubber-free homopolymer and/or a copolymer of a monomer of an alkyl ester, an unsaturated carboxylic acid and a derivative of an unsaturated carboxylic acid such as an acid anhydride and a quinone imine.

Particularly suitable for the following (co)polymers C.1 C.1.1 based on the (co)polymer C.1 is from 50 to 90 wt.%, preferably from 60 to 80 wt.%, especially from 70 to 80 At least one monomer of wt.% selected from a vinyl aromatic compound (such as styrene, α-methylstyrene), a cyclically substituted vinyl aromatic compound (such as p-methyl styrene, a group of p-chlorostyrene) and (C ₁ -C ₈ )-alkyl (meth)acrylate (such as methyl methacrylate, n-butyl acrylate, and tributyl acrylate), And C.1.2 is based on (co)polymer C.1 from 1 to 50 wt.%, preferably from 20 to 40 wt.%, in particular from 20 to 30 wt.% of at least one monomer selected from Vinyl cyanide (such as unsaturated nitriles such as acrylonitrile and methacrylonitrile), (C ₁ -C ₈ )-alkyl (meth)acrylate (like methyl methacrylate, butyl methacrylate) A group consisting of a base ester, a third butyl acrylate, a derivative of an unsaturated carboxylic acid and an unsaturated carboxylic acid such as maleic anhydride and N-phenylmaleimide.

The (co)polymer C.1 is a resinous, thermoplastic and rubber-free. Particularly preferred are copolymers of C.1.1 styrene and C.1.2 acrylonitrile.

Such (co)polymers C.1 are well known and can be prepared by free radical polymerization, in particular by emulsification, suspension, solution or bulk polymerization. The (co)polymer preferably has an average molecular weight M _w (weight average molecular weight, as measured by GPC) of from 15,000 to 250,000 g/mol.

The rubber-free (co)polymer C.1 can be used in powder form and/or in particulate form.

The rubber-modified vinyl (co)polymer according to the component C.2 is selected from the group consisting of at least one polymer C.2.1 in the form of particles, and C.2.2 is selected according to the component C.1. Precompounds in the form of particles of at least two components of the group consisting of the graft polymer C.2.2.1 and the rubber-free vinyl (co)polymer.

The graft polymer according to the components C.2.1 and C.2.2.1 corresponds in each case to the graft polymer described in the chemical structure corresponding to the component B, whereas the preparation of the components C.2.1 and C.2.2.1 is The description of ingredient B is different in that the graft polymer in C.2.1 is in the form of particles, and C.2.2.1 is present in the form of particles or powder.

In the context of the present invention, "pre-compound" means a mixture of graft polymer C.2.2.1 and a rubber-free vinyl (co)polymer which is, for example, a kneading reaction in a mixing unit. Or a twin-screw extruder, heated by a supply of heat and/or mechanical energy to a temperature of from 180 ° C to 300 ° C, preferably from 200 ° C to 280 ° C, particularly preferably from 220 ° C to 260 ° C, and then with each other Melt, mix and disperse, then cool again and granulate. In a preferred embodiment, the graft polymer C.2.2.1 is used in a wet state (i.e., in the presence of water) according to the method described in EP 0 768 157 A1 and EP 0 867 463 A1.

The pre-compound according to component C.2.2 preferably contains (in each case based on the pre-compound) from 10 to 70 parts by weight, particularly preferably from 20 to 60 parts by weight, most particularly preferably from 25 to 55 parts by weight. The graft polymer C.2.2.1, and preferably contains (in each case based on the pre-compound) from 30 to 90 parts by weight, particularly preferably from 40 to 80 parts by weight, most particularly preferably from 45 to 75. Parts by weight of rubber-free vinyl (co)polymer C.1.

Ingredient D

As the component D, at least one kind of Bronsted acid compound is used.

The Bronsted acid compound may preferably be a mineral acid, more preferably a phosphoric acid compound, that is to say a compound having at least one POH functional group.

Examples of such compounds are: - phosphoric acid P(O)(OH) ₃ , - phosphorous acid HP(O)(OH) ₂ , - hypophosphorous acid H ₂ P(O)(OH), - having the general formula RP(O (OH) ₂ , R(H)P(O)(OH) and R(R')P(O)(OH) phosphorous acid and an organophosphorous acid compound of hypophosphorous acid, wherein R and R' are each independently It may be any optionally substituted alkyl, aryl or alkylaryl group, or it may be a cyclic or linear oligomeric or polymeric compound, an acid salt, and an acid partial esterified compound of the aforementioned compounds. . R and R' are particularly preferably independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl radicals.

In a preferred embodiment, it may be a Bronsted phosphoric acid compound wherein the oxidation state of phosphorus is +3 or +5. It is especially preferred that the oxidation state is +5.

For example, particularly preferred as the Bronsted phosphorus compound may be orthophosphoric acid, metaphosphoric acid, oligomeric and polyphosphoric acid, phosphorous acid, methylphosphonic acid CH ₃ P(O)(OH) ₂ , acidic salts of the above compounds and Has a monovalent and/or divalent metal cation such as NaH ₂ PO ₄ , Na ₂ HPO ₄ , KH ₂ PO ₄ , K ₂ HPO ₄ , Mg _0.5 H ₂ PO ₄ , MgHPO ₄ , Ca _0.5 H ₂ PO ₄ , CaHPO ₄ , Zn _0.5 H ₂ PO ₄ , ZnHPO ₄ , NaH ₂ PO ₃ , KH ₂ PO ₃ , Mg _0.5 H ₂ PO ₃ , Ca _0.5 H ₂ PO ₃ , Zn _0.5 H ₂ PO ₃ , may also be part of the above compound Esterates such as P(O)(OH)(OR)(OR'), P(O)(OH) ₂ (OR), HP(O)(OH)(OR), and CH ₃ P(O)( OH)(OR), wherein R, R' are as defined above.

In a preferred embodiment, the Bronsted phosphoric acid compound is orthophosphoric acid or phosphorous acid, and in a particularly preferred embodiment, it is orthophosphoric acid.

Ingredient E

A commercially available polymer additive as component E may be included in the composition.

Suitable commercial polymer additives according to the additives of component E are, for example, flame retardants (for example compounds of phosphorus or halogens), flame retardant synergists (for example metal oxides of the nano-grade), additives for suppressing smoke (for example boric acid). Or borate), anti-drip agents (such as fluorinated polyolefins, polyfluorenes and polyarsenite fibers), internal and external lubricants, mold release agents (eg, pentaerythritol tetrastearyl) Acid esters, montan wax or polyethylene wax), flow aids (such as low molecular weight vinyl (co)polymers), antistatic agents (such as ethylene oxide and propylene oxide, other polyethers or Polyhydroxyether, polyether decylamine, block copolymer of polyester decylamine or sulfonate), conductive additive (eg conductive black or carbon nanotube), stabilizer (eg UV/light stabilizer, heat) Stabilizers, antioxidants, transesterification inhibitors, hydrolysis stabilizers), antibacterial additives (such as silver or silver salts), additives to improve scratch resistance (for example, eucalyptus oil or hard fillers such as (hollow) ceramic balls ), IR absorbers, optical brighteners, fluorescent additives, fillers and reinforcements (E.g., talc, optionally ground glass or carbon fibers, (hollow) glass or ceramic spheres, mica, kaolin, CaCO ₃ and glass flakes) as well as colorants and pigments (such as carbon black, titanium dioxide or iron oxides) or more a mixture of the above additives.

It is preferred to use a phosphorus-containing compound depending on the component E as a flame retardant. Such compounds are preferably selected from the group consisting of monomers and oligomeric phosphoric acid and phosphonates, phosphonate amines and phosphazenes, which may also be selected from one or more different groups selected from the group The mixture acts as a flame retardant. Other halogen-free phosphorus compounds not specifically mentioned may be used singly or in any combination with other halogen-free phosphorus compounds in the present invention.

Preferred monomers and oligomeric phosphoric acid and phosphonates are phosphorus compounds having the following general formula (IV) Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a selectively halogenated C ₁ - to C ₈ -alkyl group, a C ₅ - to C ₆ -cycloalkyl group, a C ₆ - to C ₂₀ -aryl or C ₇ - to C ₁₂ -arylalkyl, each of which is optionally substituted with an alkyl group, preferably a C ₁ - to C ₄ -alkyl group, and/or a halogen, preferably It is chlorine or bromine. Each substituent n may be independently 0 or 1, q represents 0 to 30, and X represents a mono- or poly-nuclear aromatic group having 6 to 30 carbon atoms, or has 2 to 30 carbon atoms. Linear or branched aliphatic groups which may have OH-substituents and have up to 8 ether linkages.

R ¹ , R ² , R ³ and R ⁴ each independently preferably represent a C ₁ - to C ₄ -alkyl group, a phenyl group, a naphthyl group or a phenyl-C ₁ -C ₄ -alkyl group. The aromatic groups R ¹ , R ² , R ³ and R ⁴ may be substituted by halogen and/or alkyl, preferably chlorine, bromine and/or C ₁ - to C ₄ -alkyl. Particularly preferred aryl groups can be tolyl, phenyl, xylyl, propylphenyl or butylphenyl, as well as their corresponding brominated and chlorinated derivatives.

X preferably represents a mono- or poly-nuclear aromatic group having 6 to 30 carbon atoms in the formula (IV). Preferred are diphenols derived from formula (I).

Each of the substituents n in the formula (IV) is independently and may be 0 or 1; n is preferably 1. q represents 0 to 30, preferably 0.3 to 20, particularly preferably 0.5 to 10, particularly 0.5 to 6, and most particularly preferably 1.1 to 1.6. X is particularly preferred Or a chlorinated or brominated derivative thereof; X is particularly derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. X is particularly preferred to be derived from bisphenol A.

According to the invention, a mixture of different phosphates can be used as component E.

The phosphorus compound of the formula (IV) is in particular tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl tolyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethyltoluene phosphate A base ester, tris-(isopropylphenyl) phosphate, a resorcinol-bridged oligomeric phosphate, and a bisphenol A-bridged oligomeric phosphate. It is especially preferred to use an oligomeric phosphate of formula (IV) derived from bisphenol A.

Most preferred as component E is a bisphenol A-oligophosphate based on formula (IVa).

Phosphorus compounds according to the component E are conventionally known (see, for example, EP-A 0 363 608, EP-A 0 640 655) or can be produced in a similar manner according to known methods. Preparation (e.g. Ullmanns Enzyklopädie der technischen Chemie, Vol. 18, p. 301 ff 1979; Houben-Weyl, Methoden der organischen Chemie, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177).

When a mixture of different phosphorus compounds and an oligomeric phosphorus compound are used, the specified q value is the average q value. The average q value can be determined by measuring the composition of the phosphorus compound by a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)), and It calculates the average of q.

Phosphonate amines and phosphazenes are also used as flame retardants as described in WO 00/00541 and WO 01/18105.

The flame retardant may be used alone or in any mixture with another flame retardant, or in a mixture mixed with other flame retardants.

In a preferred embodiment, the flame retardant is used in combination with polytetrafluoroethylene (PTFE) as a drop inhibiting agent.

The present invention is further directed to the application of the Bronsted acid of component D to component B during the compounding and thermoplastic processes for stabilizing the polymer mixture, comprising alkaline impurities, at least one to polymerize. A polymer prepared by a condensation method.

Example Ingredient A-1

A linear polycarbonate based on bisphenol A having a weight average molecular weight Mw of 28,000 g/mol (using dichloromethane as a solvent and using gel permeation chromatography) (GPC) is measured and polycarbonate is used as a standard).

Ingredient B1

A powdery ABS graft polymer having a core-shell structure is prepared by emulsion polymerization, which comprises 40 wt.% of a styrene-acrylonitrile copolymer having a ratio of styrene to acrylonitrile of 72:28 wt.%. The shell was grafted onto a 60 wt.% pure polybutadiene rubber particle having a mean particle size d ₅₀ of 0.3 μm.

Ingredient B2 (comparative example)

A polycarbonate powder obtained by mechanically grinding a linear polycarbonate based on bisphenol A having a weight average molecular weight Mw of 31,000 g/mol (measured with dichloromethane as a solvent and using GPC, and polycarbonate) Ester is a standard).

Ingredient C1

A blend of acrylonitrile:butadiene:styrene in a ratio of 21:15:64 wt.%, comprising an ABS polymer prepared by emulsion polymerization and recovered in an alkaline medium, by polymerization as a whole ABS polymer and SAN polymer.

Ingredient C2

35.62 parts by weight of a component C1 and 2.97 parts by weight of a blend of component B1, wherein all components B1 have been treated with a SAN polymer from component C1 in a weight ratio of 1:1 to form a pre-compound in the form of particles, and Used in the same way as in component C2.

Ingredient D1

An aqueous phase phosphoric acid solution of 0.2 wt.% H ₃ PO ₄ was used.

Ingredient D2

2 wt.% concentration of aqueous phosphoric acid solution of H3PO4.

Ingredient D3

An aqueous phase phosphoric acid solution of 5 wt.% H ₃ PO ₄ .

Ingredient D4

10 wt.% strength aqueous solution of H ₃ PO ₄ in phosphoric acid.

Ingredient D5

A 10 wt.% strength aqueous solution of H ₃ PO ₄ was concentrated in a phosphoric acid solution.

Ingredient D6

The bisphosphonate of bis-(2-hydroxy-3-cyclohexyl-5-methyl-phenyl)-methane is of the formula:

Ingredient E1

Pentaerythritol tetrastearate is used as a lubricant/release agent.

Ingredient E2

Heat stabilizer, Irganox® B900 (80% Irgafos® 168 and 20% Irganox® 1076 mixture; BASF AG; Ludwigshafen/Irgafos® 168 (2,4-di-t-butyl-phenyl) phosphite / Irganox® 1076 (2,6-di-t-butyl-4-(octadecyloxycarbonylethyl)-phenol) (Ludwigshafen, Germany).

Ingredient E3

Heat stabilizer, Irganox® 1076 (2,6-di-t-butyl-4-(octadecyloxycarbonylethyl)-phenol), BASF (Ludwigshafen, Germany).

Preparation of molding composition

In a first method step (i), a composition of components B and D is prepared using a LAB CM 3-12-MB laboratory vessel mixer (from Mixaco Dr. Herfeld GmbH & Co. KG Maschinenfabrik (Neuenrade, Germany)). Physical mixture. The ingredients E1 to E3 in the special composition mentioned are added to the mixture and mixed again with a Mixaco mixer. In a second method step (ii), the flowable powder mixture from step (i) is introduced by means of a separate metering funnel and introduced together with ingredients A and C via a separate dose funnel into a ZSK25 twin screw extruder ( From the entry zone of Coperion GmbH (Stuttgart, Germany). The resulting mixture was sent to the melting zone of the extruder and the kneading zone at 260 ° C, and melted and kneaded at this temperature, whereby the plastic components were dispersed between each other. The thus-mixed mixture is degassed in a subsequent extruder degassing zone by applying a low pressure of 100 mbar (absolute pressure), and thus the water in the mixture is added as component D. It is then removed from the polymer alloy. At the same time, water vapor can be used as a carrier to remove volatile organic compounds (VOCs), such as residual monomers from the polymer materials used (components A, B, and C) and residual solvents. The degassed melt is then discharged from the extruder through a die, and the resulting molten strand is cooled by passing through a water bath of about 30 ° C, and then the solidified polymer strands are granulated by a strand granulator.

Preparation and testing of test samples

Each of the kneaded pellets was processed on an injection molding machine (Arburg) at a melting point of 260 ° C and 300 ° C, followed by a tool temperature (tool temperatuer) of 80 ° C to form 80 mm x 10 mm x 4 mm and 60 mm Test piece for x 40 mm x 2 mm.

iMVR is used to test the expected molecular weight degradation of polycarbonate at elevated processing temperatures, and to test the thermal stability of the composition and according to the method of ISO 1133, at a melting temperature of 300 ° C at 5 kg The plunger was loaded and the results were measured after loading at a temperature of 300 ° C for 15 minutes.

According to DIN 6174, the natural color/ contained color of the test piece (60 mm x 40 mm x 2 mm) was measured by injection molding at 260 ° C and 300 ° C. The yellow index YI was calculated according to the method of ASTM E313.

The gloss of the test piece (60 mm x 40 mm x 2 mm) was produced by injection molding at a melting temperature of 260 ° C and 300 ° C. The measurement was carried out according to the method of DIN 67530 at a measurement angle of 20° and 60°.

The relative change in gloss measured at the measurement angles of 20° and 60° can be increased as the melting temperature increases from 260°C to 300°C, and is used for testing stability and calculation according to the following : Change in gloss (260 ° C → 300 ° C) = 100% feel (gloss at 300 ° C - gloss at 260 ° C) / gloss at 260 ° C.

The change in gloss of the two test angles was measured individually.

The tendency to form a processed stripe was similarly measured by thermal measurement of a test piece (60 mm x 40 mm x 2 mm), which was produced by injection molding at a melting temperature of 300 °C.

The notched impact strength (a _k ) was measured 10 times using a test rod (80 mm x 10 mm x 4 mm) according to the ISO 180/1A method, in which the test rod was injection molded at a melting temperature of 300 ° C to simulate Increased temperature processing. The measurement was carried out at a temperature of 23 ° C, 10 ° C, 0 ° C, -10 ° C, -20 ° C and -30 ° C.

The a _k ductility-brittle transition temperature is determined from the measured values obtained in each case at a temperature at which the notched impact strength is greater than and less than 50% of the individual measured display values of 30 kJ/m ² .

According to ISO 527-1, -2, the tensile elongation of the shoulder rod (170 mm x 10 mm x 4 mm) is measured, which is produced by injection molding at a melting temperature of 300 ° C to simulate processing at elevated temperatures. .

The change in MVR measured according to ISO 1133 was used as the hydrolytic stability evaluation of the composition, which was continuously loaded on the stored particles with a 5 kg plunger at 260 ° C for 7 days, and maintained at a wet heat condition of 95 ° C and 100%. Under RH ("FWL Storage"). The corresponding increase in the MVR value before storage and the MVR after storage is calculated as ΔMVR(hydr.), which is defined as follows:

According to ISO4599, the stress crack resistance under the influence of the medium (environmental stress cracking, ESC) is measured on a test rod (80 mm x 10 mm x 4 mm), which is injection molded at a melting temperature of 300 ° C to simulate the rise in High temperature processing. The time of failure of the fracture was evaluated as stress crack resistance, which was strained by an outer outer fiber strain of 2.4% tensile plate and completely immersed in canola oil as a medium.

The data in Table 1 shows that the application of the acidic phosphorus compound to the graft polymer B in the form of an aqueous solution at an effective concentration of 0.01 wt.% (100 ppm) has a binding processing stability (to measure the stripes) according to the present invention Examples 1 to 4 , polycarbonate molecular weight degradation measurement), natural color and stability at high processing temperatures, mechanical properties (measured by the function of notched impact strength versus temperature), tear elongation, hydrolytic stability and stress Rupture stability. If the effective concentration of the acidic phosphorus compound used is too low or if the acidic phosphorus compound is omitted altogether (comparison of Example 1 with Comparative Examples C2 and C5), only a slightly better natural color is obtained, but the process is stable. Properties, especially regarding the observation of PC degradation at high processing temperatures, and stress crack resistance are significantly affected. If the acidic phosphorus compound is completely omitted (comparison of Example 1 with Comparative Example C2), the mechanical parameters are like Notched impact strength, ductile-brittle transition temperature, and tear elongation are also significantly negatively affected. On the other hand, acidic phosphorus compounds above the effective concentration are used ( Comparing Example 1 with Comparative Example 4, similarly, the deterioration of processing stability related to PC degradation, the formation of process stripes, and the reduction of stress crack resistance at the high processing temperature and the considerable natural coloration and hydrolysis were observed. Stability, notched impact strength, and damage to color and its stability to processing temperature. If the acidic phosphorus compound is used in a quantifiable solid form (Comparative Example 1), a relatively high concentration of active ingredient is required to achieve appropriate Processing stability. This in particular leads to damage to the natural color and hydrolysis stability. If the aqueous solution form acidic phosphorus compound is added to the powdered polycarbonate abrasive as a carrier component at an effective acid concentration of 0.01 wt.% instead of Into the graft polymer B (comparison of Example 1 with Comparative Example C3), it is thereby particularly advantageous to obtain a natural color which is unfavorable at a higher processing temperature and a lower color tone.

The data in Table 1 additionally shows that the application of an acidic phosphorus compound in the form of a highly diluted aqueous solution to the graft polymer B in the composition is particularly advantageous (compare Examples 1, 2 and 3, 4). If a concentrated solution of the acidic phosphorus compound (Example 4) is used, the stress crack resistance is significantly affected; on the other hand, the tear elongation has a negative influence in the intermediate concentration range (Example 3). Thus, in a particularly preferred specific time lost case, an acidic phosphorus compound in the form of an aqueous solution having a concentration of the active ingredient of less than 10 wt.% is used in the process according to the invention.

Claims (15)

A method of preparing an impact modified polymer composition comprising (A) based on a total of components A+B+C+D+E, from 10 to 98 parts by weight of at least one polymer selected from the group consisting of aromatic poly a group consisting of carbonates, aromatic polyester carbonates, and aromatic polyesters and mixtures thereof; (B) based on the sum of components A+B+C+D+E, from 0.5 to 50.0 parts by weight a powdered rubber-modified vinyl (co)polymer; (C) based on the sum of the components A+B+C+D+E, from 0 to 80 parts by weight of the rubber selected from the granular form At least one component of a vinyl (co)polymer and a rubber-free vinyl (co)polymer; (D) based on the sum of the components A+B+C+D+E, from 0.002 to 0.200 parts by weight a lincoln acid; (E) based on the sum of the components A+B+C+D+E, from 0.1 to 40.0 parts by weight of the additive, except for the acid added by the component D; wherein, in the composition The sum of the parts by weight of the component A+B+C+D+E is 100; comprising the steps of: (i) preparing an acidic compound solution according to D, the concentration is from 0.3 to 30 wt.%; (ii) from the step ( i) the acidic compound D solution and the total or partial amount of the graft according to component B a powder, and optionally a physical blend of one or more of the total or partial amounts of the further powdered component of the polycarbonate-ABS composition; (iii) from the step of the mixing unit The mixture of (ii) and the remaining component AE of the composition are melted, mixed and dispersed between each other, optionally Also premixed, wherein the solvent which has been added to the composition by the acidic compound solution is removed again by applying a low pressure in the degassing zone of the kneading unit, and the polymer melt thus prepared is subsequently borrowed It is solidified by cooling and then granulated. The method according to claim 1, characterized in that in the step (ii), in addition to the component D solution, the stabilizer of the further component E is also mixed with B. The method according to claim 1, characterized in that in the step (ii), the component B and the solution (i) are first mixed before the powdery component is further added, The method according to claim 1, characterized in that the amount of the component B in the step (ii) is not more than 10 parts by weight based on the total composition. The method according to claim 1, characterized in that the amount of the component B in the step (ii) is from 1.5 to 5.0 parts by weight based on the total composition. A method according to any one of the preceding claims, characterized in that the component D solution is used in the mixture prepared in the step (ii) based on the sum of the components B and D in the mixture, the amount of which is not More than 30 parts by weight. A method according to any one of the preceding claims, characterized in that the component D solution is used in the mixture prepared in the step (ii) based on the sum of the components B and D in the mixture, the amount of which is not More than 20 parts by weight. A method according to any one of the preceding claims, characterized in that the solvent in (i) is an inorganic solvent. A method according to any one of the preceding claims, characterized in that the solvent in (i) is water. A method for preparing an impact modified polymer composition according to claim 1, comprising From 55 to 65 parts by weight of component A; from 1.5 to 5.0 parts by weight of component B; from 20 to 40 parts by weight of component C; from 0.007 to 0.020 parts by weight of component D; from 0.5 to 3.0 parts by weight The additive, except for the conventionally added acid in component E; and wherein the sum of the components A+B+C+D+E in the composition is 100. The method according to claim 1, characterized in that in the step (i), the solution of the acidic compound D is prepared at a concentration of from 1 to 6 wt.%. A method according to any one of the preceding claims, characterized in that the component D is selected from the group consisting of phosphorus compounds of Bronsted, wherein the phosphorus has an oxidation state of +3 or +5. A method according to any one of the preceding claims, characterized in that component D is orthophosphoric acid. A use of a component D of Brunsten acid applied to component B to stabilize a polymer mixture comprising a basic impurity comprising at least one polymer prepared by polycondensation in a kneading and thermoplastic form . A composition prepared by the method according to one of claims 1 to 13, and a molded object produced therefrom.