TW201333104A - Stabilised polycarbonate compositions with blends of silica and an inorganic acid - Google Patents

Abstract

The present invention relates to polycarbonate compositions having improved processing stability, increased heat stability and a good natural colour, and to their preparation and use, wherein the polycarbonate compositions contain an adsorber or absorber and an acid. The present invention relates further to a compounding process for the preparation of heat stabilised polycarbonate compositions containing constituents having a basic action, using acids applied to an adsorber or absorber. The present invention relates further to the use of Br ?? nsted acids applied to an adsorber or absorber for the heat stabilisation of polymer mixtures, containing basic impurities, containing at least one polymer prepared by polycondensation, during compounding and thermal shaping.

Description

Stabilized polycarbonate composition having a blend of vermiculite and inorganic acid

The present invention relates to a polycarbonate composition, and to a process for the preparation and use thereof, wherein the polycarbonate composition contains an adsorbent or absorbent and an acid.

The invention further relates to a compounding process for the preparation of a stabilized polycarbonate composition comprising a composition having a basic effect, the method being applied to an adsorbent or absorbent using an acid. For example and preferably by applying the adsorbent or absorbent with an acid which wets the adsorbent or absorbent, or with an acid solution which wets the adsorbent or absorbent, the acid is applied to the adsorbent or absorbent. . In a preferred embodiment, the blends are pulverulent and pourable.

The composition obtained according to the present invention or by the kneading method according to the present invention has improved processing stability, particularly with improved processing gloss, improved gloss stability, and improved thermal stability and good Natural color.

In the processing of polymers, kneading refers to the preparation of finished plastic molding compositions (compounds), from a variety of polymeric materials and selected additive polymer additives, such as, for example, Fillers and reinforcing materials, adhesion promoters, lubricants, stabilizers, etc. The kneading is carried out, for example, in a kneader or extruder, and includes a process of feeding, melting, dispersing, mixing, degassing, and pressure build-up. The kneading is generally followed by solidification of the formulation by cooling and granulation.

Impact modifiers for the preparation/kneading of polycarbonate compositions typically contain alkaline impurities produced by their preparation methods, which contain, for example, residual amounts A basic substance which acts as a polymerization aid, for example as an emulsifier in an emulsion polymerization or as an auxiliary substance in a treatment procedure. In some cases, alkaline additives such as lubricants and release agents can also be purposefully added to the ABS polymer. Also, many commercially available fillers such as, for example, talc, or other commercially available polymeric additives such as, for example, some antistatic agents (e.g., polyether amides), lubricants (e.g. Base bis-stearate, stabilizers (eg benzotriazoles used as light stabilizers), pigments (eg titanium dioxide), nitrogen-containing organic colorants (eg azo compounds or pyrazolones) )) and nitrogen-containing flame retardants (such as phosphonate amines) which exhibit alkaline behavior or contain basic impurities.

At elevated temperatures, such alkaline acting additives or impurities can cause catalytic decomposition of the polycarbonate, such as occurs substantially in the preparation and processing of polycarbonate molding compositions. Such polycarbonate degradation is also generally caused by molecular weight degradation and surface modification, which degrades the properties of the molded composition, particularly mechanical parameter properties such as ductility and tensile elongation properties. As a result, the selectivity to the materials available for use in such polycarbonate compositions is greatly limited.

In order to neutralize the adverse effects of an alkaline additive or impurity, it is known in the prior art to add an acidic compound such as, for example, citric acid to a polycarbonate composition, and to add such an acid to the polycarbonate. The composition often results in unfavorable properties such as, for example, streaking on the surface, significant molecular weight degradation, and/or natural color damage.

EP-A 576 950 A1 and WO-A 2007/065579 describe compositions comprising polycarbonate and acrylonitrile-butadiene-styrene (ABS) polymers which contain basic impurities and utilize polyfunctional organic The carboxylic acid is stabilized. At high processing temperatures, such compositions have good thermal stability with respect to the molecular weight of the polycarbonate component, but they form surface defects (speckles) on the molded article produced by injection molding thereof. The tendency.

US 2006/0287422 describes thermoplastic compositions comprising polycarbonates, impact modifiers (optionally containing vinyl copolymers, mineral fillers and acids or acid salts) which have a tendency to have improved mechanical properties and low thermal degradation. The application also discloses that suitable acids are the phosphorus compounds of the general formula H _m P _t O _n , and in particular also include phosphoric acid. This application discloses that the composition according to the present invention can be obtained by the method described in the prior art.

WO-A 2010/063381, which describes an impact-modified polycarbonate composition having a combination of improved hydrolysis and processing stability, the composition comprising a polycarbonate, an emulsified graft polymer containing a basic impurity, And an acidic phosphorus-containing compound having at least one P-OH functionality. The application states that certain cyclic organophosphite compounds and inorganic or organic phosphorus-containing compounds can be used as acidic phosphorus-containing compounds such as, for example, phosphoric acid or phosphates.

EP 2 257 590 A1 discloses polycarbonate compositions having a combination of improved natural colour, hydrolysis stability and process stability, which comprise polycarbonate, residues derived from fatty acid salt emulsifiers from the preparation process thereof A rubber-modified graft polymer, and an acidic additive, wherein the graft polymer has a pH greater than 7 in the aqueous dispersion. In this application, hydroxy-functionalized mono- and poly-carboxylic acids and phosphoric acid are disclosed as acidic additives.

EP 1 141 107 A1 discloses polycarbonate compositions having improved resistance to thermal deformation, elongation at break and stress crack resistance, which comprise polycarbonate, graft polymer, optionally vinyl copolymer and 0.1 Up to 30 parts by weight of a ruthenium compound such as, for example, ruthenium dioxide having a mean particle diameter of 3 to 50 nm. This application does not address the use of the acid in the composition.

However, none of the paragraphs already mentioned describe the compositions of the invention or their methods of manufacture.

Accordingly, it is an object of the present invention to provide a polycarbonate composition and a process for the same thereof which do not have the above disadvantages and thus exhibit particularly improved processing stability (by varying the processing temperature, glossiness) Stability measured), improved thermal stability and good natural color.

Surprisingly, it has been found that a polymer composition comprising the following composition Desirable property profile: A) 10 to 100 parts by weight of at least one polymer selected from the group consisting of aromatic polycarbonates, aromatic polyester carbonates, and aromatic poly The ester, preferably 30 to 95 parts by weight, more preferably 40 to 80 parts by weight, particularly preferably 55 to 65 parts by weight, based on the total of the components A+B in each case, B) 0 to 90 parts by weight At least one selected rubber-modified vinyl (co)polymer, preferably 5 to 70 parts by weight, more preferably 20 to 60 parts by weight, particularly preferably 35 to 45 parts by weight, in each case Based on the sum of the components A+B, C) 0.00025 to 0.080 parts by weight of at least one inorganic or organic adsorbent, or absorbent, preferably 0.001 to 0.050 parts by weight, particularly preferably 0.001 to 0.010 parts by weight, in each case. Based on the sum of the components A+B, D) 0.001 to 0.300 parts by weight of at least one Brönsted acid compound, preferably 0.005 to 0.200 parts by weight, particularly preferably 0.005 to 0.05 parts by weight, each In the example, based on the sum of the components A+B, E) 0.1 to 40.0 parts by weight of at least one additive (except for the components C, D and F) Preferably from 0.2 to 10.0 parts by weight, particularly preferably from 0.3 to 2.0 parts by weight, based on the total of the components A+B in each case, F) from 0 to 50 parts by weight of talc, preferably from 3 to 40 parts by weight. More preferably, it is 8 to 30 parts by weight, and in each case, based on the sum of the components A+B, the sum of the components A+B in the composition is 100.

Preferably, component D is used in an amount of at least 25 parts by weight, more preferably at least 50 parts by weight, especially at least 60 parts by weight, based on the total of components C and D.

According to the method of producing the composition of the present invention, in a preferred embodiment, the Brinell-Acid compound according to Component D is applied to the adsorbent or absorbent according to Component C. This is usually carried out by physically incorporating the components C and D, wherein the adsorbent or absorbent according to component C needs to be wetted with a Brinell-acidic compound according to component D. In order to achieve wettability, the Brinell-acidic compound according to component D is optionally dissolved in a suitable inorganic or organic solvent or blended with an inorganic or organic liquid. Water is a preferred solvent.

In order to achieve better wetting of component C, if component D is applied to component C as a solution, the content of component D above is based on a pure acid containing no solvent.

In a preferred embodiment, the blend of the Brinell-acidic compound according to component D, or the solution of the Brinell-acidic compound according to component D, and the adsorbent or absorbent according to component C are powders. Shaped and pourable.

Within the scope of the present invention, "powder" or "powder" is understood to mean a mixture of one or more components present in a solidified state and the particles therein Having a particle size of less than 2 mm, preferably less than 1 mm, especially less than 0.5 Mm.

Ingredient A

According to the invention, suitable aromatic polycarbonates and polyestercarbonates according to component A are known in the literature or can be obtained by methods known in the literature (for the production of aromatic polycarbonates) See, for example, 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; for the production of aromatic polyester carbonates, see, for example, DE-A 3 077 934).

The method for producing the aromatic polycarbonates and the polyester carbonates is, for example, a diphenol and a carbonic acid halide (preferably phosgene), and/or an aromatic dicarboxylic acid dihalide (preferably The reaction of the benzenedicarboxylic acid dihalide) is carried out by selectively using a chain terminator (for example, a monophenol) according to an interfacial method, and selectively using a branching agent having three or more functionalities (for example, Trisphenols or tetraphenols). A method of producing a reaction of a diphenol with, for example, a diphenyl carbonate by a melt polymerization reaction can also be carried out.

For the aromatic polycarbonate and/or aromatic polyester carbonate The second phenol of the production method is preferably a compound of the formula (I)

Wherein A is a single bond, C ₁ - to C ₅ -alkylene, C ₂ - to C ₅ -alkylidene, C ₅ - to C ₆ -cycloalkylidene, O-, SO-, -CO-, -S-, -SO ₂ -, C ₆ - to C ₁₂ -arylene, fused to an additional aromatic ring optionally containing a hetero atom, Or, the radical of formula (II) or (III)

B is, in each case, a C ₁ - to C ₁₂ -alkyl group, preferably a methyl group, a halogen (preferably chlorine and/or bromine), each of which is independently 0, 1 or 2, and p is 1 Or 0, and R ⁵ and R ⁶ , each of X 1 may be individually selected and independently of each other hydrogen or C ₁ - to C ₆ -alkyl, preferably hydrogen, methyl or ethyl, X ¹ is Carbon, and m is an integer of 4 to 7, preferably 4 or 5, provided that at least one atom X ¹ , R ⁵ and R ^{6 are} simultaneously an alkyl group.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyl)-C ₁ -C ₅ -alkanes, bis-(hydroxyphenyl) )-C ₅ -C ₆ -cycloalkanes, bis-(hydroxyphenyl)ethers, bis-(hydroxyphenyl)anthracenes, bis-(hydroxyphenyl)ketones, bis-(hydroxyphenyl) - anthraquinones and alpha, alpha-bis-(hydroxyphenyl)-diisopropyl-benzenes, and derivatives thereof which are brominated and/or chlorinated on the ring.

Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, 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-brominated or chlorinated derivatives such as, 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 is 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A).

The diphenols may be used singly or in any mixture known from the literature or may be obtained by methods known in the literature.

A chain terminator suitable for the preparation of the thermoplastic aromatic polycarbonate is, for example, phenol, p-chlorophenol, p-third-butylphenol or 2,4,6-tribromophenol, and is also long Alkyl phenols of the chain, such as 4-[2-(2,4,4-trimethylpentyl)]-phenol, 4-(1,3-tetramethylbutyl) according to DE-A 2 842 005 a phenol, or a monoalkyl phenol or a dialkyl phenol having a total of 8 to 20 carbon atoms in the alkyl substituent, such as 3,5-di-tertiary-butylphenol, p-iso Octyl phenol, p-third-octyl phenol, p-dodecyl phenol and 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl) -phenol. The content of the chain terminator to be used is usually from 0.5 mol% to 10 mol%, based on the total number of moles of the diphenols used in the specific examples.

The thermoplastic aromatic polycarbonates may be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol% of a compound having three or more functionalities (for example, having three or more phenolic groups) ) based on the sum of the diphenols used.

Both homopolycarbonates and copolycarbonates are suitable. For the preparation of the copolycarbonates of the component A according to the invention, it is possible to use from 1 to 25 wt.%, preferably from 2.5 to 25 wt.%, of polydiorganotoxioxane having a hydroxyaryloxy end group. Class, based on the total amount of diphenols to be used. These are known (US 3 419) 634) and a method for producing the polydiorganotoxime-containing copolycarbonate can be obtained by a method known in the literature, which is described in DE-A 3 334 782.

In addition to the bisphenol A homopolycarbonate, preferred polycarbonates are copolycarbonates of bisphenol A and up to 15 mol% of diphenols (other than the above preferred or particularly preferred), with the diphenol Based on the sum of the molar numbers of the classes, especially 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-propane.

For the preparation of the aromatic polyester carbonate, the aromatic dicarboxylic acid dihalide is preferably isophthalic acid, p-nonanoic acid, diphenyl ether 4,4'-dicarboxylic acid and naphthalene-2,6. - Dicarboxylic acid diacid dichloride.

A mixture of isophthalic acid and p-acid diacid dichloride is particularly preferred in a ratio of from 1:20 to 20:1.

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

In addition to the monophenols already mentioned, chain terminators suitable for the preparation of the aromatic polyester carbonates may also be acid chlorides of the chlorocarbonates and aromatic monocarboxylic acids, optionally It is substituted by C ₁ - to C ₂₂ -alkyl or by a halogen atom, and may be an aliphatic C ₂ - to C ₂₂ -monocarboxylic acid chloride.

In each case, the chain terminator is contained in an amount of 0.1 to 10 mol%, based on the number of diphenols in the case of the phenolic chain terminator, and in the case of the monocarboxylic acid chloride chain terminator. The molar number of the carboxylic acid dichloride is based on the number of moles.

The aromatic polyester carbonates may also contain a hydroxycarboxylic acid incorporated therein.

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

Can be used as a branching agent, for example, having three or more functionalities Carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3',4,4'-benzophenone-tetra a carboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride in an amount of 0.01 to 1.0 mol% (based on the dicarboxylic acid used) Chloride as a benchmark); or a phenol with three or more functionalities, such as phloroglucinol (phloroglucinol), 4,6-dimethyl-2,4,6-tris-(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl)-heptane, 1,3,5-tris-(4-hydroxyphenyl)-benzene, 1,1,1-tris-(4-hydroxy-phenyl)-ethane, three -(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-methyl-phenol, 2-(4 -hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxy)-methane, 1,4-double [4,4'-Dihydroxytriphenyl)-methyl]-benzene, in an amount of from 0.01 to 1.0 mol%, based on the diphenols used. The phenolic branching agent can be placed in a reaction vessel containing diphenols; the acid chloride branching agent can be fed together with the acid dichloride.

The amount of the carbonate building block in the thermoplastic aromatic polyester carbonate may vary as desired, and the amount of the carbonate group is preferably at most 100 mol%, particularly at most 80 mol%, particularly preferably at most 50 mol% based on the sum of ester groups and carbonate groups. The esters and carbonates contained in the aromatic polyester carbonates may be polycondensation products in the form of blocks or random random forms.

The relative solution viscosity (η _rel ) of the aromatic polycarbonates and polyester carbonates is preferably in the range of 1.18 to 1.4, particularly preferably in the range of 1.20 to 1.32 (in 0.5 g of polycarbonate or polyester). The carbonate was measured in 100 ml of a solution of methylene chloride at 25 ° C). The weight-average molecular weight Mw of the aromatic polycarbonates and polyester carbonates is preferably in the range of from 15,000 to 35,000, more preferably in the range of from 20,000 to 33,000, particularly preferably in the range of from 23,000 to 30,000, in terms of GPC ( Gel permeation chromatography was determined in dichloromethane using polycarbonate as a standard.

In a preferred embodiment, according to the present invention, the aromatic polyester suitable as component A is a polyalkylene terephthalates. In particular embodiments, they are reaction products of aromatic dicarboxylic acids or reactive derivatives thereof, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols, and A mixture of reaction products.

Particularly preferred polyparaphthalic acid alkyl esters containing at least 80 wt.%, preferably at least 90 wt.% of a decanoic acid group, based on the dicarboxylic acid component, and at least 80 Wt.%, preferably at least 90 mol% of ethylene glycol and/or 1,4-butanediol base, based on the diol component.

Also containing a decanoic acid group, preferred polyalkylene terephthalate diesters may contain up to 20 mol%, preferably up to 10 mol% of other aromatic or cycloaliphatic dicarboxylates having from 8 to 14 carbon atoms. An acid radical, or an aliphatic dicarboxylic acid radical having 4 to 12 carbon atoms, such as, for example, citric acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylate The base of acid, succinic acid, adipic acid, azelaic acid, sebacic acid, and cyclohexane diacetic acid.

Also containing ethylene glycol and/or 1,4-butanediol base, preferred polyparaphthalic acid alkyl esters may contain up to 20 mol%, preferably up to 10 mol%, having from 3 to 12 carbon atoms Other aliphatic diol or cycloaliphatic diol having 6 to 21 carbon atoms, such as 1,3-propane diol, 2-ethyl-1,3-propane diol, 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-hydroxypropoxyphenyl) - the base of propane (DE-A 2 407 674, 2 407 776, 2 715 932).

The polyparaphthalic acid alkyl esters can be branched by incorporation of relatively small amounts of tri- or tetra- or alcohols, for example according to DE-A 1 900 270 and US-PS. 3 692 744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylol-ethane and -propane and pentaerythritol.

Particularly suitable are polyparaphthalic acid alkyl esters which have been completely supported by citric acid and its reactive derivatives (for example, its dialkyl esters) with ethylene glycol and /1,4-butanediol. Prepared, and for this purpose a mixture of polyparaphthalic acid diesters.

The mixture of polyparaphthalic acid alkyl esters contains 1 to 50 wt.% (preferably 1 to 30 wt.%) of polyethylene terephthalate and 50 to 99 wt.% (preferably to 70 to 99 wt.%) of polybutylene terephthalate.

More suitable polyparaphthalic acid diesters usually have an ultimate viscosity The limiting viscosity is from 0.4 to 1.5 dl/g, preferably from 0.5 to 1.2 dl/g, as measured by Ubbelohde viscosity in phenol/o-dichlorobenzene (1:1 part by weight) at 25 °C.

The polyparaphthalic acid diesters can be obtained by a method known per se (see, for example, Kunststoff-Handbuch, Volume VIII, p. 695 ff, Carl-Hanser-Verlag, Munich 1973).

Ingredient B

Component B is a rubber-modified graft polymer B.1, or a rubber-free vinyl (co)polymer B.2, or a mixture of a plurality of such polymers.

The rubber-modified graft polymer B.1 as component B comprises B.1.1 5 to 95 wt.%, preferably 15 to 92 wt.%, especially 25 to 60 wt.%, of at least one ethylene. The base monomer, based on the component B.1, is grafted to one or more rubbery forms of B.1.2 95 to 5 wt.%, preferably 85 to 8 wt.%, especially 75 to 40 wt.%. The graft base, preferably based on component B.1, preferably has a glass transition temperature of <10 ° C, more preferably < 0 ° C, and particularly preferably < -20 ° C.

The glass transition temperature is measured by means of differential scanning calorimetry (DSC) according to standard DIN EN 61006 at a heating rate of 10 K/min, with Tg defined as mid-point temperature (tangent method) ).

The graft base B.1.2 generally has an average particle diameter (d ₅₀ value) of from 0.05 to 10 μm, preferably from 0.1 to 5 μm, particularly preferably from 0.2 to 1 μm.

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

The monomer B.1.1 is preferably a mixture of the following B.1.1.1 50 to 99 parts by weight, preferably 60 to 80 parts by weight, particularly 70 to 80 parts by weight, of the vinyl aromatic compound and/or a vinyl aromatic compound substituted on the ring (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene), and/or a methacrylic acid (C ₁ -C) ₈ )-alkyl esters (such as methyl methacrylate, ethyl methacrylate), based on B.1.1, and B.1.1.2 1 to 50 parts by weight, preferably 20 to 40 parts by weight Parts, especially 20 to 30 parts by weight, of vinyl cyanide (unsaturated nitriles such as acrylonitrile and methacrylonitrile), and/or (meth)acrylic acid (C ₁ -C ₈ )-alkane Base esters (such as methyl methacrylate, n-butyl acrylate, tri-butyl acrylate), and/or derivatives of unsaturated carboxylic acids (such as anhydrides and quinones), for example Maleic anhydride and N-phenyl-maleimide, based on B.1.1.

Preferably, the monomer B.1.1.1 is selected from at least one of the following monomers: styrene, α-methylstyrene and methyl methacrylate, and preferably the monomer B.1.1.2 is selected from the group consisting of At least one of the following monomers: acrylonitrile, maleic anhydride, and methyl methacrylate, particularly preferred monomers B.1.1.1 are styrene and B.1.1.2 is acrylonitrile.

The graft base B.1.2 to which the graft polymer B.1 is applied is, for example, a diene rubber, an EP(D)M rubber, in other words, an exoethyl/extended propyl group and a selected diene, acrylate, Polyurethane, anthrone, chloroprene and ethyl/vinyl acetate rubber as substrates, and anthrone/acrylate composite rubber.

Preferred graft bases B.1.2 are diene rubbers, for example based on butadiene and isoprene, or a mixture of diene rubber or a copolymer of diene rubber, or copolymerizable with another A mixture of monomers (for example according to B.1.1.1 and B.1.1.2).

Pure polybutadiene rubber is particularly suitable as graft base B.1.2.

A particularly preferred polymer B.1 is, for example, an ABS or MBS polymer, as described, for example, in DE-OS 2 035 390 (corresponding to US-PS 3 644 574) or in DE-OS 2 248 242 (corresponding to GB-PS 1 409 275) or as described in Ullmanns, Enzyklopädie der Technischen Chemie, Vol. 19 (1980), p. 280 ff.

The graft copolymer B.1 is obtained by free radical polymerization, for example by emulsification, suspension, solution or bulk polymerization, preferably by emulsification or bulk polymerization, in particular by emulsion polymerization.

The gel content of the graft base B.1.2 is at least 30 wt.%, preferably at least 40 wt.%, especially at least 60 wt.%, in each case, based on B.1.2 The insoluble portion was measured in toluene.

The gel content of the graft base B.1.2 is determined to be insoluble in the solvent at 25 ° C in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I und II, Georg Thieme -Verlag, Stuttgart 1977).

Further, a particularly suitable graft base is an ABS polymer which is prepared by a redox initiation reaction system using an organic hydroperoxide and ascorbic acid initiator system according to US Pat. No. 4,937,285. Got it.

As is known, since the grafting monomer does not need to be completely grafted onto the grafted substrate during the grafting reaction, it is understood that, according to the present invention, the grafted polymer B.1 is present in the grafted substrate. The product obtained by the (co)polymerization of the graft monomer is used as a product obtainable by the treatment. Accordingly, such products may also contain a free (co)polymer of a grafting monomer, in other words, a (co)polymer that is not chemically bonded to the rubber.

Suitable acrylate rubbers according to B.1.2 are preferably polymers of alkyl acrylates, optionally with up to 40 wt.% (based on B.1.2) of other polymerizable ethylenically unsaturated monomers. The polymer of the body. The preferred polymerizable acrylate-based esters include: C ₁ - to C ₈ -alkyl esters such as methyl, ethyl, butyl, n-octyl and 2-ethylhexyl ester; Base esters, preferably halo-C ₁ -C ₈ -alkyl esters, such as chloroethyl acrylate, and mixtures of such monomers.

For cross-linking, monomers having more than one polymerizable double bond can be copolymerized. Preferred examples of the crosslinking monomer are: an ester of an unsaturated monocarboxylic acid having 3 to 8 carbon atoms and an unsaturated monohydric alcohol having 3 to 12 carbon atoms, or 2 to 4 OH groups and 2 to 20 a polyester of a saturated carbon polyol such as ethylene glycol dimethacrylate or allyl methacrylate; a polyunsaturated heterocyclic compound such as trivinyl and melamine Trialyl cyanurate; polyfunctional vinyl compounds such as di- and tri-vinylbenzene; also triallyl phosphate and diallyl citrate Phthalate). Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least three ethylenically unsaturated groups. a particularly preferred crosslinking monomer is a cyclic monomer triallyl. Cyanate ester, triallyl isocyanate, triacryloylhexahydro-s-triazine, triallyl benzene. The content 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.1.2. In the case of a cyclic crosslinking monomer having at least three ethylenically unsaturated groups, an advantageous content is limited to less than 1 wt.% of the graft base B.1.2.

In addition to the propylene-based acid esters, preferred "other" polymerizable, ethylenically unsaturated monomers which can be optionally used in the preparation of the graft base B.1.2 are acrylonitrile, styrene, alpha-methylbenzene. Ethylene, acrylamide, vinyl C ₁ -C ₆ -alkyl ethers, methyl methacrylate, butadiene. A preferred acrylate rubber as graft base B.1.2 is an emulsified polymer having a gel content of at least 60 wt.%.

According to B.1.2, a further suitable graft base is an anthrone rubber having a graft-active site, such as DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539 as described.

According to the component B.2, the rubber-free vinyl (co)polymer is preferably a rubber-free and/or co-polymer: vinyl aromatic selected from at least one monomer comprising the following group; a compound, a vinyl cyanide (unsaturated nitrile), a (meth)acrylic acid (C ₁ to C ₈ )-alkyl ester, an unsaturated carboxylic acid, and a derivative of an unsaturated carboxylic acid (such as an acid anhydride) Terpenoids).

Particularly suitable are the following (co)polymers B.2 B.2.1 in each case based on the total weight of the (co)polymer B.2, 50 to 99 wt.%, preferably 60 to 80 wt. .%, especially 70 to 80 wt.%, selected from at least one monomer comprising the following group: a vinyl aromatic compound such as, for example, styrene, α-methylstyrene; substituted on the ring Vinyl aromatic compounds such as, for example, p-methylstyrene, p-chlorostyrene; and (meth)acrylic acid (C ₁ -C ₈ )-alkyl esters such as, for example, Methyl methacrylate, n-butyl acrylate, tri-butyl acrylate, and B.2.2 in each case based on the total weight of (co)polymer B.2, 1 to 50 wt.% Preferably, 20 to 40 wt.%, especially 20 to 30 wt.%, of at least one monomer selected from the group consisting of vinyl cyanide, such as, for example, an unsaturated nitrile such as, for example, propylene. Nitrile and methacrylonitrile; (meth)acrylic acid (C ₁ -C ₈ )-alkyl esters such as, for example, methyl methacrylate, n-butyl acrylate, acrylic acid third-butyl Base ester; unsaturated carboxylic acid and derivative of unsaturated carboxylic acid Such as (for example) of maleic anhydride and N- phenyl - maleic acyl imine.

These (co)polymers B.2 are resinous, thermoplastic and rubber-free, and particularly preferred are copolymers of the B.2.1 styrene and B.2.2 acrylonitrile.

Such (co)polymers B.2 are known and can be prepared by free radical polymerization, in particular by emulsification, suspension, solution or bulk polymerization. The (co)polymer preferably has a molecular weight Mw (weight average, as measured by GPC, using polystyrene as a standard) of from 15,000 to 250,000 g/mol, preferably from 80,000 to 150,000 g/mol.

Ingredient C

At least one adsorbent or absorbing inorganic or organic material is used as the component C.

In a preferred embodiment, component C is a finely divided and/or porous material having a large outer and/or internal surface area.

Such materials are preferably thermally inert inorganic materials such as, for example, oxides or mixed oxides of metal or transition metals, silicates, sulfides, nitrides.

In a preferred embodiment, component C is a finely divided and/or microporous natural or synthetic source of vermiculite or ceria or strontium.

According to the invention, the finely divided cerium oxide which is suitable as a natural source of component C is, for example, kieselguhr, which is a white, powdery substance, mainly oxidized by fossil diatoms. The crucible is composed of a majority of amorphous (non-crystalline) cerium oxide (SiO ₂ ) and has a highly porous structure.

In a preferred embodiment, precipitated vermiculite and silicates of synthetic origin and pyrogenic silica are used as component C.

Synthetic precipitated vermiculite (tank) and phthalates are finely divided, loose, white powders which can also be made into comminuted form for specific applications. Their particles are amorphous. Chemically, such vermiculite and silicates consist of up to about 99% cerium oxide (SiO ₂ ).

The starting material for producing vermiculite by wet method is an alkaline citrate solution, preferably sodium water glass, from which an amorphous vermiculite is precipitated by adding an acid. After filtration, washing and drying, the precipitated product consists of 86 to 88% SiO ₂ and 10 to 12% water, which are simultaneously physically bonded to the molecular unit and to the surface.

Metal citrates, such as calcium citrate and aluminum citrate, are prepared by substituting an acid for precipitation of all or part of the metal salt, which forms a sparingly soluble precipitate of aqueous glass.

The precipitated vermiculite suspension is transferred to a filter press where the salt formed during the precipitation is washed out and the water is removed as much as possible. The filter cake will still contain significant levels of water which is evaporated during subsequent drying. Drying is carried out by different methods depending on the nature of the desired vermiculite product. Subsequently, the grinding, meshing and/or granulating steps are often carried out.

An alternative method for the preparation of finely divided cerium oxide, suitable for the flame hydrolysis of ruthenium tetrachloride (SiCl ₄ ) or other volatile chloroalkanes in the oxyhydrogen flame process ("Aerosil" method) As component C. In this process, the formation of so-called pyrolytic vermiculite typically has a primary particle diameter of about 5 to 50 nm and a specific surface area of about 30 to 600 m ² /g. By varying the concentration of the reactants, it affects the flame temperature and the residence time of the vermiculite in the combustion chamber, the particle size of the pyrolytic vermiculite, the particle size distribution, the specific surface area and the surface quality.

The primary particles fused in the flame form large units (aggregates) of diameters of 100 to 1000 nm, and once cooled, sequentially form floccules, mesoporous grades having a diameter of about 1 to 250 μm. Structure (agglomerates).

In a particularly preferred embodiment, the precipitated vermiculite is used as component C. These may have a hydrophilic surface or may be in a hydrophobic form upon modification of the surface of the organic molecule.

In a particularly preferred embodiment, since component D is a hydrophilic nature and is preferably used in the form of an aqueous solution, in this particular case, it is recommended to use a hydrophilic precipitated vermiculite as component C.

However, in order to achieve the optimum wetting of the component C by using the component D, it is also possible to use a precipitated vermiculite having a hydrophobic surface in a favorable case.

In this preferred embodiment, the precipitated vermiculite as component C preferably has a specific BET surface area of from 150 to 600 m ² /g, in particular from 300 to 600 m ² /g, according to ISO 5794-1. Adsorption assay. Furthermore, they have an oil absorption number of preferably from 150 to 500 g/100 g, in particular from 300 to 400 g/100 g, determined by absorption of dibutyl phthalate (DBP) according to DIN 53601. . The suitable hydrophilic precipitated vermiculite further preferably has a pH in the acidic range (i.e., <7), particularly in the range of 6 to 7, as determined by a 5 wt.% suspension of vermiculite in water according to ISO 787-9. .

Ingredient D

At least one type of Brinell-acidic compound is used as the component D.

In a preferred embodiment, component D in a solution of an inorganic or organic solvent, preferably water, is applied to carrier C.

A suitable concentration of the Brinell-acidic compound for the solution is from 0.2 to 90 wt.%, preferably from 1 to 90 wt.%, particularly preferably from 10 to 90 wt.%, especially from 50 to 90 wt.%, In each case, based on the solution, in other words, based on the total of the component D and the solvent.

In the case of an acid used in a solution, the component D content is calculated as a solvent-free pure acid.

The Brinell-acidic compound is preferably a mineral acid, more preferably a phosphoric acid compound, in other words, a compound having at least one POH functionality.

Examples of such compounds are --phosphoric acid P(O)(OH) ₃ ,-phosphite HP(O)(OH) ₂ ,-phosphoric acid H ₂ P(O)(OH),-organic phosphorus compounds , having the general formula RP(O)(OH) ₂ , R(H)P(O)(OH), and R(R')P(O)(OH) phosphorous acid and hypophosphorous acid, wherein R and R' are each other Independently representing any desired optionally substituted alkyl, aryl or alkaryl group, and cyclic or linear oligomeric or polymeric compounds, acid salts of the above compounds and acid partial esters. R and R' are, independently of each other, particularly preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl groups.

In a preferred embodiment, the Brinell-acidic phosphorus-containing compound wherein the phosphorus-containing compound has an oxidation state of +3 or +5, particularly preferably an oxidation state of +5.

Suitable as a particularly good Brinell-acid phosphorus compound are, for example, n-phosphoric acid, meta-phosphoric acid, oligo- and poly-phosphoric acid, phosphorous acid, methylphosphonic acid CH ₃ P(O)(OH) ₂ , An acid salt of the above compound having a monovalent and/or divalent metal cation, such as, for example, 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 And partial esters of the above compounds, such as, for example, 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 Brinell-acidic phosphorus-containing compound is n-phosphoric acid or phosphorous acid, and in a particularly preferred embodiment, it is a n-phosphoric acid, preferably in the form of concentrated phosphoric acid.

Ingredient E

The composition may contain a commercially available polymer additive as component E.

In addition to ingredients C and D, it is suitable as a commercially available polymer additive according to the ingredient E additive, such as, for example, a flame retardant (such as a phosphorus or halogen compound), a flame-retardant synergist, Suppressing smoke additives (such as boric acid or borate), antidripping agents (such as fluorinated polyolefins, anthrone, and aramid fibers), internal and external lubricants, and demolding Agents (such as pentaerythritol stearate, Montan wax or polyethylene wax), flow aids (such as low molecular weight vinyl (co)polymers), antistatic agents (such as ethylene oxide and Block copolymers of propyl oxide, other polyethers or polyhydroxy ethers, polyether amides, polyester amides or sulfonates), conductive additives (eg conductive carbon black or carbon) Nanotubes), stabilizers (such as UV/light stabilizers, heat stabilizers, antioxidants, transesterification inhibitors, hydrolysis stabilizers), antibacterial additives (such as silver or silver salts), improve scratch resistance Additives (such as fluorenone oil, or hard fillers such as (hollow) pottery Ball), IR absorbers, optical brighteners, fluorescent additives, in addition to a filler component F and the reinforcing material (e.g., ground glass (ground glass) or carbon fiber, (hollow) glass or ceramic spheres, mica, kaolin, CaCO ₃ and glass a tablet), and a coloring agent and pigment (such as carbon black, titanium dioxide or iron oxide), or a mixture of a plurality of the above additives.

As the flame retardant according to the component E, it is preferred to use a phosphorus-containing compound. Compound. Such compounds are preferably selected from the group consisting of monomeric and oligomeric phosphorus and phosphine esters, phosphate amines and phosphazene, and may also be selected from the group consisting of A mixture of one or more components acts as a flame retardant. Other halogen-free phosphorus-containing compounds not specifically mentioned herein may also be used alone or in combination with other halogen-free phosphorus-containing compounds in any desired combination.

Preferred monomeric and oligomeric phosphorus and phosphine esters are phosphorus compounds such as general formula (IV) Wherein R ¹ , R ² , R ³ and R ⁴ , in each case, independently of each other represent a selectively halogenated C ₁ - to C ₈ -alkyl group, or a C ₅ - to C ₆ -cycloalkyl group, C ₆ - to C ₂₀ -aryl or C ₇ - to C ₁₂ -aralkyl, each optionally by alkyl (preferably C ₁ - to C ₄ -alkyl) and/or by halogen (preferably chlorine or Bromine), each substituent number n independently represents 0 or 1, q represents 0 to 30, and X represents a mono- or poly-nuclear aromatic radical having 6 to 30 carbon atoms, or has 2 to A linear or branched aliphatic base of 30 carbon atoms which may be OH-substituted and may contain up to 8 ether linkages.

R ¹ , R ² , R ³ and R ⁴ preferably independently of one another represent C ₁ - to C ₄ -alkyl, phenyl, naphthyl or phenyl-C ₁ -C ₄ -alkyl. The aromatic groups R ¹ , R ² , R ³ and R ⁴ may be optionally substituted by halogen and/or alkyl, preferably chlorine, bromine and/or C ₁ - to C ₄ -alkyl. Particularly preferred aryl groups are cresyl, phenyl, xylyl, propylphenyl or butylphenyl groups and their corresponding brominated and chlorinated derivatives.

In the formula (IV), X preferably represents a mono- or poly-cyclic aromatic group having 6 to 30 carbon atoms, preferably derived from the diphenol of the formula (I).

In the formula (IV), the number of substituents n may be 0 or 1 independently of each other; n is preferably 1.

q represents a value of from 0 to 30, preferably from 0.3 to 20, particularly preferably from 0.5 to 10, particularly from 0.5 to 6, most preferably from 1.1 to 1.6.

X is particularly representative Or a chlorinated or brominated derivative thereof; in particular X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol, and X is particularly preferably derived from bisphenol A.

Mixtures of different phosphates can also be used as component F according to the invention.

The phosphorus-containing compound of the formula (IV) is in particular tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl-2 Ethyl cresyl phosphate, tris-(isopropylphenyl) phosphate, resorcinol-bridged oligophosphate, and bisphenol A-bridged oligophosphate. Particularly preferred are oligomeric phosphates of formula (IV) derived from bisphenol A.

The most preferred ingredient F is bisphenol A based oligophosphate according to formula (IVa)

The phosphorus-containing compound according to the component F is known (cf., for example, EP-A 0 363 608, EP-A 0 640 655) or can be obtained according to known methods in a similar manner (for example 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-containing compounds is used, and in the case of an oligomeric phosphorus-containing compound, the labeled q value is a mean q value. The average q value can be determined by a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)) to determine the composition of the phosphorus-containing compound (molecular weight Distribution) detection, and the average of q is calculated therefrom.

Phosphate amines and phosphorus-nitrogen rings can also be used as flame retardants, as described in WO 00/00541 and WO 01/18105.

The flame retardant can be used alone or in any mixture with the other or with other flame retardants.

In a preferred embodiment, the flame retardant is used in combination with polytetrafluoroethylene (PTFE) as an anti-drip agent.

Ingredient F

As component F, naturally occurring or synthetically prepared talc is optionally used as the filler.

The pure talc has a chemical composition of 3MgO‧4SiO ₂ ‧H ₂ O, and thus has a MgO content of 31.9 wt.%, a SiO ₂ content of 63.4 wt.%, and a chemically bonded water content of 4.8 wt.%, which has Layer structure of citrate.

Naturally occurring talc materials generally do not have the desired composition as described above because they are partially substituted for other elements of magnesium, such as partially substituted Contamination of aluminum, and/or other minerals such as, for example, dolomite, magnesite, and chlorite.

A talc type having an extremely high purity is suitable as the component F, and such a talc type is characterized by a MgO content of 28 to 35 wt.%, preferably 30 to 33 wt.%, particularly preferably 30.5 to 32 wt.%, and SiO _{2 .} The content is 55 to 65 wt.%, preferably 58 to 64 wt.%, particularly preferably 60 to 62.5 wt.%. A particularly preferred type of talc is further distinguished by an Al ₂ O ₃ content of less than 5 wt.%, particularly preferably less than 1 wt.%, especially less than 0.7 wt.%.

It is particularly advantageous to use talc in a finely ground form having an average particle size d ₅₀ of <10 μm, preferably <5 μm, particularly preferably <2 μm, optimally <1.5 μm.

To ensure good compatibility with the polymer, the talc can be surface treated, such as decaneized.

With regard to the processing and preparation of the molded composition, it is advantageous to use compressed talc.

The invention further relates to a method for producing a polycarbonate composition according to the invention, characterized in that in the first method step, component C is mixed with component D of wet component C, and component D is thus applied to component C, 2. In a second (subsequent) process step, a mixture of the components C and D in powder form is admixed with another component of the composition in a kneading unit, preferably a counter-rotating twin screw extruder. It is preferably carried out under the conditions conventionally used for the production method of the polycarbonate blend.

In a further preferred embodiment, in the intermediate step, the powdered ingredients B, E and optionally F, or a component thereof, are first mechanically pre-formed with the previously prepared powdered blend of ingredients C and D. The mixing, and the resulting powdered, pourable mixture and additional ingredients are fed to the mixing unit.

In a preferred embodiment, in step 1, a solution of component D in an organic or inorganic solvent, preferably water, is first mixed with component C.

In another preferred embodiment, in the degassing zone of the kneading unit, the application of the low pressure is again applied to the group using the acidic compound solution according to component D. The solvent of the product is removed.

The invention further relates to the use of a Brookfield acid according to component D, which is applied to component C, for the thermal stabilization of a polymer mixture, which comprises alkaline impurities, self-polycondensation, kneading and thermoforming. At least one polymer.

Example

Ingredient A

a linear polycarbonate based on bisphenol A having a weight-average molecular weight Mw of 28,000 g/mol (determined by gel permeation chromatography (GPC), using dichloromethane as a solvent, and using polycarbonate as a solvent Standard).

Ingredient B

ABS blend contains acrylonitrile: butadiene: styrene ratio of 20:19:61 wt.% (based on blend), with SAN polymer, containing ABS polymer by emulsion polymerization and in alkali It is prepared by treatment in a medium, and the ABS polymer is obtained by an overall polymerization reaction.

Ingredient C

According to ISO 5794-1, the hydrophilic vermiculite powder has a specific BET surface area of 475 m ² /g as measured by nitrogen, a pH of 6 in a 5% aqueous suspension according to ISO 787-9, and according to DIN 53601, oil absorption number measured using dibutyl phthalate (DBP) was 335 g / 100 g.

Ingredient D

The concentrated aqueous phosphoric acid has a H ₃ PO ₄ concentration of 85 wt.%.

Ingredient E1

Pentaerythritol tetrastearate is used as a lubricant/release agent.

Ingredient E2

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

Ingredient E3

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

Preparation of molding composition

Ingredients C and D are first mixed together while stirring to form a pourable powder.

The powdered ingredients B, E1 to E3 are mechanically pre-mixed with the previously prepared powdered blends of ingredients C and D; the resulting mixture is powdered and pourable.

In a further method step, the prepared powder mixture is fed together with the components A and B by means of a separate metering feeder, likewise fed into the ZSK25 twin screw extrusion by means of a separate metering feeder. Intake zone (available from Coperion GmbH (Stuttgart, Germany)).

The resulting mixture was passed to a melting and kneading zone of an extruder at a temperature of 260 ° C, at which temperature, melting and kneading, and the plasticized components were thus dispersed in each other.

In the subsequent degassing zone of the extruder, by applying a low pressure of 100 mbar (absolute) to the melt, the blended mixture is degassed, and the water introduced into the mixture via component D is again from the polymerization. The object was removed.

The degassed melt is then discharged from the extruder via a die, and the resulting melt strand is cooled through a water bath at a temperature of about 30 ° C, and the solidified polymer strip is subsequently produced by stripping. Granulator means granulation.

Preparation and testing of test samples

The granulates produced by each mixing were processed on an injection-molding machine (Arburg) at a melting temperature of 260 ° C and 300 ° C and a tool temperature of 80 ° C to form a measured 80 mm x 10 mm x Test samples of 4 mm and 60 mm x 40 mm x 2 mm.

The iMVR acts as a desired degradation of the polycarbonate molecular weight at high processing temperatures, and, depending on the thermal stability of the composition, and at a melt temperature of 300 ° C according to ISO 1133, with a plunger load For 5 kg, at The temperature was maintained at 300 ° C for 15 minutes and then detected.

The natural/inherent color is measured by reflectance on a 60 mm x 40 mm x 2 mm sheet according to DIN 6174, which is obtained by injection molding at a melt temperature of 260 ° C; the yellowness index is calculated according to ASTM E313 YI.

Gloss was measured on a sheet of 60 mm x 40 mm x 2 mm, which was prepared by injection molding at a melt temperature of 260 ° C and 300 ° C; according to DIN 67530, the angle of detection was 20 ° and 60 ° Measured at reflectance.

The relative change in gloss measured at a detection angle of 20° and 60° was raised to 300 ° C at a melting temperature of 260 ° C in injection molding as a measurement of processing stability and calculation according to the following: gloss (260 ° C → 300 ° C) change = 100% feel (300 ° C gloss - 260 ° C gloss) / 260 ° C gloss.

The change in gloss is measured at two detection angles.

From the data in Table 1, the composition according to the present invention (Example 1) has improved processing stability in terms of the stability of gloss to processing temperature, and does not contain a phosphate compound as compared with the three comparative examples. Comparative Example 1 in which C does not contain vermiculite D, the composition according to Example 1 of the present invention additionally exhibits significantly improved thermal stability in terms of molecular weight degradation of the polycarbonate at high processing temperatures; The phosphoric acid compound C itself (Comparative Example 2) can largely eliminate defects, but in terms of the stability of the gloss to the processing temperature, the loss of processing stability cannot be eliminated; moreover, with the composition according to the present invention (Example 1) In comparison, Comparative Example 2 has a poor natural color; according to Example 1 of the present invention and Comparative Example C3 (compared to Example 1, wherein the blend of the phosphate compound C and the vermiculite D is used at a higher concentration) Comparison, when limiting the total amount of phosphoric acid and vermiculite, only the desired combination of properties is shown; at higher concentrations (Comparative Example 3), the positive effect of the addition of the blend of phosphate compound and vermiculite is reversed, In other words, heat stability is observed. Of (molecular weight degradation of the polycarbonate), the processing stability (gloss stability of the processing temperature) degradation and natural color (yellow index) of action.

Claims (15)

A method for producing a polymer composition comprising A) 10 to 100 parts by weight of at least one polymer selected from the group consisting of aromatic polycarbonates, aromatic polyester carbonates, and aromatic polyesters The group, based on the sum of the components A+B, B) 0 to 90 parts by weight of at least one rubber-modified vinyl (co)polymer, based on the sum of the components A+B, C) 0.00025 to 0.080 parts by weight of at least one inorganic or organic adsorbent or absorbent based on the sum of the components A+B, D) 0.001 to 0.300 parts by weight of at least one Brinell-acid compound, and the sum of the components A+B For reference, E) 0.1 to 40.0 parts by weight of at least one additive other than components C, D and F, based on the sum of components A+B, F) 0 to 50 parts by weight of talc, with component A+B The sum is the basis, wherein the sum of the parts by weight of the component A+B in the composition is 100, and the method comprises the steps of: - mixing the component C with the component D, the component D wetting the component C, - a commercially available kneading In the unit, a mixture of the powder forms of the components C and D and the other components of the composition are blended. The method of claim 1, wherein the component D is first prepared in a solution of an organic or inorganic solvent, and the solution is mixed with the component C, and the solution of the component D is wetted with the component C. The method of claim 1 or 2, wherein in the intermediate step, the powdery ingredients B, E and optionally F, or a component thereof, are prepared in the prior art. The powdery blends of the powder blends of C and D or the solutions of component C and component D are first mechanically premixed, and the prepared powdery, castable mixture is fed to a mixing unit containing additional components. in. The method according to any one of the preceding claims, wherein, in the degassing zone of the kneading unit, the solvent added to the composition by the solution of the acid compound D is removed again by applying a low pressure. According to the method of claim 1, which is used for producing a polymer composition comprising 55 to 65 parts by weight of component A, 35 to 45 parts by weight of component B, 0.001 to 0.010 part by weight of component C, 0.005 to 0.05 The component D in parts by weight, 0.3 to 2.0 parts by weight of the component E, and 0 to 50 parts by weight of the component F, wherein the sum of the components A + B by weight in the composition is 100. A polymer composition comprising A) 10 to 100 parts by weight of at least one polymer selected from the group consisting of aromatic polycarbonates, aromatic polyester carbonates, and aromatic polyesters, with component A Based on the sum of +B, B) 0 to 90 parts by weight of at least one selected rubber-modified vinyl (co)polymer based on the sum of components A+B, C) 0.00025 to 0.080 parts by weight At least one inorganic or organic adsorbent or absorbent based on the sum of components A+B, D) 0.001 to 0.300 parts by weight of at least one Brinell-acidic compound, based on the sum of the components A+B, E) 0.1 to 40.0 parts by weight of at least one additive other than the components C, D and F, with the component A The total of +B is based on the total, and F) 0 to 50 parts by weight of talc, based on the total of the components A+B, wherein the sum of the components A+B in the composition is 100. The polymer composition according to claim 6 of the patent application, comprising 55 to 65 parts by weight of the component A, 35 to 45 parts by weight of the component B, 0.001 to 0.010 part by weight of the component C, 0.005 to 0.05 part by weight of the component D, 0.3 to 2.0 parts by weight of the component E, and 0 to 50 parts by weight of the component F. The polymer composition according to claim 6 or the seventh aspect of the patent application, wherein the organic adsorbent or absorbent of the component C is different from the component A or B. The polymer composition according to any one of claims 6 to 8, wherein the component D is used in an amount of at least 25 parts by weight based on the total of the components C and D. The polymer composition according to any one of claims 6 to 8, wherein the component D is used in an amount of at least 60 parts by weight based on the total of the components C and D. The polymer composition according to any one of claims 6 to 10, wherein the component C is selected from the group consisting of a thermally inert inorganic material, an oxide of a metal or a transition metal, a mixed oxide, a cerium salt, and a vulcanization. a group of matter, nitride, and mixtures thereof. The polymer composition according to any one of the preceding claims, wherein the component C is selected from the group consisting of finely dispersed and microporous vermiculite, ceria, and strontium salts of natural or synthetic origin, and a group of its mixtures. The polymer composition according to any one of claims 6 to 10, wherein component C is selected from the group consisting of precipitated vermiculite having a specific BET surface area as determined by nitrogen adsorption according to ISO 5794-1 150 to 600 m ² /g, based on the absorption of dibutyl phthalate according to DIN 53601, the oil absorption number is from 150 to 500 g / 100 g, and according to ISO 787-9, the suspension of 5 wt.% vermiculite in water The pH of the solution was <7. The polymer composition according to any one of claims 6 to 13, wherein the component D is selected from the group consisting of: a Brinell-acidic phosphorus-containing compound, wherein the phosphorus-containing compound has an oxidation state of +3 or + 5. A use of B-acid according to component D for the application of component C for the thermal stabilization of a polymer mixture during kneading and thermoforming, comprising basic impurities, comprising at least one polymer obtained by polycondensation.