KR20030040491A - Copolycarbonate-based composition - Google Patents

Abstract

The present invention relates to a thermoplastic copolycarbonate composition and a molded article having improved stress cracking resistance and thermal stability.

Description

Copolycarbonate-based composition {COPOLYCARBONATE-BASED COMPOSITION}

Stress cracking resistance of molded articles made from polymers is always important when the molded article comes into contact with oils, detergents and alcohols in the manufacture of the molded article and in use of the molded article. Particularly molded articles that are as resistant to chemicals as possible, on the one hand, stable at low temperatures and on the other hand high thermal stability, have long been explored in automotive assembly and other exterior applications. Therefore, the objective is to improve stress cracking resistance and improve thermal stability, as compared to polycarbonate blends containing polycarbonates formed from pure 2,2-bis (4-hydroxyphenyl) -propane as bisphenols, while providing excellent low temperature. It is to find a polycarbonate blend that retains the advantageous properties of a polycarbonate blend such as toughness.

Copolycarbonates based on 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxyphenyl) -propane are particularly described as being chemically resistant, thermally stable and flame retardant. (See JP-A 5 117 382, EP-A 0 544 407, US-A 5,470,938, US-A5,532,324 and US-A 5,401,826) and are commercially available, formed from pure bisphenol A Compared to polycarbonate, they have equally good mechanical properties and transparency. However, the prior art does not contain any indication that these copolycarbonates can be advantageously used in polycarbonate blends while retaining particularly good low temperature properties.

JP-A 03 126 756 describes thermoplastic resin compositions with improved heat resistance, impact strength, and resistance to oils and water. Such resins consist of aromatic polyester resins, aromatic polycarbonates and butadiene rubbers.

EP-A 0 403 837 discloses substituted polyhydroxydiphenylcycloalkanes, other aromatic polycarbonates (eg based on bisphenol A), and thermoplastic polybased based grafted granular diene rubbers. Carbonate molding compositions and their use for the production of thermoplastic molded articles are described. Because of the dihydroxydiphenylcycloalkanes, these molding compositions have excellent notch impact strength while improving heat resistance.

The present invention relates to molded articles containing thermoplastic polycarbonate compositions and thermoplastic polycarbonate compositions having increased stress cracking resistance and thermal stability.

It is an object of the present invention to provide a thermoplastic polycarbonate composition with improved stress cracking resistance and improved thermal stability.

This object is A) thermoplastic aromatic copolycarbonates 2 to 2, consisting of from 0.1 mole% to 46 mole% of the compound of formula (I) and the remaining amount, ie 99.9 mole% to 54 mole%, of diphenols different from the compounds of formula (I) 98 parts by weight, preferably 5 to 97 parts by weight, particularly preferably 30 to 95 parts by weight, and B) B1) 5 to 90 parts by weight of one or more vinyl monomers and B2) a rubber having a glass transition temperature of 10 ° C. or less It is achieved by a copolycarbonate composition containing 0.5 to 50 parts by weight, preferably 2 to 40 parts by weight, particularly preferably 5 to 30 parts by weight of at least one graft polymer consisting of 95 to 10 parts by weight:

Where

R ¹ to R ⁸ independently represent hydrogen, halogen, C ₁ to C ₈ alkyl, C ₁ to C ₅ cycloalkyl, C ₆ to C ₁₀ aryl and C ₇ to C ₁₂ aralkyl.

Surprisingly, even if the polycarbonate composition contains a small amount of the structural unit according to formula (I), the stress cracking resistance of the molded article obtained therefrom is considerably improved.

The copolycarbonates according to the invention preferably contain 11 to 34 mole%, particularly preferably 26 to 34 mole% of the compounds of the formula I according to component A).

Thus, diphenols different from the compounds of the formula (I) are contained in residual amounts, i.e. 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 represent hydrogen, C ₁ -C ₄ alkyl, phenyl, substituted phenyl or halogen, particularly preferably hydrogen, methyl or tert-butyl, particularly preferably All represent the same radical.

Particularly preferred compounds of formula I are 4,4'-dihydroxydiphenyl (DOD) and 4,4'-dihydroxy-3,3 ', 5,5'-tetra- (tert-butyl) -di Phenyl.

Preferred diphenols different from the compounds of formula I are the diphenols of formula II:

Where

A is C ₁ -C ₅ alkylene, C ₂ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO _2- , C ₆ -C ₁₂ arylene (wherein an additional aromatic ring optionally containing heteroatoms may be condensed) or a radical of formula IIa or formula IIb,

B in each case represents C ₁ -C ₁₂ alkyl, preferably methyl, halogen, preferably chlorine and / or bromine,

x is 0, 1 or 2 independently of each other in each case,

p is 0 or 1.

Where

R ⁵ and R ⁶ may be selected individually for each X ¹ and independently of one another represent hydrogen or C ₁ -C ₆ alkyl, preferably hydrogen, methyl or ethyl,

X ¹ represents carbon,

m is an integer of 4 to 7, preferably 4 or 5, provided that at least one atom of X ¹ , R ⁵ and R ⁶ is alkyl at the same time.

Preferred compounds of formula II 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-hydroxy-phenyl) cyclohexane, in particular 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

One compound of formula (I) may be used in the form of a binary copolycarbonate, or a plurality of compounds of formula (I) may be used.

One compound of formula II and a plurality of compounds of formula II in binary copolycarbonate form may also be used.

The vitreous of Formula (I) and Formula (II) may clearly contain impurities resulting from the synthesis. However, a high degree of purity is desirable and should be targeted, so vitreous bodies with the highest possible purity are used.

According to DE-A 2 119 779, the preparation of polycarbonates is carried out with the involvement of the monomers of the formula (I), preferably in solution, and more particularly according to the phase interface method and homogeneous method.

Details of polycarbonate preparation according to the phase interface method are described, for example, in "Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964 and Polymer Reviews, Volume 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York, 1965, Chap. VIII, p. 325 and EP 971 790.

The polycarbonates may also be produced by known melt preparation methods (so-called melt transesterification methods) described, for example, in DE-A 19 64 6401 or DE-A 1 42 38 123. In addition, transesterification methods (acetate method and phenyl ester method) are, for example, US-A 3 494 885, 4 386 186, 4 661 580, 4 680 371 and 4 680 372, EP-A 26 120, 26 121, 26 684, 28 030, 39 845, 91 602, 97 970, 79 075, 146 887, 156 103, 234 913 and 240 301, and DE- A 1 495 626 and 2 232 977.

Copolycarbonates according to the invention may contain various terminal groups. These are introduced by chain stoppers. The chain stopper is a compound of formula III in the present invention.

Where

R, R 'and R "are independently of each other H, optionally branched C ₁ -C ₃₄ alkyl (cycloalkyl), C ₇ -C ₃₄ alkaryl or C ₆ -C ₃₄ aryl, for example butyl phenol, tri Methyl phenol, cumyl phenol, phenol, octyl phenol, preferably butyl phenol or phenol.

The polycarbonate may contain from 0.02 to 3.6 mole percent (relative to dihydroxy compound) of minor branches. Suitable branching agents are compounds suitable for the production of polycarbonates containing at least 3 functional groups, preferably compounds containing at least 3 phenol OH groups, for example 1,1,1-tri- (4-hydroxy Phenyl) ethane and isatin biscresol.

Thermoplastic aromatic polycarbonates have an average molecular weight (eg, weight average molecular weight M _W measured by ultracentrifugation or light scattering 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 composition according to the invention is the graft polymer according to component B, which may comprise one or more graft polymers.

Monomer B.1 is preferably B.1.1) a vinyl aromatic compound and / or a nuclear-substituted vinyl aromatic compound (eg styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or 50 to 99 parts by weight of methacrylic acid- (C ₁ -C ₈ ) -alkyl esters (eg methyl methacrylate, ethyl methacrylate) and B.1.2) vinyl cyanide (acrylonitrile and methacrylonitrile) Such as unsaturated nitriles) and / or (meth) acrylic acid- (C ₁ -C ₈ ) -alkyl esters (e.g. methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or derivatives (e.g. : A mixture of 1 to 50 parts by weight of anhydrides and imides of unsaturated carboxylic acids such as maleic anhydride and N-phenylmaleimide.

Preferred monomers B.1.1 are selected from one or more styrene, α-methylstyrene and methyl methacrylate monomers, and preferred monomers B.1.2 are selected from one or more acrylonitrile, maleic anhydride and methyl methacrylate monomers. Particularly preferred monomers are B.1.1 styrene and B.1.2 acrylonitrile.

Suitable graft bases B.2 for graft polymers (B) are, for example, diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and optionally acrylates, polyurethanes, silicones, chloroprene and Ethylene / vinyl acetate rubber.

Preferred graft bases B.2 are, for example, diene rubbers, preferably butadiene or mixtures of isoprene or diene rubbers, or copolymers of diene rubbers or further copolymerizable monomers thereof (e.g. B. In accordance with 1.1 and B.1.2). Component B.2 preferably has a glass transition temperature of less than about 0 ° C, particularly preferably less than -20 ° C. Graft base B.2 generally has an average particle size (d ₅₀ value) of from 0.05 to 10 μm, preferably from 0.1 to 5 μm, particularly preferably from 0.2 to 1 μm. Especially preferred are pure polybutadiene rubbers containing up to 30% by weight (relative to rubber base) of comonomers, optionally selected from styrene, acrylonitrile, methyl methacrylate or mixtures thereof.

Particularly preferred polymers B are described, for example, in DE-A 2 035 390 or DE-A 2 248 242 or in Ullmanns Encyclopaedia of Industrial Chemistry, Vol. 19 (1980), p. 280 ff.] ABS polymers (emulsified, bulk and suspended ABS). The gel ratio of graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).

Graft copolymer B is produced by free-radical polymerization, for example by emulsification, suspension, solution or bulk polymerization, preferably by emulsification or bulk polymerization.

Particularly suitable graft rubbers are also ABS polymers produced by redox initiation by an initiator system comprising organic hydroperoxide and ascorbic acid according to US-A 4 937 285.

Since the graft monomer in the graft reaction, as is known, is not necessarily completely grafted onto the graft base, according to the invention the graft polymer B is also in the presence of the graft base (co) polymerization of the graft monomer It is understood to include the products obtained by and produced in the workup.

Suitable acrylate rubbers according to B.2 of polymer B are preferably polymers of acrylic acid alkyl esters, optionally containing up to 40% by weight (relative to B.2) of other polymerizable ethylenically unsaturated monomers. Preferred polymerizable acrylic esters are C ₁ -C ₈ alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters, halogenated alkyl esters, preferably halogen (C ₁ -C ₈ ) alkyls Esters such as chloroethyl acrylate, and mixtures of these monomers.

Monomers having more than one polymerizable double bond can be copolymerized for crosslinking. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms (e.g. ethylene glycol Dimethacrylate, allyl methacrylate); Polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; Polyfunctional vinyl compounds such as divinyl benzene and trivinyl benzene; And triallyl phosphate and diallyl phthalate.

Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate, and heterocyclic compounds containing at least three ethylenically unsaturated groups.

Particularly preferred crosslinking monomers are cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallyl benzene. The amount of crosslinking monomer is preferably 0.02 to 5% by weight, in particular 0.05 to 2% by weight relative to graft base B.2.

For cyclic crosslinking monomers having three or more 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 may optionally be used in the production of graft base B.2 in addition to acrylic esters are, for example, acrylonitrile, styrene, α-methylstyrene, acrylamide, vinyl-C _1- C ₆ -alkyl ether, methyl methacrylate and butadiene. Preferred acrylate rubbers as graft base B.2 are emulsion polymers having a gel content of at least 60% by weight.

Further suitable graft bases according to B.2 are grafs, such as those described in DE-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3 631 539. Silicone rubber with a t-active site.

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

The average particle size d ₅₀ is in each case the upper and lower diameters in which 50% by weight of the particles are present and can be determined by ultracentrifugation measurements (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).

The copolycarbonate composition may contain, as an additional component, the polymer according to component C.

Component C comprises at least one thermoplastic vinyl (co) polymer C.1 and / or polyalkylene terephthalate C.2.

The copolycarbonate composition may contain up to 45 parts by weight, preferably up to 35 parts by weight (relative to the total composition) of the polymer according to component C).

Suitable as vinyl (co) polymer C.1 are vinyl aromatics, vinyl cyanide (unsaturated nitrile), (meth) acrylic acid- (C ₁ -C ₈ ) -alkyl esters, unsaturated carboxylic acids and derivatives such as unsaturated carboxyl Anhydrides of acids and imides). Particularly suitable are C.1.1) vinyl aromatics and / or nucleo-substituted vinyl aromatics (eg styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid- (C ₁ 50-99 parts by weight, preferably 60-80 parts by weight, and C.1.2) vinyl cyanide (unsaturated nitrile) (examples: -C ₈ ) -alkyl esters (eg methyl methacrylate, ethyl methacrylate) : acrylonitrile and methacrylonitrile), and (or) a (meth) acrylic acid - (C ₁ -C ₈₎ - alkyl esters (such as methyl methacrylate, n- butyl acrylate, t- butyl acrylate), And / or 1 to 50 parts by weight of unsaturated carboxylic acids such as maleic acid and / or derivatives such as anhydrides and imides of unsaturated carboxylic acids such as maleic anhydride and N-phenylmaleimide. And preferably 20 to 40 parts by weight of the (co) polymer.

The (co) polymer C.1 is like a resin, is thermoplastic and contains no rubber. Especially preferred are copolymers of C.1.1 styrene and C.1.2 acrylonitrile.

The (co) polymers according to C.1 are known and can be produced by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The (co) polymer preferably has an average molecular weight (M _W , weight average determined by light scattering or sedimentation) of 15,000 to 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 with aliphatic, cycloaliphatic or araliphatic diols, and mixtures of these reaction products.

Preferred polyalkylene terephthalates are at least 80% by weight of terephthalic acid radicals, preferably at least 90% by weight (relative to the dicarboxylic acid component), and at least 80% by weight of ethylene glycol radicals and / or butanediol-1,4 radicals, preferably Contains 90 mol% or more (relative to the diol component).

Preferred polyalkylene terephthalates are, in addition to terephthalic esters, radicals of other aromatic or alicyclic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms (e.g. phthalic acid, isophthalic acid, naphthalene-2). , 6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azeraic acid or cyclohexanediacetic acid) 20 mol% or less, preferably 10 mol% It may contain the following.

Preferred polyalkylene terephthalates are, in addition to ethylene glycol radicals or butanediol-1,4 radicals, other aliphatic diols having 3 to 12 carbon atoms or alicyclic diols having 6 to 21 carbon atoms, for example propanediol-1,3, 2- Ethyl propanediol-1,3, neopentyl glycol, pentanediol-1,5, hexanediol-1,6, cyclohexanedimethanol-1,4, 3-ethylpentanediol-2,4, 2-methylpentanediol -2,4, 2,2,4-trimethylpentanediol-1,3, 2-ethylhexanediol-1,3, 2,2-diethylpropanediol-1,3, hexanediol-2,5, 1 , 4-di- (β-hydroxyethoxy) -benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy-1,1,3,3-tetra 20 mol% or less of radicals of methylcyclobutane, 2,2-bis (4-β-hydroxyethoxyphenyl) -propane and 2,2-bis- (4-hydroxypropoxyphenyl) -propane, preferably It may contain up to 10 mol% (DE-A 2 407 674, 2 407 776, 2 715 932).

Polyalkylene terephthalates are branched by introducing relatively small amounts of trivalent or tetravalent alcohols or trivalent or tetravalent carboxylic acids, for example according to DE-A 1 900 270 and US-A 3 692 744. Can be. Preferred crosslinkers are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.

Particularly preferred are only terephthalic acid and its reactive derivatives (eg its dialkylyl esters) and polyalkylene terephthalates produced from ethylene glycol and / or butanediol-1,4, and mixtures of these polyalkylene terephthalates .

The mixture of polyalkylene terephthalates is 1 to 50% by weight, preferably 1 to 30% by weight, and 50 to 99% by weight of polybutylene terephthalate, preferably 70 to 99% by weight of polyethylene terephthalate.

Polyalkylene terephthalates which are preferably used generally have an inherent viscosity of 0.4 to 1.5 dl / g measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. in an Ubbelohde viscometer. , Preferably it is 0.5-1.2 dl / g.

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

The polycarbonate composition according to the invention may contain a flame retardant, and particularly preferably may contain a phosphorus-containing flame retardant.

The phosphorus-containing flame retardant in the present invention is particularly preferably selected from the group consisting of monomeric and oligomeric phosphoric and phosphonic acid esters, phosphonateamines and phosphazenes, mixtures of several components selected from one or more of these crowds also It can be used as a flame retardant. Other halogen-free phosphorus compounds not specifically mentioned herein can also be used alone or in any mixture with other halogen-free phosphorus compounds.

Preferred monomeric and oligomeric phosphoric acid and / or phosphonic acid esters are phosphorus compounds of formula IV:

Where

R ⁹ , R ¹⁰ R ¹¹ and R ¹² in each case are independently halogenated C ₁ -C ₈ alkyl, or in each case optionally alkyl, preferably C ₁ -C ₄ alkyl and / or halogen, Preferably C ₅ -C ₆ cycloalkyl, C ₆ -C ₂₀ aryl or C ₇ -C ₁₂ aralkyl substituted by chlorine or bromine,

n is 0 or 1 independently of each other,

q is 0 to 30,

X represents a mononuclear or polynuclear aromatic radical having 6 to 30 carbon atoms, or a linear or branched aliphatic radical having 2 to 30 carbon atoms which may be OH-substituted and may contain up to 8 ether bonds.

Preferably, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² independently of _one another represent C ₁ -C ₄ alkyl, phenyl, naphthyl or phenyl-C ₁ -C ₄ -alkyl. The aromatic groups R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may be substituted by halogen and / or alkyl groups, preferably chlorine, bromine and / or C ₁ -C ₄ -alkyl. Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl, and their corresponding brominated and chlorinated derivatives.

X in formula IV preferably represents a mononuclear or polynuclear aromatic radical having 6 to 30 carbon atoms. It is preferably derived from diphenols of formula (II).

In formula (IV) n is 0 or 1 independently of each other, n is preferably 1.

q represents the value of 0-30. When using mixtures of different components of formula IV, preferably mixtures with a number average of q values of 0.3 to 20, particularly preferably 0.5 to 10, in particular 0.5 to 6 can be used.

X is particularly preferably

Or chlorinated or brominated derivatives thereof, in particular X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. X is particularly preferably derived from bisphenol A.

The use of oligomeric phosphate esters of formula IV derived from bisphenol A is particularly advantageous because the compositions containing such phosphorus compounds have particularly high stress cracking resistance and hydrolysis resistance, which form a crust during injection molding processing. This is because the tendency is low. In addition, particularly high heat resistance can be achieved by these flame retardants.

Monophosphate (q = 0) and oligophosphate (q = 1-30) can also be used as mixtures.

The monoin compounds of formula IV are especially tributyl phosphate, tris- (2-chloroethyl) -phosphate, tris- (2,3-dibromopropyl) -phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcreate Silphosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri- (isopropylphenyl) -phosphate, halogen-substituted aryl phosphate, methylphosphonic acid dimethyl ester, methyl-phosphonic acid diphenyl ester, phenyl Phosphonic acid diethyl ester, triphenyl-phosphine oxide or tricresylphosphine oxide.

Phosphorus compounds according to formula IV are known (EP-A 363 608, EP-A 640 655) or can be produced in a similar manner by known methods (for example, Ullmanns Encyclopaedia of Industrial Chemistry , Vol. 18, p. 301 ff., 1979; See Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177).

The average q value determines the composition of the phosphate mixture (molecular weight distribution) by a suitable method (gas chromatography (GC), high pressure chromatography (HPLC), gel permeation chromatography (GPC)), from which the average value of q is calculated. Can be found by

The phosphonateamine is preferably a compound of formula (V):

A _3-y -NB ¹ _y

Where

A represents a radical of the formula Va or formula Vb,

y represents an integer 0, 1 or 2,

B ¹ is independently hydrogen, optionally halogenated C ₂ -C ₈ alkyl, or unsubstituted or substituted C ₆ -C ₁₀ aryl, B ¹ is preferably independently hydrogen, ethyl, which may be substituted by halogen, n-propyl or iso-propyl, unsubstituted C ₆ -C ₁₀ aryl or C ₆ -C ₄ alkyl and / or halogen substituted C ₆ -C ₁₀ aryl, especially phenyl or naphthyl.

Where

R ¹¹ and R ¹² are independently of each other unsubstituted or substituted C ₁ -C ₁₀ alkyl or unsubstituted or substituted C ₆ -C ₁₀ aryl,

R ¹³ and R ¹⁴ are independently of each other unsubstituted or substituted C ₁ -C ₁₀ alkyl or unsubstituted or substituted C ₆ -C ₁₀ aryl, or R ¹³ and R ¹⁴ together are unsubstituted or substituted C ₃ -C ₁₀ alkylene.

Alkyl at R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently represents preferably methyl, ethyl, n-propyl, iso-propyl, n-, iso-, secondary or tert-butyl, phenyl or hexyl .

Alkyl substituted at R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is independently C ₁ -C ₁₀ alkyl, preferably substituted by halogen, in particular methyl substituted once or twice, methyl, ethyl, n-propyl, iso -Propyl, n-, iso-, secondary, or tert-butyl, pentyl or hexyl.

C ₆ -C ₁₀ aryl at R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently preferably substituted by phenyl, naphthyl or vinaphthyl, especially halogen (generally once, twice) Or substituted three times) o-phenyl, o-naphthyl, o-binafyl.

R ¹³ and R ¹⁴ may form a ring structure with an oxygen atom to which they are directly bonded, and a phosphorus atom.

The following compounds may preferably be mentioned by way of example: 5,5,5 ', 5', 5 ", 5" -hexamethyltris- (1,3,2-dioxaphosphorinane- of formula Va-1 Methane) amino-2,2 ', 2 "-trioxide (experimental product XPM 1000 from Solutia Inc., St. Louis, USA), 1,3,2-dioxaphosphorinane-2 -Methanamine, N-butyl-N [(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl) methyl] -5,5-dimethyl-, P, 2-dioxide; 1 , 3,2-dioxaphosphorin-2-methanamine, N-[[5,5-dimethyl-1,3,2-dioxaphosphorin-2-yl) methyl] -5,5-dimethyl -N-phenyl-, P, 2-dioxide; 1,3,2-dioxaphosphorinane-2-methanamine, NN-dibutyl-5,5-dimethyl-, 2-oxide, 1,3,2 Dioxaphosphorin-2-methanamine, N-[(5,5-dimethyl-1,3,2-dioxaphosphorin-2-yl) methyl] -N-ethyl-5,5-dimethyl -, P, 2-dioxide, 1,3,2-dioxaphosphorinane-2-methanamine, N-butyl-N-[(5,5-dichloromethyl-1,3,2-dioxaphosphory Nan-2-day) me ] -5,5-dichloromethyl-, P, 2-dioxide; 1,3,2-dioxaphosphorinane-2-methanamine, N-[(5,5-dichloromethyl-1,3,2- Dioxaphosphorin-2-yl) methyl] -5,5-dichloromethyl-N-phenyl, P, 2-dioxide; 1,3,2-dioxaphosphorin-2-methanamine, N, N -Di- (4-chlorobutyl) -5,5-dimethyl-2-oxide; 1,3,2-dioxaphosphorin-2-methaneimine, N-[(5,5-dimethyl-1,3 , 2-dioxaphosphorinan-2-yl) methane] -N- (2-chloroethyl) -5,5-di (chloromethyl)-, P2-dioxide.

Also preferred are compounds of formula Va-2 or formula Va-3:

Where

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have the meanings given above.

Especially preferred are compounds of formula Va-2 and Va-1.

The preparation of phosphonateamines is described, for example, in US-A 5 844 028.

Phospagens are compounds of the formulas (VIa) and (VIb):

Where

R is the same or different at each occurrence and is amino (in each case optionally halogenated, preferably fluorinated), C ₁ -C ₈ alkyl, or C ₁ to C ₈ alkoxy, C ₅ to C ₆ Cycloalkyl (in each case optionally substituted by alkyl, preferably C ₁ -C ₄ alkyl, and / or halogen, preferably chlorine and / or bromine), C ₆ to C ₂₀ aryl, preferably Represents phenyl or naphthyl, C ₆ to C ₂₀ aryloxy, preferably phenoxy, naphthyloxy, or C ₇ to C ₁₂ aralkyl, preferably phenyl-C ₁ -C ₄ -alkyl,

k represents 0 or an integer from 1 to 15, preferably an integer from 1 to 10.

The following may be mentioned by way of example: propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene and fluoroalkylphosphazene.

Phenoxyphosphazenes are preferred.

Phosphagens can be used alone or as a mixture. The radicals R may always be the same or two or more radicals in formulas Ia and Ib may be different.

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

Flame retardants may be used alone or in any mixture with each other, or may be mixed with other flame retardants.

The molding compositions according to the invention may contain one or more conventional additives such as lubricants and release agents (eg pentaerythritol tetrastearate), nucleating agents, antistatic agents, stabilizers, fillers and reinforcing agents, and colorants and pigments.

The filled or reinforced molding composition may contain up to 60% by weight of filler and / or reinforcing agent, preferably 10 to 40% by weight (relative to the filled or reinforced molding composition). Preferred reinforcing agents are glass fibers. Preferred fillers that may have a reinforcing action are glass spheres, mica, silicates, quartz, talc, titanium dioxide and wollastonite.

The molding composition according to the present invention may further contain up to 35% by weight (relative to the total composition), optionally a synergistically acting flame retardant. Examples of additional flame retardants that may be mentioned include 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 and Al hydroxides, inorganic compounds such as antimony oxide, barium metaborate, hydroxylantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate Date, zinc borate, ammonium borate, barium metaborate, talc, silicate, silicon dioxide and tin oxide, and siloxane compounds, such phosphorus compounds are described in EP-A 363 608, EP-A 345 522 and DE-OS 197. 21 628.

The composition according to the invention is prepared by mixing the individual components in a known manner and then melt-blending and melt extruding the mixture in conventional apparatus such as internal mixers, extruders and twin screw extruders. Mixing of the individual components can occur continuously or simultaneously in a known manner, more specifically at about 20 ° C. (room temperature) and elevated temperature.

The thermoplastic molding compositions according to the invention are suitable for the production of molded articles which meet the stringent requirements for all types of molded articles, in particular mechanical properties, due to their excellent flame retardancy, in particular their short reburn time, and their good mechanical and high heat resistance. Do.

The molding composition can be used to make any type of molded article. In particular molded articles can be produced by injection molding. Examples of moldings that can be produced include all types of housing parts, for example for home appliances (such as juice presses, coffee-makers, mixers) or for company machines (such as monitors, printers, copiers), Or coverplates in construction and parts in the automotive sector.

The molding compositions according to the invention also comprise internal structural parts for armored vehicles, wheelcaps, housings of electrical devices containing small transformers, housings for information dispensing and delivery devices, housings and linings for medical purposes, massage devices And housings thereof, children's toy cars, two-dimensional wall elements, housings for safety devices, rear spoilers, heat-insulated transport containers, devices for accommodating or caring for small animals, moldings for sanitary ware and bathroom accessories, exhaust It can be used to manufacture cover grids for openings, molded articles for outdoor sperm and warehouses, and housings for garden tools.

The following additional uses are possible:

Data technology and filing devices: telecommunications devices (e.g. telephone and telefax, computers, printers, scanners, plotters, monitors, keyboards, typewriters, oral recorders, etc.)

Electrical devices: power supplies, charging devices, miniature transformers for computers and maintenance electronics, low voltage transformers, etc.

Garden tools: garden furniture, lawn mower housings, hoses and housings for garden watering equipment, outdoor sperm, blade trimmers, shredders, choppers, sprayers, etc.

Furniture sectors: workbenches, furniture stacks, roller shutter devices, office furniture, tables, chairs, seats, cabinets, shelves, door devices, window devices, bed boxes, etc.

Sports / Game Device: Toy Car, Seat, Pedal, Sports Device, Bicycle, Table Tennis Table, Home Training Device, Gold Caddy, Snowboard, Boat Exterior Parts, Camping Device, Beach Basket, etc.

Interior / exterior applications in the building sector: household appliances, profiled strips, pipework, cables, rolling shutter devices, letter boxes, lamp housings, roof tiles, flagstone pavements, split walls, cable conduits, floors Engraving and border, plug socket etc

Automotive / armor applications: wall linings, roof linings, seat frames, seats, benches, tables, cargo compartments, heel caps, rear spoilers, fenders, rear wings, bonnets, side parts, etc.

Another form of processing of the molding composition is the production of molded articles by thermoforming from prefabricated sheets or films.

The present invention therefore also provides the use of the molding compositions according to the invention for the production of shaped articles of all types, preferably the abovementioned types, and the molded articles formed from the compositions according to the invention.

The following examples are provided to illustrate the present invention in more detail.

ingredient:

30 mol% of 4,4'-dihydroxydiphenyl (DOD) and 70 mol% of bisphenol A having a mean molecular weight (weight average) of 24970 determined by gas permeation chromatography on polystyrene as the A1 reference material. Bonate.

The copolycarbonate of A1 wherein A2 M _W is 25620.

The copolycarbonate of A1 wherein A3 M _W is 25190.

The copolycarbonate of A1 wherein A4 M _W is 25050.

Polycarbonates based on A5 bisphenol A (Markrolon® 2600, Bayer AG, Leverkusen, Germany).

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 of granular crosslinked polybutadiene rubber (d ₅₀ = 0.28 μm) produced by B emulsion polymerization.

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

Additives (stabilizers, release agents).

The polycarbonate composition according to the invention was prepared by combining the components and additives at 240 to 300 ° C. in a twin screw extruder.

This composition is shown in Table 1 below.

Example One 2 3 4 Comparative example A1 70 - - - - A2 - 70 - - - A3 - - 70 - - A4 - - - 70 - A5 - - - - 70 B 13 13 13 13 13 C 17 17 17 17 17 additive 0.85 0.85 0.85 0.85 0.85

Table 2 below shows the results of the investigation on the external fiber strain. Samples were subjected to an external fiber strain selected in an isooctanol / toluene mixture (1: 1) over 5 minutes. Edge cracking was caused by 1% external fiber deformation in the comparative sample, whereas this sample did not show any cracking. At 1.2% strain, the comparative sample ruptured. The sample according to the invention did not show any negative viscosity. At an outer fiber strain of 2.4%, the samples according to the invention also exhibited cracks over 68 to 150 minutes.

OR: no crack, KR: edge crack. The time indicates how long the sample remains in the solvent mixture at the specified strain until cracks or ruptures occur. "-" Indicates no result.

Outer fiber strain Example One 2 3 4 5 (Comparative Example) 1.00% - - - - Rupture after KR / OR 5 minutes 1.20% - - - - Burst after 5 minutes 2.4% Burst after 150 minutes Ruptured after 113 minutes Ruptures after 87 minutes Rupture after 68 minutes

In further experiments the samples were held in isooctanone / toluene (1: 1) for 14 days and then the time (minutes) until cracking occurred at an external fiber strain of 2.4%. The results obtained are shown in Table 3 below.

Example One 2 3 4 5 (Comparative Example) Outer fiber strain 2.4% rupture time After 76 minutes 30 minutes later 38 minutes later 33 minutes later Immediately

Notched impact strength according to ISO 180 1A of samples according to the invention and comparative examples was measured at room temperature and 0 ° C. The results given in Table 4 below show no degradation over the comparative sample within the measurement accuracy range.

Notched impact strength a _k Example One 2 3 4 5 (Comparative Example) a _k [kJ / ㎡] At room temperature 80 88 84 82 84 At 0 ℃ 65 62 61 63 68

The thermal stability of the samples was measured at 290 ° C and 300 ° C. The results are shown in Table 5 below. Small sample plates were prepared at various temperatures by injection molding and then visually evaluated.

Thermal stability Example One 2 3 4 5 (Comparative Example) 290 ℃ 4 3 2 2 4 300 ℃ 2 2 One 2 4-5

As indicated by the defects on the surface, the larger the number, the greater the damage to the sample. Numbers 1 and 2 are numbers for minimal surface defects or streak formation, while numbers 4 or 5 represent indications for very pronounced streak formation. It can be seen that all molding compositions according to the present invention have improved thermal stability compared to Comparative Example 5.

Claims (15)

A) 2 to 98 parts by weight of a thermoplastic aromatic copolycarbonate consisting of 0.1 mole% to 46 mole% of a compound of formula (I) and a residual amount, i.e., 99.9 mole% to 54 mole%, of a diphenol different from the compound of formula (I) And B) 1 to 50 parts by weight of one or more graft polymers consisting of B1) 5 to 90 parts by weight of at least one vinyl monomer and B2) 95 to 10 parts by weight of rubber having a glass transition temperature of 10 ° C. or less. Bonate Composition: <Formula I> Where R ¹ to R ⁸ independently represent hydrogen, halogen, C ₁ to C ₈ alkyl, C ₁ to C ₅ cycloalkyl, C ₆ to C ₁₀ aryl and C ₇ to C ₁₂ aralkyl. The copolycarbonate composition of claim 1, wherein component A consists of a diphenol of formula II in addition to the diphenol of formula I: <Formula II> Where A is C ₁ -C ₅ alkylene, C ₂ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO _2- , C ₆ -C ₁₂ arylene (wherein further aromatic rings optionally containing heteroatoms may be condensed) or formula IIa or formula IIb <Formula IIa> <Formula IIb> Represents a radical of B in each case represents C ₁ -C ₁₂ alkyl or halogen, x is 0, 1 or 2 independently of each other in each case, p is 0 or 1, R ⁵ and R ⁶ can be selected individually for each X ¹ , independently of one another represent hydrogen or C ₁ -C ₆ alkyl, X ¹ represents carbon, m is an integer of 4 to 7 provided that at least one atom of X ¹ , R ⁵ and R ⁶ is alkyl at the same time. The copolycarbonate composition of claim 2, wherein the diphenol of formula (II) is 2,2-bis (4-hydroxyphenol) propane (bisphenol A). Copolycarbonate composition of any one of Claims 1-3 containing 0.1-40 weight part of thermoplastic resins (C). The method of claim 4, wherein the thermoplastic resin C is C1) C1.1) aromatic vinyl and (or) a nuclear-substituted vinyl aromatic and (or) a (meth) acrylic acid (C ₁ -C ₈₎ alkyl ester, 50 to 99 parts by weight And C1.2) vinyl cyanide and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters and / or anhydrides of unsaturated carboxylic acids and mixtures of 1 to 50 parts by weight of a copolymer or copolymer of imide And C2) a polyalkylene terephthalate or a mixture of polyalkylene terephthalates, or a mixture thereof. 6. The copolycarbonate composition according to claim 1, wherein rubber B.2 is a diene rubber, an acrylate rubber, a silicone rubber or an ethylene-propylene-diene rubber, or a mixture thereof. 7. The copolycarbonate composition according to any one of claims 1 to 6, containing a halogen-free flame retardant. The copolycarbonate composition of claim 7, wherein the flame retardant is a phosphorus compound of formula IV: <Formula IV> Where R ¹⁵ , R ¹⁶ R ¹⁷ and R ¹⁸ independently of _one another represent C ₁ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl, C ₆ -C ₁₀ aryl or C ₇ -C ₁₂ aralkyl, n is 0 or 1 independently of each other, q is an integer from 1 to 5, or in the case of mixtures an average of from 1 to 5, X represents a mononuclear or polynuclear aromatic radical having 6 to 30 carbon atoms. 6. The copolycarbonate composition of claim 1, wherein the copolycarbonate component consists of 34 to 26 mole percent monomer of formula (I), and a residual amount of monomer of formula (II). 7. Use of a copolycarbonate composition according to any one of claims 1 to 9 for the production of shaped articles. Use of a copolycarbonate composition according to any one of claims 1 to 9 for exterior use. Use of the copolycarbonate composition according to any one of claims 1 to 9 in the automotive field. Use of the copolycarbonate composition according to any one of claims 1 to 9 in the field of electrical engineering. Molded article containing the thermoplastic copolycarbonate composition of any one of Claims 1-9. Housing part containing the thermoplastic copolycarbonate composition according to claim 1.