EP1325080A1

EP1325080A1 - Copolycarbonate-based composition

Info

Publication number: EP1325080A1
Application number: EP01967335A
Authority: EP
Inventors: Holger Warth; Thomas Eckel; Dieter Wittmann; Silke Kratschmer
Original assignee: Bayer AG
Current assignee: Covestro Deutschland AG
Priority date: 2000-09-26
Filing date: 2001-09-13
Publication date: 2003-07-09
Also published as: CN100537663C; BR0114145A; WO2002026886A1; JP2004510025A; TW562836B; CN1476468A; CA2423012A1; AU2001287732A1; MXPA03002581A; US6583257B2; US20020123567A1

Abstract

The invention relates to thermoplastic copolycarbonate compositions and to shaped bodies containing the same that have improved stress fracture resistance and thermostability.

Description

Composition based on copolycarbonates

The invention relates to thermoplastic polycarbonate compositions and moldings containing them with increased stress crack resistance and thermal stability.

The resistance to stress cracking of molded articles made of polymers is always important in the manufacture and use of the molded articles when there is contact with oils, cleaning agents and alcohols. In particular for automotive construction and other outdoor applications, chemical-resistant molded articles have long been sought, which on the one hand are resistant to low temperatures and on the other hand have high thermal stability. The task was therefore to find a polycarbonate blend which, on the other hand, shows improved stress cracking behavior and increased thermal stability in comparison to polycarbonate blends which contain polycarbonate from pure 2,2-bis (4-hydroxyphenyl) propane as bisphenol but maintains the beneficial properties of polycarbonate blends, such as excellent low-temperature toughness.

Copolycarbonates based on 4,4'-dihydroxydiphenyl and 2,2-

Bis (4-hydroxyphenyl) propane is described as particularly resistant to chemicals, heat-resistant and flame-retardant (cf. JP-A 5 117 382, EP-A 0 544407, US-A 5,470,938, US-A 5,532,324 and US-A 5,401,826), in comparison to commercially available polycarbonate made from pure bisphenol A, with the same mechanical properties and transparency. However, there is no indication in the prior art that these copolycarbonates can advantageously be used in polycarbonate blends while maintaining the particularly good low-temperature properties.

JP-A 03 126 756 describes thermoplastic resin compositions with improved heat resistance, impact resistance, oil and water resistance. These resins are composed of aromatic polyester resin, aromatic polycarbonate and butadiene rubber.

EP-A 0 403 837 describes thermoplastic polycarbonate molding compositions based on substituted dihydroxydiphenylcycloalkanes, other aromatic ones

Polycarbonates, for example based on bisphenol-A, and grafted, particulate diene rubbers and their use for the production of thermoplastic molded bodies. Because of the dihydroxydiphenylcycloalkanes, these molding compositions have improved heat resistance while maintaining good Ke b impact strength.

The present invention has for its object to provide thermoplastic polycarbonate compositions with improved stress crack resistance and improved thermal stability.

This object is achieved by copolycarbonate compositions containing

A) 2 to 98, preferably 5 to 97, particularly preferably 30 to 95 parts by weight of a thermoplastic aromatic copolycarbonate, composed of 0.1 mol% to 46 mol% of compounds of the formula (I)

wherein

R ¹ to R ⁸ independently of one another are hydrogen, halogen, to C ₈ alkyl,

Ci to C ₅ cycloalkyl, C ₆ to C ₁₀ aryl and C ₇ to C ₁₂ aralkyl and complementary amounts, ie 99.9 mol% to 54 mol% of diphenols other than Nerbindungen of formula (T),

B) 0.5 to 50, preferably 2 to 40, particularly preferably 5 to 30 parts by weight of at least one graft polymer of

B 1) 5 to 90 parts by weight of at least one vinyl monomer and

B2) 95 to 10 parts by weight of a rubber with a glass transition temperature of <10 ° C.

Surprisingly, it was found that even a small proportion of structural units of the formula (I) in the polycarbonate composition significantly improves the stress crack resistance of the molded articles obtained therefrom.

The copolycarbonates according to component A) according to the invention preferably contain 11 to 34 mol% and particularly preferably 26 to 34 mol% of Nerbindungen of formula (I).

Diphenols which are different from Nerbindungen of formula (I) are correspondingly contained in complementary amounts, that is 99.99 to 54 mol%, preferably 89 to 66 mol%, particularly preferably 74 to 66 mol%.

R ¹ to R ⁸ in formula (I) independently of one another preferably represent hydrogen, C 1 -C 4 -alkyl, phenyl, substituted phenyl or halogen, particularly preferably hydrogen, methyl or tert-butyl, particularly preferably all represent same rest.

Particularly preferred compounds of the formula (I) are 4,4'-dihydroxydiphenyl (DOD) and 4,4 ^, -dihydroxy-3,3 ^, -5,5'-tetra- (tert-butyl) diphenyl. Preferred diphenols other than compounds of the formula (I) are diphenols of the formula (II)

in which

A Cι-C5-alkylene, C2-C5-alkylidene, Cs-Cö-cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO -, C6-Ci2-aryl ^en _> ^to the further aromatic optionally rings containing heteroatoms can be condensed,

or a radical of the formula (Ila) or (over)

5 '

R R °

B each C 1 -C 2 alkyl, preferably methyl, halogen, preferably chlorine and / or bromine

x each independently of one another 0, 1 or 2, p are 1 or 0, and

R5 and R6 can be selected individually for each X, independently of one another hydrogen or C -C -alkyl, preferably hydrogen, methyl or ethyl,

X ¹ carbon and

m is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X ¹ , R ¹ and R 6 are simultaneously alkyl.

Preferred compounds of the formula (IT) are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane and 1,3-bis [2- (4- hydroxyphenyl) -2-propyl] benzene, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, in particular 2,2-bis (4- hydroxyphenyl) propane (bisphenol A).

Both one compound of the formula (I), with formation of binary copolycarbonates, and several compound compounds of the formula (I) can be used.

Likewise, both a compound of formula (II), forming binary

Copolycarbonate, as well as several compounds of formula (IT) can be used.

The starting materials of the formula (I) and (II) can of course contain impurities due to the synthesis. A high level of purity is desirable and desirable, which is why these educts are used with the highest possible level of purity.

According to DE-A 2 119779, the production of polycarbonates with the participation of monomers of the formula (I) is preferably carried out in solution, specifically by the interfacial process and the homogeneous phase process. For the production of polycarbonates according to the phase interface process, examples include "Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Nol. 9, interscience Publishers, New York, London, Sydney 1964 and on Polymer Reviews, Volume 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York 1965, chap. Vffi, p. 325 and EP

971 790.

In addition, it is also possible to manufacture in the melt by the known polycarbonate production process (so-called climelium transesterification process), which, for example, is described in DE-A 19 64 6401 or in DE-A 1 42 38 123. Be next to it

Transesterification processes (acetate process and phenyl ester process), for example in US Pat. Nos. 3,494,885, 4,386,186, 4,661,580, 4,680,371, and 4,680,372, in EP-A 26,120, 26,121, 26,684, 28,030, 39,845 , 91 602, 97 970, 79 075, 146 887, 156 103, 234913 and 240 301 and in DE-A 1 495 626 and 2232 977.

The copolycarbonates according to the invention can contain different end groups. These are introduced by chain breakers. Chain terminators in the sense of the invention are those of the formula (Tfl)

in which

R, R and R "can independently represent H, optionally branched C1-C34-alkyl / cycloalkyl, C ₇ -C ₃₄ -alkaryl or C ₆ -C ₃ -aryl, for example butylphenol, tritylphenol, cumylphenol, phenol, octylphenol , preferably butylphenol or phenol.

The polycarbonates can contain small amounts of 0.02 to 3.6 mol% (based on the Dihydroxy compound) contained on branching. Suitable branching agents are the compounds suitable for polycarbonate production with three or more functional groups, preferably those with three or more than three phenolic OH groups, for example l, l, l-tri- (4-hydroxyphenyι) ethane and isatin biscresol.

The thermoplastic, aromatic polycarbonates have average molecular weights (weight average M _w , measured for example by an ultracentrifuge or scattered light measurement) of 10,000 to 200,000, preferably 15,000 to 80,000.

The thermoplastic, aromatic copolycarbonates can be used alone or in any mixture.

Another component of the polycarbonate compositions according to the invention is the graft polymer according to component B, which can comprise one or more graft polymers.

Monomers B.l are preferably mixtures of

B1 to 50 to 99 parts by weight of vinyl aromatics and / or core-substituted vinyl aromatics (such as styrene, methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C ₁ -C ₈ ) alkyl esters, such as methyl methacrylate , Ethyl methacrylate) and

B12 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C 1 -C ₈ ) alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or derivatives such as anhydrides and imides of unsaturated carboxylic acids such as maleic anhydride and N-phenyl-maleimide.

Preferred monomers B.l.l are selected from at least one of the monomers

Styrene, α-methylstyrene and methyl methacrylate, preferred monomers Bl2 selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate. Particularly preferred monomers are B1 styrene x B1 B1 acrylonitrile.

Examples of graft bases B.2 suitable for the graft polymers B are

Diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and optionally acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.

Preferred graft bases B.2 are diene rubbers, for example and preferably based on butadiene or isoprene or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers, for example according to B1 and B.1.2. Component B.2 preferably has a glass transition temperature of about <0 ° C, particularly preferably of <-20 ° C. The graft base B.2 has an average particle size (d ₅ o value) microns in general from 0.05 to 10, preferably from 0.1 microns to 5, particularly preferably 0.2 to 1 micron. Pure polybutadiene rubber is particularly preferred, optionally with up to 30% by weight (based on the rubber base) of comonomer selected from styrene, acrylonitrile, methyl methacrylate or mixtures thereof.

Particularly preferred polymers B are e.g. ABS polymers (emulsion, bulk and suspension ABS), as described in DE-A 2 035 390 or in DE-A 2 248 242 or in Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 19 (1980), P. 280 ff. Are described. The gel fraction of the graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).

The graft copolymers B are prepared by radical polymerization, for example by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization. ABS polymers which are produced by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285 are also particularly suitable graft rubbers.

Since, as is well known, the graft monomers are not necessarily grafted completely onto the graft base in the graft reaction, graft polymers B are also understood according to the invention to mean those products which are obtained by (co) polymerizing the graft monomers in the presence of the graft base and are also obtained in the working up.

Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers made from alkyl acrylates, optionally with up to 40% by weight, based on B.2, of other polymerizable, efhylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include C 1 -C ₈ -alkyl esters, for example methyl, ethyl, butyl, n-octyl xmd 2-ethylhexyl ester; Haloalkyl esters, preferably halogen (C ₁ -C ₈₎ alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.

Monomers with more than one polymerizable double bond can be copolymerized for crosslinking. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as ethylene glycol dimethacrylate, allylneth - acrylate; polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.

Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least three ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes. The amount of crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2,% by weight, based on the graft base B.2.

In the case of cyclic crosslinking monomers with at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base B.2.

Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters can optionally be used to prepare the graft base B.2, are, for example, acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl -CC ₆ -alkyl ethers, methyl methacrylate, butadiene. Preferred acrylate rubbers as the graft base B.2 are emulsion polymers which have a gel content of at least 60% by weight.

Further suitable graft bases according to B.2 are silicone rubbers with graft-active sites, as are described in DE-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3 631 539.

The gel content of the graft base B.2 is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krämer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).

The average particle size d ₅₀ is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-1796).

The copolycarbonate composition can contain polymers according to component C as further constituents. Component C comprises one or more thermoplastic vinyl (co) polymers Cl and / or polyalkylene terephthalates C.2.

The copolycarbonate compositions can be up to 45, preferably up to

35 parts by weight (based on the total composition) of polymers according to component C).

Suitable vinyl (co) polymers C.I. polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles),

(Meth) acrylic acid (C ₁ -C ₈ ) alkyl esters, unsaturated carboxylic acids and derivatives such as anhydrides and imides of unsaturated carboxylic acids. (Co) polymers of are particularly suitable

Cll 50 to 99, preferably 60 to 80 parts by weight of vinyl aromatics and or core-substituted vinyl aromatics such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (-C-C ₈ ) alkyl esters such as Methyl methacrylate, ethyl methacrylate), and

Cl2 1 to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile xmd / or (meth) acrylic (C ₁ -C ₈ ) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-Butyl acrylate, xmd / or unsaturated carboxylic acids such as maleic acid and / or derivatives such as anhydrides and imides, more unsaturated

Carboxylic acids such as maleic anhydride and N-phenylmaleimide).

The (co) polymers Cl are resin-like, thermoplastic and rubber-free. The copolymer of Cl. 1 styrene xmd C.1.2 acrylonitrile is particularly preferred. The (co) polymers according to Cl are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The (co) polymers preferably have average molecular weights M _w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.

The polyalkylene terephthalates of component C.2 are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.

Preferred polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component terephthalic acid residues xmd at least 80% by weight, preferably at least 90 mol%, based on the diol component of ethylene glycol and or butanediol 1 , 4-residues.

In addition to terephthalic acid residues, the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, of residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.

In addition to ethylene glycol or butanediol 1,4-residues, the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, of other aliphatic ones

Contain diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms, for example residues of 1,3-propanediol, 2-ethylpropanediol, 1,3, neopentylglycol, 1,5-pentanediol, 1,6-hexanediol , Cyclohexane-dimethanol-1,4,3-ethylpentanediol-2,4,2-methylpentanediol-2,4,2,2,4-trimethylpentanediol-1,3,2-ethylhexanediol-1,3,2,2-diethyl propanediol -1,3, hexanediol-2,5,1,4-di- (β-hydroxyethoxy) benzene, 2,2-bis- (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-l, 1,3 , 3-tetramethyl-cyclobutane, 2,2-bis (4-β-hydroxyethoxy-phenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (DE-A 2 407 674, 2 407 776, 2 715 932).

The polyalkylene terephthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-A

1 900270 and US-A 3 692 744. Examples of preferred branching agents are Tiϊmesinsäxxre, trimellitic acid, trimethylolethane and -propane and pentaerythritol.

Particularly preferred are polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkylene terephthalates.

Mixtures of polyalkylene terephthalates contain 1 to 50% by weight, preferably

1 to 30% by weight, polyethylene terephthalate xmd 50 to 99% by weight, preferably 70 to 99% by weight, polybutylene terephthalate.

The polyalkylene terephthalates preferably used generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in

Phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C in an Ubbelohde viscometer.

The polyalkylene terephthalates can be prepared by known methods (Kunststoff-Handbuch, Volume VIII, p. 695 ff., Carl-Hanser-Verlag, Munich 1973).

The polycarbonate composition according to the invention can contain flame retardants; phosphorus-containing flame retardants are particularly preferred.

Phosphorus-containing flame retardants in the sense of the invention are particularly preferably selected from the groups of the mono- and oligomeric phosphorus and phosphonic acid esters, phosphonate amines and phosphazenes, mixtures of several components selected from one or different of these groups can be used as flame retardants. Other halogen-free phosphorus compounds not specifically mentioned here can also be used alone or in any combination with other halogen-free phosphorus compounds.

Preferred mono- and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (TV)

embedded image in which

R ^, RIO, RI I and R ¹ ^ independently of one another each optionally halogenated Ci to Cg alkyl, in each case optionally substituted by alkyl, preferably C1 -C4 alkyl, and / or halogen, preferably chlorine, bromine, C5 bis Cg-cycloalkyl, Cβ to C2 () aryl or C7 to C12 aralkyl,

n independently of one another, 0 or 1

0 to 30 and

X is a mono- or polynuclear aromatic radical with 6 to 30 C atoms, or a linear or branched aliphatic radical with 2 to 30 C atoms, which can be OH-substituted and can contain up to 8 ether bonds. R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are preferably independently of one another C 1 -C 4 -alkyl, phenyl, naphthyl or phenyl-C 1 -C 4 -alkyl. The aromatic groups R ⁹ , R ¹⁰ , R ¹¹

1 and R in turn can be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C1-C4-alkyl. Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.

X in the formula (IV) preferably denotes a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms. This is preferably derived from diphenols of the formula (JJ).

n in the formula (TV), independently of one another, can be 0 or 1, preferably n is 1.

q stands for values from 0 to 30. When using mixtures of different

Components of the formula (IN) can be used in mixtures, preferably number-average q values of 0.3 to 20, particularly preferably 0.5 to 10, in particular 0.5 to 6.

X particularly preferably stands for

or their chlorinated or brominated derivatives, in particular X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. X is particularly preferably derived from bisphenol A. The use of oligomeric phosphoric acid esters of the formula (TV), which are derived from bisphenol A, is particularly advantageous since the compositions equipped with this phosphorus compound have a particularly high resistance to stress cracking and hydrolysis and a particularly low tendency to form deposits in injection molding processing. Furthermore, a particularly high heat resistance can be achieved with these flame retardants.

The monophosphates (q = O) and oligophosphates (q = 1 - 30) can also be used as mixtures.

Monophosphorus compounds of the formula (IN) are, in particular, tributyl phosphate, tris (2-chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyloctyl phosphate, diphenyl 2-ethylcresyl (isopropyl) phosphate ) -phosphate, halogen-substituted aryl phosphates, dimethyl methylphosphonate, diphenyl methylphosphate,

Phenylphosphonic acid diethyl ester, triphenylphosphine oxide or tricresylphosphine oxide.

The phosphorus compounds of the formula (IN) are known (EP-A 363 608, EP-A 640 655) or can be prepared in an analogous manner by known methods

(e.g. Ullmann's Encyclopedia of Industrial Chemistry, vol. 18, p. 301 ff. 1979; Houben-Weyl, Methods of Organic Chemistry, vol. 12/1, p. 43; Beilstein vol. 6, p. 177).

The mean q values can be determined by using a suitable method

(Gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)) the composition of the phosphate mixture (molecular weight distribution) is determined and the mean values for q are calculated therefrom.

Phosphonatamines are preferably compounds of the formula (N) A ₃ . _y -NBl _y (V) in which

A for a residue of the formula (Va)

or (Vb)

stands,

RU and R ¹ ^ independently of one another for unsubstituted or substituted

Cj-C iQ-alkyl or unsubstituted or substituted Cß-C \ Q-aryl,

Rl3 and Rl4 independently of one another represent unsubstituted or substituted C 1 -C IQ-alkyl or unsubstituted or substituted Cö-Ci o-aryl or

R ^χ 3 and Rl4 together represent unsubstituted or substituted C3-Ci Q-alkylene,

y are the numerical values 0, 1 or 2 and ßl independently represents hydrogen, optionally halogenated C2-Cg-alkyl, unsubstituted or substituted Cg-Ci Q-aryl.

ßl preferably independently represents hydrogen, ethyl, n- or iso-propyl, which can be substituted by halogen, unsubstituted or by C1-C4-alkyl and / or halogen-substituted Cö-Ci o-aryl, especially phenyl or naphthyl.

Alkyl in R ^{1 1} , R ¹ ^, Rl3 and R 4 independently preferably represents methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- or tert-butyl, pentyl or hexyl.

Substituted alkyl in R ^Ü , R ^ _? R1 and R14 _s t _s t independently preferably substituted by halogen, C1 -C Q alkyl, in particular mono- or disubstituted methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec- or tert -butyl.,

Pentyl or hexyl.

Cg-Ci _Q- aryl in R ¹¹ , R ^, R ¹ ^ and R * 4 independently preferably represents phenyl, naphthyl or binaphthyl, in particular o-phenyl, o-naphthyl, o-binaphthyl, which by halogen (in general -, Two or three times) can be substituted.

R ^χ 3 and Rl4 can form a ring structure together with the oxygen atoms to which they are directly attached and the phosphorus atom.

The following are mentioned by way of example and preferably: 5,5,5 ', 5', 5, "5" -hexamethyltris

(1,2,3-dioxaphosphorinane-methane) amino-2,2 ', 2 "-trioxide of the formula (Na-1)

(Test product XPM 1000 from Solutia Inc., St. Louis, USA) 1,3,2-dioxaphosphorinan-2-methanamine, Ν-butyl-Ν [(5,5-dimethyl-l, 3,2-dioxaphosphorinane -2-yl) methyl] -5,5-dimethyl-, P, 2-dioxide; l, 3,2-dioxaphosphorinane-2-methanamine, N- [[5 "5-dimemyl-l, 3,2-dioxaphosphorinan-2-yl) methyl] -5,5-dimethyl-N-phenyl-, P, 2-dioxide; l, 3,2-dioxaphosphorinan-2-methanamine, N, N-dibutyl-5,5-dimethyl-, 2-oxide, l, 3,2-dioxaphosphorinan-2-methanimine, N - [(5,5-dimethyl -l, 3,2-dioxaphosphorinan- 2-yl) methyl] -N-ethyl-5,5-dimethyl-, P, 2-dioxide, 1, 3,2-dioxaphosphorinan-2-methane amine, N-butyl -N - [(5,5-dichloromethyl-l, 3,2-dioxaphosphorinan-2-yl) methyl] -5,5-di-chloromethyl-, P, 2-dioxide, l, 3,2-dioxaphosphorinane 2-methanamine, N - [(5,5-di-chloromethyl-l, 3,2-dioxoaphosphorinan-2-yl) methyl] -5,5-di-chloromethyl-N-phenyl-, P, 2- dioxide; 1,2,2-dioxaphosphorinane-2-methanamine, N, N-di- (4-chlorobutyl) -5,5-dimethyl-2-oxide; 1, 3,2-dioxaphosphorinan-2-methanimine, N - [(5,5-dimethyl-1, 3,2 dioxaphosphorinan-2-yl) methane] -N- (2-chloroethyl) -5,5-di ( chloromethyl) -, P2- dioxide.

Also preferred are:

Nerbindungen of the formula (Na-2) or (Na-3)

in which

Rl 1, R ¹ ^, R md R ¹ ^ have the meanings given above. Ner compounds of the formulas (Na-2) and (Na-1) are particularly preferred.

The preparation of the phosphonate amines is described, for example, in US Pat. No. 5,844,028.

Phosphazenes are compounds of the formulas (NIa) and (NTb)

wherein

R is the same or different and represents amino, in each case optionally halogenated, preferably with fluorine halogenated C _\ - to Cg alkyl, or C ^ - to Cg alkoxy, each optionally substituted by alkyl, preferably Ci- C4 alkyl, and / or Halogen, preferably chlorine and / or bromine, substituted C5 to Cö-cycloalkyl, Cß to C2 ₍₎ aryl, preferably phenyl or naphthyl, Cg to C2 () aryloxy, preferably phenoxy, naphthyloxy, or C7 to Cχ2 Aralkyl, preferably phenyl-C4-alkyl, k represents 0 or a number from 1 to 15, preferably a number from 1 to 10.

Examples include: propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene and fluoroalkylphosphazenes. Phenoxyphosphazene is preferred.

The phosphazenes can be used alone or as a mixture. The radical R can always be the same or 2 or more radicals in the formulas (Ia) and (Ib) can be different.

Phosphazenes and their preparation are described, for example, in EP-A 728 811, DE-A 1 961 668 and WO 97/40092.

The flame retardants can be used alone or in any mixture with one another or in a mixture with other flame retardants.

The molding compositions according to the invention can at least contain one of the customary additives, such as lubricants and mold release agents, for example pentaerythritol tetrastearate,

Contain nucleating agents, antistatic agents, stabilizers, fillers and nerve reinforcements as well as dyes and pigments.

The filled or reinforced molding compositions can contain up to 60, preferably 10 to 40% by weight, based on the filled or reinforced molding composition, of fillers and / or ner reinforcing materials. Glass fibers are preferred ner reinforcing materials. Preferred fillers, which can also have a reinforcing effect, are glass balls, mica, silicates, quartz, talc, titanium dioxide, wollastonite.

The molding compositions according to the invention can contain up to 35% by weight, based on the

Overall composition, another, possibly synergistic Flame retardant included. Examples of other flame retardants are organic halogen compounds, such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds, such as ammonium bromide, nitrogen compounds, such as melamine, melamine formaldehyde resins, inorganic hydroxide compounds, such as Mg, Al hydroxide, inorganic compounds such as antimony oxides, barium metaborate, hydroxoantbutonate, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide and zirconium oxide , Arnmonixxmmolybdat, zinc borate, ammonium borate, barium metaborate, talc, silicate, silicon oxide and tin oxide as well as siloxane compounds. Such phosphorus compounds are described in EP-A 363 608, EP-A 345 522 and DE-OS 197 21 628.

The compositions according to the invention are produced by mixing the respective constituents in a known manner and melt-compounding xmd melt-extruding them at temperatures from 200 ° C. to 300 ° C. in conventional units such as internal kneaders, extruders and twin-screw extruders. The individual components can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.

The thermoplastic molding compositions according to the invention are suitable on account of their excellent flame resistance, in particular the short afterburning time, and their good mechanical properties and their high heat resistance, for the production of moldings of all kinds, in particular those with increased demands on mechanical properties.

The molding compositions can be used to produce moldings of any kind. In particular, moldings can be produced by injection molding. Examples of moldings that can be produced are: Housing parts of all types, for example for household appliances such as juicers, coffee machines, mixers, for office machines such as monitors, printers, copiers or cover plates for the construction sector and parts for the automotive Sector. They can also be used in the field of electrical engineering because they have very good electrical properties.

Furthermore, the molding compositions according to the invention for the production of interior components for rail vehicles, hubcaps, housings for small transformers containing electrical appliances, housings for devices for disseminating and transmitting information, housings and cladding for medical purposes, massagers and housings therefor, toy vehicles for children, flat wall elements, housings for safety devices, rear spoiler, heat-insulated transport containers, device zxxr for keeping or supplying small animals, molded parts for sanitary and bathing equipment, cover grilles for ventilators, molded parts for garden and tool sheds, housings for garden tools.

Further applications are possible

as file technology devices: telecommunication devices such as telephone devices and faxes, computers, printers, scanners, plotters, monitors, keyboards, typewriters, dictation devices, etc.,

as electrical devices: power supplies, chargers, small transformers for computers and

Consumer electronics, low voltage transformers, etc.,

as garden tools: garden furniture, lawn mower housings, pipes and housings for garden irrigation, garden houses, leaf vacuums, shredders, shredders, sprayers etc.,

in the furniture sector: worktops, furniture laminates, roller shutter elements, office furniture, tables, chairs, armchairs, cupboards, shelves, door elements, window elements, bed frames etc., as sports / play equipment: toy vehicles, seats, pedals, sports equipment, bicycles, table tennis, exercise bikes, golf caddies, snow boards, boat parts, camping articles, beach chairs etc.,

Inside / outside in the construction sector: house cladding, profile strips, pipes, cables, roller shutter elements, letter boxes, lamp housings, roof tiles, tiles, partitions, cable ducts, floor strips, sockets, etc.

in the field of motor vehicles / rail vehicles: wall, ceiling cladding, seat shells, seats, benches, tables, luggage racks, hubcaps, rear spoilers, fenders, tailgates, bonnets, side parts, etc.

Another form of processing is the production of molded articles by deep drawing from previously produced sheets or foils.

Another object of the present invention is therefore the use of the molding compositions according to the invention for the production of moldings of any kind, preferably those mentioned above, and the moldings from the compositions according to the invention.

The following examples serve to further explain the invention.

Examples

components:

Al copolycarbonate from 30 mol% 4,4'-dihydroxydiphenyl (DOD) and 70 mol%

Bisphenol A with an average molecular weight (weight average) of 24970, determined by means of gas permeation chromatography against polystyrene as standard.

A2 copolycarbonate like AI but with M _w of 25620.

A3 copolycarbonate like AI but with M _w of 25190.

A4 copolycarbonate like AI but with M _w of 25050.

A5 polycarbonate based on bisphenol A (Makrolon ^® 2600, Bayer AG, Leverkusen, Germany).

B Graft polymer of 40 parts by weight of a copolymer of styrene and acrylonitrile in a ratio of 73:27 to 60 parts by weight crosslinked in particulate form

Polybutadiene rubber (d ₅₀ = 0.34 μm) made by emulsion polymerization.

C styrene / aryl nitrile copolymer with a styrene / acrylonitrile ratio of 72:28 and an intrinsic viscosity of 0.55 dl / g measured in dimethylformamide at 20 ° C.

Additives (stabilizer, mold release agent). The polycarbonate compositions according to the invention are produced by compounding the constituents and additives at from 240 ° C. to 300 ° C. in a twin-screw extruder.

The composition is shown in Table 1.

Table 1

Table 2 shows the results of the investigations with regard to the edge fiber elongation. The samples are exposed in an isooctanol / toluene mixture (1: 1) over a period of 5 minutes to selected marginal fiber stretches. In the comparative sample, the edge fiber elongation results in 1% edge cracks, otherwise the sample was without cracks. Breakage occurs at an elongation of 1.2%. The samples according to the invention show no negative results. With an edge fiber elongation of 2.4%, cracks also occurred in the samples according to the invention over a period of 68 to 150 minutes.

OR: without crack; KR: Edge tear. The time indicates how long the sample is held in the solvent mixture at the specified elongation until cracks or breaks occur. "-" means no finding. Table 2 Edge fiber elongation

In a further test, the samples are conditioned in isooctanone / toluene (1: 1) for 14 days and then the time in minutes is determined for cracks after a marginal fiber elongation of 2.4%. The results obtained are shown in Table 3.

Table 3

The impact strength according to ISO 180 1A of the samples according to the invention and of the comparison are determined at room temperature and 0 ° C. The results shown in Table 4 show no deterioration compared to the comparison sample within the scope of the measurement accuracy.

Table 4: Notched impact strength a _t

The thermal stability of the samples is measured at 290 and 300 ° C. The results are shown in Table 5. Pattern platelets are produced in the various temperatures by injection molding and then visually assessed.

Table 5: Thermostability

The larger the numbers, the more damaged the sample, which is shown by defects on the surface. The numbers 1 and 2 mean no to minimal surface defects or streaking, 4 to 5 mean strong to very strong streaking.

It can be seen that all of the molding compositions according to the invention have better thermal stability than Comparative Example 5.

Claims

claims

1. Copolycarbonate compositions containing

A) 2 to 98 parts by weight of a thermoplastic aromatic copolycarbonate, composed of 0.1 mol% to 46 mol% of compounds of the formula (I)

wherein

R to R independently of one another are hydrogen, halogen, to C ₈ -alkyl, dbis Cs-cycloalkyl, C ₆ to C ₁₀ -aryl and C ₇ to C ₁₂ -aryalkyl

and complementary amounts, ie 99.9 mol% to 54 mol% of diphenols other than compounds of the formula (I), and

B) 1 to 50 parts by weight of at least one graft polymer from

B1) 5 to 90 parts by weight of at least one vinyl monomer and

2. Copolycarbonate compositions according to claim 1, wherein component A in addition to the diphenol of the formula (I) is composed of diphenols of the formula (II) in which

A Ci-Cs-alkylene, C2-C5-alkylidene, Cs-Cö-cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO ₂ -, C6-Ci2-arylene, to the further aromatic rings optionally containing heteroatoms can be condensed,

or a radical of the formula (YES yes) or (YYb)

5 '

R R °

B are each C \ -C \ 2-alkyl or halogen,

x each independently of one another 0, 1 or 2,

p are 1 or 0, and R5 and R6 individually selectable for each oil, independently of one another hydrogen or C \ -Cß-alkyl,

Kohlenstoffl carbon and

m is an integer from 4 to 7, with the proviso that at least one atom X ¹ , R ^ and R ^ are simultaneously alkyl.

3. Copolycarbonate composition according to claim 2, wherein the diphenol of the formula (II) is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

4. Copolycarbonate composition according to claim 1 to 3, wherein 0.1 to 40 parts by weight of thermoplastic resin C is contained.

5. The copolycarbonate composition according to claim 4, wherein the thermoplastic resin C is selected from

C 1) copolymer or mixtures of copolymers

Cl.l) 50 to 99 parts by weight of vinyl aromatics and / or core-substituted

Vinyl aromatics and / or (Metfyactylsäxxre ^ -C ^ alkyl ester xmd

C1.2) 1 to 50 parts by weight of vinyl cyanides and / or (meth) acrylic acid (C ₈ -C ₈ ) alkyl esters xmd / or anhydrides and imides of unsaturated carboxylic acids and

C2) polyalkylene terephthalate or mixtures of polyalkylene terephthalates,

or mixtures thereof. Copolycarbonate composition according to any one of claims 1 to 5, wherein the rubber B.2 is a diene rubber, acrylate rubber, silicone rubber or ethylene-propylene-diene rubber or mixtures thereof.

Coplycarbonate composition according to one of the preceding claims, containing halogen-free flame retardant.

8. A copolycarbonate composition according to claim 7, wherein the flame retardant is a phosphorus compound of the formula (TV)

worm

R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ independently of one another Q to C ₈ alkyl, C ₅ to C ₆ cycloalkyl, C ₆ to C ₁₀ aryl or C ₇ to C ₁ aralkyl,

n independently of one another 0 or 1

a number from 1 to 5 or, in the case of mixtures, an average between 1 and 5

X is a mono- or polynuclear aromatic radical with 6 to 30 carbon atoms

mean.

9. copolycarbonate composition according to any one of claims 1 to 5, wherein the copolycarbonate component of 34 to 26 mol% of monomer of formula (T), and a complementary content of monomer of formula (II) are constructed.

10. Use of the copolycarbonate composition according to claims 1 to 9 for the production of moldings.

11. Use of the copolycarbonate composition according to claims 1 to 9 for outdoor applications.

12. Use of the copolycarbonate composition according to claims 1 to 9 in the automotive field.

13. Use of the copolycarbonate composition according to claims 1 to 9 in the electrical field.

14. Shaped body containing a thermoplastic copolycarbonate composition according to one of claims 1 to 9.

15. Housing parts containing a thermoplastic copolycarbonate composition according to any one of claims 1 to 9.