Ternary blends.

The present invention relates to ternary mixtures containing<ul id="ul0001" list-style="none"><li>A) 49.9 to 96.9% by weight, preferably 59.9 to 96.9% by weight and in particular 79.6 to 94.9% by weight of thermoplastic, aromatic polycarbonates and / or thermoplastic, aromatic polyester carbonates,</li><li>B) 3 to 50% by weight, preferably 3 to 40% by weight and in particular 5 to 20 wt .-% of glass fibers and</li><li>C) 0.1 to 10% by weight, preferably 0.1 to 5% by weight and in particular 0.4 to 3% by weight of C₂-C₈-olefin-acrylic acid ester-maleic anhydride terpolymers,</li></ul> the sum of the% by weight of components A) + B) + C) being 100% by weight.

Glass fiber-containing polycarbonates with the addition of polyanhydride resins are known (see US Pat. No. 4,420,584 and EP-B1-0 063 769). These molding compounds have improved impact strength and greater elongation at break. In the hot air aging test, however, these polycarbonate molding compounds change color strongly, which is associated with molecular degradation of the polycarbonate matrix.

In contrast to this, the mixtures according to the invention have not only good impact strength but also a stable color locus after hot air aging.

The components

The polycarbonate component A) is both a homocopolycarbonate and a copolycarbonate, mixtures of polycarbonates of both homopolycarbonates and copolycarbonates also being suitable.

The polycarbonates according to component A) should have weight average molecular weights M_w (determined, for example, in a known manner via the relative solution viscosity or by gel chromatography after prior calibration) from 10,000 to 200,000, preferably from 20,000 to 80,000.

The polycarbonates according to component A) are those based on the diphenols of the formula a)         HO ― D ― OH a), in which D is a divalent aromatic radical of 6 to 50 C atoms, in particular of 12 to 45 C atoms, which may also contain heteroatoms or C-containing hetero segments which are not subsumed under the 6 to 50 C atoms.

The polycarbonates thus have bifunctional structural units of the formula b)<chemistry id="chem0001" num="0001"><img file="EP0472064A2_D0001.tif" /></chemistry> where D has the meaning given above.

The polycarbonates of component A) can moreover in a known manner (see for example DE-PS 2 500 092 and US-PS 4 185 009) by incorporating small amounts, preferably between 0.05 and 2 mol%, based on the diphenols used , on three or more than three-functional compounds, for example those with three or more than three OH groups.

Some of the compounds used with three or more than three phenolic hydroxyl groups are, for example, phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenol) ) -benzene, 1,1,1-tri- (4-hydroxyphenyl) ethane, 2,6-bis (2'-hydroxy-5'-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl ) -2- (2,4-dihydroxyphenyl) propane and 1,4-bis (4,4'-dihydroxytriphenylmethyl) benzene.

Some of the other three-functional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (4-hydroxy-3-methylphenyl) -2-oxo-2,3-dihydroindole.

Suitable diphenols of the formula a) are, for example, those of the formula a) 1)<chemistry id="chem0002" num="0002"><img file="EP0472064A2_D0002.tif" /></chemistry> in which Z is a single bond, an alkylene radical with 1 to 8 C atoms, an alkylidene radical with 2 to 12 C atoms, a cyclohexylidene radical, a benzylidene radical, a methylbenzylidene radical, a bis ( phenyl) methylene radical, -S-, -SO₂, -CO- or -O-, wherein the phenylene cores linked by Z can also be mono- or disubstituted by methyl, bromine or chlorine.

Suitable diphenols of the formula a) are also those of the formula a) 2)<chemistry id="chem0003" num="0003"><img file="EP0472064A2_D0003.tif" /></chemistry> wherein<dl id="dl0001"><dt>R₁ and R₂</dt><dd>independently of one another hydrogen, halogen, preferably chlorine or bromine, C₁, -C₆-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₀-aryl, preferably phenyl, and C₇-C₁₂-alkyl, preferably phenyl-C₁-C₄-alkyl, in particular Benzyl,</dd><dt>m</dt><dd>an integer from 4 to 7, preferably 4 or 5,</dd><dt>R₃ and R₄,</dt><dd>individually selectable for each X, independently of one another hydrogen or C₁-C₆-alkyl</dd></dl> and<dl id="dl0002"><dt>X</dt><dd>Carbon mean</dd></dl> with the proviso that on at least one atom X R₃ and R₄ simultaneously mean alkyl.

Here are 1 to 2 atoms X, especially only one atom X, R₃ and R₄ alkyl at the same time. The preferred alkyl radical is methyl; the X atoms in the α-position to the diphenyl-substituted C atom (C-1) are preferably not dialkyl-substituted, whereas the alkyl disubstitution in the β-position to C-1 is preferred.

In particular, preference is given here to dihydroxydiphenylcycloalkanes having 5 and 6 ring carbon atoms in the cycloaliphatic radical (m = 4 or 5 in formula a) 2)), for example the diphenols of the formulas<chemistry id="chem0004" num="0004"><img file="EP0472064A2_D0004.tif" /></chemistry> the 1,1-bis (4-hydroxyphenyl) -3.3.5-trimethylcyclohexane (formula a) 2) 1)) being particularly preferred.

The diphenols of the formula a) 2), their preparation and their use, if appropriate in combination with other diphenols, for the preparation of homopolycarbonates and copolycarbonates is the subject of German Offenlegungsschrift 3 832 396 (Le A 26 344).

The preparation of the other polycarbonates of component A), for example from the diphenols of the formula a) 1), is also known from the literature. (See, for example, H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York, 1964 or U.S. Patents 3,028,365 and 3,275,601.)

Examples of diphenols of the formula a) are Hydroquinone, Resorcinol, Dihydroxydiphenyls, Bis (hydroxyphenyl) alkanes, Bis (hydroxyphenyl) cycloalkanes, Bis (hydroxyphenyl) sulfides, Bis (hydroxyphenyl) ether, Bis (hydroxyphenyl) ketones, Bis (hydroxyphenyl) sulfones, Bis (hydroxyphenyl) sulfoxides, α, α'-bis (hydroxyphenyl) diisopropylbenzenes, and their nuclear alkylated and nuclear halogenated compounds.

These and other suitable diphenols of the formula a) are described, for example, in US Pat. Nos. 3,028,365, 2,999,835, 3,148,182, 3,275,601, 2,991,273, 3,271,367, 3,062,781, 2,970,131 and 2,999 846, in German laid-open publications 1 570 703, 2 063 050, 2 063 052, 2 211 095, French patent specification 1 561 518 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" described.

Preferred diphenols of the formula a) are, for example: 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, Bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, α, α'-bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane as well as the diphenols a) 2) 1), a) 2) 2) and a) 2) 3).

Examples of particularly preferred diphenols of the formula a) are: 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane of the formula a) 2) 1).

In particular, 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane are preferred.

The diphenols of the formula a) can be used either individually or in a mixture.

In a known manner, monofunctional compounds in conventional concentrations serve as chain terminators for regulating the molecular weight. Suitable compounds are, for example, phenol, tert-butylphenols or other alkyl-C₁-C₇-substituted phenols.

Small amounts of phenols of the formula c) are particularly suitable for regulating the molecular weight<chemistry id="chem0005" num="0005"><img file="EP0472064A2_D0005.tif" /></chemistry> wherein R represents a branched C₈ and / or C₉ alkyl radical.

Preferably, the proportion of CH₃ protons in the alkyl radical R between 47 and 89% and the proportion of CH and CH₂ protons between 53 and 11%; R is likewise preferably in the o- and / or p-position to the OH group, and particularly preferably the upper limit of the ortho fraction 20%. The chain terminators are generally used in amounts of 0.5 to 10, preferably 1.5 to 8 mol%, based on the diphenols used.

Thermoplastic, aromatic polyester carbonates according to component A) of the present invention are those obtainable in a known manner on diphenols, phosgene, aromatic dicarboxylic acid dichlorides, chain terminators and optionally branching agents. Suitable diphenols are those of formula a) already mentioned for polycarbonate production.

Suitable chain terminators are, for example, monophenols, as are also suitable for the production of polycarbonate.

Suitable branching agents are the three or more than three-functional compounds mentioned above for the production of polycarbonate, it being possible to use aromatic tricarboxylic acid chlorides or aromatic tetracarboxylic acid chlorides or acid chlorides of even higher quality aromatic carboxylic acids in addition to phenolic compounds. They are used in amounts of 0.01 to 1 mol%, based on the aromatic dicarboxylic acid dichlorides used, while if phenolic branching agents are used, their amount of 0.01 to 1 mol% relates to the diphenols used to prepare the aromatic polyester carbonate.

Suitable aromatic dicarboxylic acid dichlorides are terephthalic acid dichloride, isophthalic acid dichloride, o-phthalic acid dichloride, diphenyl-dicarboxylic acid dichloride, naphthalenedicarboxylic acid dichloride and mixtures thereof.

Preferred mixtures are those of terephthalic acid dichlorides with isophthalic acid dichlorides in a ratio of 20: 1 to 1:20, in particular from 7: 3 to 3: 7.

The aromatic polyester carbonates for the purposes of the present invention have up to about 80 mol%, preferably up to about 50 mol%, of carbonate groups, based on the molar sum of carbonate groups and aromatic carboxylic acid ester groups.

Both the ester and the carbonate content of the aromatic polyester carbonates according to the invention can be present in the form of blocks or randomly distributed in the polycondensate.

The relative solution viscosity (η_rel) the aromatic polyester carbonate is in the range 1.18 to 1.4, preferably 1.22 to 1.3 (measured on solutions of 0.5 g polyester carbonate in 100 ml CH₂Cl₂ solution at 25 ° C).

The polyester carbonate component A) is both a homopolyester carbonate and a polyester carbonate based on several diphenols, both a polyester carbonate based on only one aromatic dicarboxylic acid and also based on several dicarboxylic acids. The polyester carbonates of component A) and their preparation are known (see, for example, EP-OS 0 036 080 (Le A 20 203), DE-OS 3 007 934 (Le A 20 203), US Pat. No. 3 169 121 and German patent application P 3 903 103 .9 (Le A 26 313) for the polyester carbonates from the diphenols of the formula a) 2)).

Suitable glass fibers for the molding compositions of the present invention are all commercially available types and types of glass fibers, that is to say cut glass types (long glass fibers), provided that they are made compatible with polycarbonate by suitable sizes. The glass fibers used to manufacture the molding compounds are made from E-glass. According to DIN 1259, e-glass is an aluminum-boron-silicate glass with an alkali oxide content of less than 1% by weight. The glass fibers used have a diameter between 8-20 µm and a length of 3-6 mm (chopped strands). If necessary, sized or unsized short glass can also be used.

Suitable C₂-C₈ olefins for the preparation of the terpolymers according to component C) are, for example, ethylene, propylene, hexene, butadiene, isoprene and chloroprene.

Acrylic acid esters for the preparation of the terpolymers according to component c) are, for example, esters of acrylic acid with C₁-C₈ alcohols such as methanol, ethanol, n-butanol and n-octanol.

Suitable proportions according to the invention for the production of the terpolymers are<ul id="ul0002" list-style="none"><li>1) 40 to 90% by weight of C₂-C₈ olefins,</li><li>2) 5 to 40% by weight of acrylic acid ester and</li><li>3) 0.1 to 30% by weight, preferably 0.1 to 20% by weight and in particular 1 to 15% by weight of maleic anhydride, the sum of the% by weight of components 1) + 2) + 3) in each case 100% by weight .% is.</li></ul>

The terpolymers according to component C) which are suitable according to the invention are rubber-like, ie they have elastic properties.

The terpolymers of component C) are either copolymers or graft polymers.

Here, the maleic anhydride can be terpolymerized during the synthesis with the ethylene and the acrylic acid ester or can be polymerized onto a pre-formed graft base by a customary grafting reaction.

The terpolymers containing acid anhydride groups according to the invention can be prepared by all known polymerization processes (emulsion, solution, bulk, suspension, precipitation polymerization) and by combinations of these processes.

When the terpolymers containing acid anhydride groups are prepared by grafting, the monomer to be grafted is polymerized in the presence of the pre-formed graft base.

In addition to the actual graft polymer, free homopolymer is also formed. The graft product is thus understood to be the sum of the actual graft copolymers and the free polymers. The amount of the grafted-on monomer and its molecular weight can be influenced within wide limits by variations in the polymerization conditions. Above all, this includes: type of polymerization process, temperature, activator system, molecular weight regulator, stirring conditions and type of monomer metering.

Particularly preferred terpolymers are those which are made from<ul id="ul0003" list-style="none"><li>1) 40 to 90% by weight of ethylene,</li><li>2) 5 to 40% by weight of one or more C₁-C₈ alkyl acid and</li><li>3) 0.1 to 30% by weight, preferably 0.1 to 20% by weight and particularly preferably 1 to 15% by weight of maleic anhydride,</li></ul> where the sum of the% by weight of components 1) + 2) + 3) is in each case 100% by weight.

The terpolymers to be used according to the invention should be essentially uncrosslinked, ie they should be at least 90% soluble in hot solvents such as toluene, ethylbenzene or tetrachlorethylene. The terpolymers according to component C) have melting points from 40 to 160 ° C., preferably from 60 to 150 ° C. The melting points were determined by the DSC method (differential scanning calorimeter method).

The Vicat temperatures of the terpolymers to be used according to the invention are in the range between 30 to 110 ° C., preferably 35 to 90 ° C., measured in accordance with DIN 53 460.

The mixtures according to the invention from components A), B) and C) are prepared in such a way that the polycarbonate with the glass fibers and the terpolymer containing acid anhydride groups is obtained at temperatures between 260 ° C and 360 ° C, preferably between 280 ° C and 320 ° C melt compounded and the mixture obtained is cooled and granulated in a known manner.

The customary twin-screw extruders which are suitable for mixing polycarbonate and glass fibers can be used to produce the mixtures according to the invention.

The present invention thus also relates to a process for the preparation of the mixtures according to the invention from components A), B) and C), which is characterized in that the polycarbonate with the glass fibers and the terpolymer containing acid anhydride groups at temperatures between 260 ° C. and 360 ° C, preferably between 280 ° C and 320 ° C melt compounded and the mixture obtained is cooled and granulated in a known manner.

The known mixtures for components A), B) and C) can also be incorporated into the mixtures according to the invention in known amounts before or during or after the preparation of the mixtures according to the invention in customary amounts.

Suitable additives are fillers such as mineral fillers, plasticizers, flow agents, stabilizers against UV light, heat, moisture and against O₂, pigments and flame retardants.

The present invention thus also relates to mixtures consisting of components A), B) and C) according to the invention and at least one additive selected from fillers, plasticizers, flow agents, stabilizers, pigments and flame retardants.

The present invention also relates to a process for the preparation of the mixtures according to the invention, consisting of components A), B) and C) according to the invention and at least one additive selected from fillers, plasticizers, flow agents, stabilizers, pigments and flame retardants, which is characterized in that that before or during or after the preparation of the mixtures according to the invention from components A), B) and C) at least one of the additives mentioned in the usual amounts for components A), B) and C) incorporated in a known manner.

The mixtures according to the invention can be processed in a known manner to give shaped articles, for example by injection molding them into different shaped articles on injection molding machines.

The mixtures according to the invention are used wherever molded articles made of glass fiber-containing polycarbonate are used, with the requirement profile of great rigidity and toughness.

Examples 1-5

<ul id="ul0004" list-style="none"><li>I) An aromatic polycarbonate dried at 120 ° C in 24 h with a relative viscosity ηrel = 1.28 (0.005 g cm⁻³ in methylene chloride, 25 ° C) is melted in a twin-screw extruder at temperatures of 300-320 ° C.</li></ul>

Then a mixture of glass fibers and terpolymer containing acid anhydride is metered directly into the polycarbonate melt. The polymer strand is cooled, granulated and processed into molded articles using techniques customary for glass fiber reinforced polycarbonates.<ul id="ul0005" list-style="none"><li>II) In the examples, polyurethane-sized glass fibers with a diameter of 14 μm and a length of 3 mm are used as glass fibers.</li><li>III) The terpolymers used in the examples are prepared by polymerizing ethylene, butyl acrylate and maleic anhydride in a high-pressure process, if appropriate in the presence of suitable catalysts.</li></ul><tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row><entry namest="col1" nameend="col4" align="center">Composition of the terpolymers used</entry></row><row><entry namest="col1" nameend="col1" align="center">Terpolymer</entry><entry namest="col2" nameend="col2" align="center">Ethylene (% by weight)</entry><entry namest="col3" nameend="col3" align="center">Acrylic acid ester (wt.%)</entry><entry namest="col4" nameend="col4" align="center">Maleic anhydride (% by weight)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">A</entry><entry namest="col2" nameend="col2" align="char" char=",">83,5</entry><entry namest="col3" nameend="col3" align="char" char=",">10,0</entry><entry namest="col4" nameend="col4" align="char" char=",">6,5</entry></row><row><entry namest="col1" nameend="col1" align="left">B</entry><entry namest="col2" nameend="col2" align="char" char=",">62,8</entry><entry namest="col3" nameend="col3" align="char" char=",">24,6</entry><entry namest="col4" nameend="col4" align="char" char=",">12,6</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">C.</entry><entry namest="col2" nameend="col2" align="char" char=",">55,4</entry><entry namest="col3" nameend="col3" align="char" char=",">32,3</entry><entry namest="col4" nameend="col4" align="char" char=",">12,3</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><img file="EP0472064A2_D0006.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0472064A2_D0007.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0472064A2_D0008.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP0472064A2_D0009.tif" /></tables><tables id="tabl0006" num="0006"><img file="EP0472064A2_D0010.tif" /></tables>