DE19540312A1 - Polycarbonate moulding material which does not form burning drips when burnt - Google Patents

Abstract

Moulding materials (MM), containing (A) 1-96.5 wt% halogen- free polycarbonate(s), (B) 1-96.5 wt% halogen-free graft copolymer consisting of (b1) 40-80 wt% rubber-elastic grafting base with a Tg of below 0 deg C and (b2) 20-60 wt% grafted shell derived from (b21) 50-95 wt% vinylaromatic monomers of formula (I), in which R = H or 1-8C alkyl; R<1> = 1-8C alkyl; n = 0, 1, 2 or 3; and/or MMA, and (b22) 5-50 wt% (meth)acrylonitrile, MMA and/or maleic anhydride, (C) 1-96.5 wt% halogen-free thermoplastic copolymer with an average mol. wt. (Mw) of less than 400,000, derived from (c1) 50-95 wt% monomer (I) and/or MMA and (c2) 5-50 wt% comonomer(s) as in (b22), (D) 0.5-30 wt% halogen-free thermoplastic copolymer with a Mw of at least 800,000 and a wide mol. wt. distribution, derived from (d1) 50-95 wt% monomer(s) (I), (d2) 5-50 wt% comonomers as in (b22) and (d3) 0-15 wt% mono-unsaturated comonomers with at least one polar functional group, (E) 1-25 wt% halogen-free phosphorus compound(s) and (F) 0-50 wt% additives. Also claimed are mouldings, film and fibres containing MM.

Description

The present invention relates to molding compositions which

• A) 1 to 96.5% by weight of at least one halogen-free poly carbonats
• B) 1 to 96.5% by weight of at least one halogen-free graft polymer, built up from
  • b₁) 40 to 80 wt .-% of a graft base made of a rubber-elastic polymer with a glass transition temperature of below 0 ° C.
  • b₂) 20 to 60 wt .-% of a graft
    • b₂₁) 50 to 95 wt .-% vinyl aromatic monomer of the general formula I wherein R is an alkyl radical with 1 to 8 G atoms or a hydrogen atom and R¹ is an alkyl radical with 1 to 8 C atoms and n is 0, 1, 2 or 3 or methyl methacrylate or mixtures thereof and
    • b₂₂) 5 to 50 wt .-% acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or mixtures thereof
• C) 1 to 96.5 wt .-% of at least one halogen-free, thermoplastic copolymer with an average molecular weight (weight average M _w ) of less than 400,000
  • c₁) 50 to 95 wt .-% vinyl aromatic monomer of the general formula I or methyl methacrylate or mixtures thereof and
  • c₂) 5 to 50 wt .-% acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or mixtures thereof
• D) 0.5 to 30% by weight of at least one halogen-free, thermoplastic copolymer with an average molecular weight (weight average M _w ) of at least 800,000 g / mol and a broad molar mass distribution
  • d₁) 50 to 95% by weight of vinyl aromatic monomers of the general formula I or mixtures thereof,
  • d₂) 5 to 50 wt .-% acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or mixtures thereof and
  • d₃) 0 to 15% by weight of monoethylenically unsaturated monomers with at least one polar functional group,
• E) 1 to 25 wt .-% of at least one halogen-free phosphorus connection,
• F) 0 to 50 wt .-% additives

consist.

Furthermore, the present invention relates to the use these molding compositions for the production of moldings, films or Fibers as well as the moldings, foils or fibers themselves. Before preferred embodiments are the dependent claims and the Be take spelling.

If thermoplastic materials are ignited, they soften (provided no cross-linking reactions occur) mostly right quickly because their viscosity is strong due to the high temperatures decreases. Parts of the material therefore often separate from the mold body off. This process is called draining or, if the Sample is still burning, called burning dripping. By from dripping material can easily ignite other objects det and so a source of fire are carried on. That’s why already made considerable efforts to effective anti-drip to develop agents for thermoplastic molding compounds.

Halogen-containing polymers such as polytetrafluorethylene work against draining, but should for environmental reasons inertia can be avoided. As a halogen-free anti-drip agent were disclosed in EP-A-305 764 polystyrenes with molecular weights of more than 400,000 g / mol and a broad molar mass distribution for blends from polyphenylene ethers and HIPS recommended. For one, put this  Anti-drip agent the tendency to drip this thermoplastic form do not yet descend enough, on the other hand they increase the Melt viscosity for those relevant for injection molding processing shear speeds. The toughness of these blends will also decreased with increasing proportion of anti-dripping agents.

Halogen-free anti-dripping agents for thermoplastic molding compositions do not have these disadvantages, are those in DE-P. . . be written polymers based on vinyl aromatic monomers with molecular weights of at least 800,000 g / mol and one towards molecular weight distribution.

Polystyrenes as described in EP-A-305 764 are not compatible with molding compounds based on polycarbonates Lich.

JP-A 06016919 shows that polycarbonate-containing form mass with a mixture of styrene copolymers, phosphorus-containing Copolymers and Teflon must be mixed to prevent dripping to prevent.

The object of the present invention was to provide thermoplastic form to provide masses based on polycarbonates, which are equipped with a halogen-free anti-drip agent, the can be easily manufactured with the other components of the Molding compound is miscible and that the mechanical properties of the thermoplastic molding compositions not affected.

This object is achieved by the molding compositions mentioned at the outset.

Component A

The inventive molding compositions of 1 contain as component A. to 96.5% by weight, preferably from 3 to 92.9% by weight, based on the Sum of components A to F, at least one polycarbonate.

Suitable halogen-free polycarbonates are, for example based on diphenols of the general formula II

wherein A 'is a single bond, a C₁ to C₃ alkylene, a C₂- to C₃-alkylidene, a C₃- to C₆-cycloalkylidene group, and -S- or -SO₂- means.

Preferred diphenols of the formula II are, for example 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxy phenyl) cyclohexane. Other preferred diphenols are hycroquinone or resorcinol. 2,2-bis (4-hydroxy) are particularly preferred phenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane as well 1,1-bis (4-hydroxyphenyl) -3,2,5-trimethylcyclohexane as well 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Both homopolycarbonates and copolycarbonates are compo nente A is suitable, in addition to the bisphenol A homopoly are preferred merisat the copolycarbonates of bisphenol A.

The suitable polycarbonates can be branched in a known manner be, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used at least trifunctional compounds, for example those with three or more than three phenolic OH groups.

Polycarbonates which have relative viscosities η _rel of 1.10 to 1.50, in particular of 1.20 to 1.40, have proven to be particularly suitable. This corresponds to average molecular weights M _w (weight average) of 10,000 to 200,000 g / mol, preferably 20,000 to 80,000 g / mol.

The diphenols of the general formula II are known per se or can be produced by known processes.

The polycarbonates can be prepared, for example, by Um settlement of the diphenols with phosgene after the phase interfaces process or with phosgene according to the process in homogeneous phase (the so-called pyridine process), which in each case molecular weight to be set in a known manner by a appropriate amount of known chain terminators is achieved. (Regarding polydiorganosiloxane-containing polycarbonates see e.g. DE-OS 33 34 782.)

Suitable chain terminators are, for example, phenol, p-t-butyl phenol but also long-chain alkylphenols such as 4- (1,3-tetramethyl butyl) phenol, according to DE-OS 28 42 005 or monoalkylphenols or Dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituted according to DE-A 35 06 472, such as p-nonylphenyl, 3,5-di-t-  Butylphenol, p-t-octylphenol, p-dodcecylphenol, 2- (3,5-dimethyl heptyl) phenol and 4- (3,5-dimethylheptyl) phenol.

Halogen-free polycarbonates in the sense of the present invention means that the polycarbonates from halogen-free diphenols, halogen-free chain terminators and halogen-free if necessary Branch are built, the content of subordinate ppm amounts of saponifiable chlorine, resulting for example from the production of the polycarbonates with phosgene after the phase interface process, not as containing halogen in the sense of the Er is to be seen. Such polycarbonates with ppm contents saponifiable chlorine means halogen-free polycarbonates present invention.

Component B

The inventive molding compositions of 1 contain as component B. to 96.5 wt .-%, preferably from 3 to 93 wt .-%, based on the Sum of components A to F, at least one halogen-free Graft polymer composed of

• b₁) 40 to 80 wt .-%, preferably from 50 to 70 wt .-%, based on the graft polymer, a graft base from a rubber-elastic polymers with a glass transition temperature temperature below 0 ° C
• b₂) 20 to 60 wt .-%, preferably from 30 to 50 wt .-%, based on the graft polymer, a graft
  • b₂₁) 50 to 95 wt .-%, preferably from 60 to 80 wt .-%, based on the graft, vinyl aromatic monomers of the general formula I or methyl methacrylate or mixtures thereof and
  • b₂₂) 5 to 50 wt .-%, preferably from 20 to 40 wt .-%, based on the graft, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or mixtures thereof.

Polymers are suitable for the graft base, their Glass transition temperature below 0 ° C, preferably below of -20 ° C. These are e.g. B. natural rubber, synthetic rubber based on conjugated dienes, if desired with others ren copolymers and elastomers based on C₁ to C₈-alkyl esters of acrylic acid, which also contain other comonomers can.  

Preferably come as a graft b₁ polybutadiene (see. DE-A 14 20 775 and DE-A 14 95 089) and copolymers of poly butadiene and styrene (see GB-A 649 166).

Furthermore, graft bases b 1 are preferred which are constructed out

• b₁₁) 70 to 99.9% by weight, preferably 70 to 80% by weight, based on the graft base, at least one alkyl acrylates with 1 to 8 carbon atoms in the alkyl radical, preferably n-butyl acrylate and / or 2-ethylhexyl acrylate, ins special n-butyl acrylate as the sole alkyl acrylate,
• b₁₂) 0 to 25% by weight, in particular 16 to 29% by weight, based on the graft base, another copoly merizable monoethylenically unsaturated monomers, such as butadiene, isoprene, styrene, acrylonitrile, methyl meth acrylate and / or vinyl methyl ether
• b₁₃) 0.1 to 5 wt .-%, preferably 1 to 4 wt .-%, based on the graft base, a copolymerizable, poly functional, preferably bifunctional or trifunctional, the crosslinking monomers.

As such bi- or polyfunctional crosslinking monomers b₁₃ Monomers are suitable, preferably two, optionally also three or more copolymerized ethylenic dop contain fur bonds that are not in the 1,3-position konju are greeded. Suitable crosslinking monomers are, for example Divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, Triallyl cyanurate, triallyl isocyanurate or triallyl isocyanurate. Acrylic has proven to be a particularly favorable crosslinking monomer Acid esters of tricyclodecenyl alcohol have been proven (cf. DE-A 12 60 135).

This type of graft base is also known per se and in described in the literature, for example in DE-A 31 49 358.

Of the grafts b₂ those are preferred in which b₂₁ Styrene or α-methylstyrene means. As the preferred monomer Ge Mainly styrene and acrylonitrile, α-methylstyrene are mixed and acrylonitrile, styrene, acrylonitrile and methyl methacrylate, Styrene and maleic anhydride used. The graft pads are available by copolymerization of components b₂₁ and b₂₂.  

In the event that the graft polymer B ₁ a graft base contains, which is made up of polybutadiene, one speaks of ABS rubbers.

The graft copolymerization can, for. B. from DE-A 31 49 358 be known in solution, suspension or preferably in emulsion gen. The soft phase of the graft copolymer shows, in which be preferred manufacture of ABS rubber and grafting in Emulsion, an average particle diameter (d₅₀ value of the inte grail mass distribution) from 50 to 180 nm. By enlargement of the particles, e.g. B. by agglomeration or in the extraction of Emulsion using the seed latex process, the d₅₀ value in Range from 200 to 500 nm can be set. In such Graft copolymerizations are at least partially chemi linking the polymerizing monomers with that already polymerized rubber, the linkage likely on the double bonds contained in the rubber. At least at least some of the monomers are grafted onto the rubber, through covalent bonds to the rubber thread molecules bound.

The grafting can also be done in multiple stages by first Part of the monomers forming the graft shell is grafted on and then the rest.

Is the graft base b₁ of the graft polymers B from the compo nenten b₁₁, optionally b₁₂ and b₁₃ constructed, one speaks of ASA rubbers. Their manufacture is known per se and for example in DE-A 28 26 925, DE-A 31 49 358 and DE-A 34 14 118 described.

The preparation of the graft polymer B can, for example, according to the method described in DE-PS 12 60 135.

The structure of the graft of the graft polymer can be or in two stages.

In the case of the one-stage structure of the graft pad, a Mixture of the monomers b₂₁ and b₂₂ in the desired weight ratio nis in the range from 99: 5 to 50:50, preferably from 90: 10 to 65:35 in the presence of the elastomer b₁, in a manner known per se (cf. e.g. B. DE-OS 28 26 925), preferably in emulsion, polymerized.

In the case of a two-stage construction of the graft b₂ makes the first stage generally from 20 to 70% by weight, preferably from 25 up to 50 wt .-%, based on b₂. For their manufacture  preferably only monoethylenically unsaturated aromatic carbons Hydrogen B₂₁ used.

The second stage of the graft generally makes 30 to 80 wt .-%, in particular 50 to 75 wt .-%, each based on b₂, out. Mixtures of the above are used for their production monoethylenically unsaturated aromatic hydrocarbons b₂₁ and monoethylenically unsaturated monomers b₂₂ in weight ratio b₂₁ / b₂₂ from generally 90: 10 to 60:40, ins special 80: 20 to 70: 30 applied.

The conditions of the graft copolymerization are preferably so chosen that particle sizes from 50 to 700 nm (d₅₀ value of the inte grail mass distribution) result. Measures for this are knows and z. B. described in DE-OS 28 26 925.

With the seed latex process, a coarse-grained Rubber dispersion can be produced.

In order to achieve products that are as tough as possible, it is often from before part, a mixture of at least two graft copolymers to use different particle sizes.

To achieve this, the particles of the rubber are in known way, e.g. B. by agglomeration, so that the Latex is bimodal (50 to 180 nm and 200 to 700 nm).

In a preferred embodiment, a mixture of two Graft polymers with particle diameters (d₅₀ value of the inte grail mass distribution) from 50 to 180 nm or 200 to 700 nm in Weight ratio 70: 30 to 30: 70 used.

The chemical structure of the two graft polymers is preferred wise the same, although the shell of the coarse graft poly merisates in particular can also be built in two stages.

Component C

The inventive molding compositions of 1 contain as component C. to 96.5 wt .-%, preferably from 1 to 91 wt .-%, based on the Sum of components A to F, at least one copolymer out

• c₁) 50 to 95 wt .-%, preferably from 60 to 80 wt .-%, based on c₁ and c₂, vinyl aromatic monomer of the general for mel I or methyl methacrylate or mixtures thereof and  
• c₂) 5 to 50 wt .-%, preferably from 20 to 40 wt .-%, based on c₁ and c₂, acrylonitrile, methacrylonitrile, methyl methacrylate, Maleic anhydride or mixtures thereof.

The copolymers C are halogen-free, thermoplastic and rubber-free. Particularly preferred copolymers C are those from styrene and acrylonitrile and optionally with methyl meth acrylate, from α-methylstyrene with acrylonitrile and optionally with methyl methacrylate or with styrene and α-methylstyrene Acrylonitrile and optionally with methyl methacrylate and from Styrene and maleic anhydride. Several of the be copolymers are used simultaneously.

The copolymers C are known per se and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. They have average molecular weights _w (weight average) of up to 400,000 g / mol. Preferred copolymers C have average molecular weights _w in the range from 50,000 to 380,000, in particular from 70,000 to 370,000 g / mol.

Component D

The molding compositions according to the invention contain from 0.5 to 30% by weight, based on the sum of components A to F, at least one Copolymers D. Preferred molding compositions according to the invention contain from 1 to 25% by weight, based on the sum of components A to F, these copolymers D.

Mixtures of Different copolymers D can be used.

The copolymers D are halogen-free and thermoplastic and are constructed according to the invention

• d₁) 50 to 95 wt .-%, preferably from 60 to 80 wt .-% vinyl flavor Table compounds of general formula I or their Mixtures,
• d₂) 5 to 50% by weight, preferably 20 to 40% by weight, acrylonitrile, Methacrylonitrile, methyl methacrylate, or mixtures thereof and
• d₃) 0 to 30 wt .-% of monoethylenically unsaturated monomers at least one polar functional group.

Particularly preferred copolymer D contains from 60 to 80 % By weight of the monomers d 1, from 20 to 40% by weight of the monomers d 2 and from 0 to 10 wt .-% of the monomers d₃.

Examples of suitable vinyl aromatic monomers are already indicated under c₁. Styrene or α-methyl is particularly preferred styrene, especially styrene, used as component d 1.

As monomers d₃ come with polar functional groups for example those with hydroxy, acid, anhydride, imidazole, Pyrrolidone or amino groups into consideration. Acrylic acid, methacrylic acid, vinylphenol, maleic anhydride, glycidyl methacrylate, Hydroxyethyl acrylate, vinyl phenol, vinyl imidazole, vinyl pyrrolidone or dimethylaminoethyl acrylate are examples of suitable monomers rer d₃. These include glycidyl methacrylate or hydroxyethyl acrylate is particularly preferred. Of course you can too Mixtures of different monomers d₃ are used.

According to the invention, the copolymers D have average molecular weights M _w (weight average) of at least 800,000 g / mol. In general, the average molecular weights are in the range from 830,000 to 150,000, in particular from 850,000 to 1,200,000 g / mol.

According to the invention, the copolymers D have a broad molar mass distribution, ie the ratio of weight-average to number-average molar masses M _w / M _n is large. The ratio M _w / M _n is preferably 2 or more. M _w / M _n is particularly preferably 2.5 or more, for example more than 3.

Copolymers D are known per se or can be per se known methods are produced. Generally they leave by free radical polymerization, preferably in solution or Emulsion.

Component E

The halogen-free phosphor used as component E. Compounds are in the molding compositions according to the invention in one Amount of 1 to 25 wt .-%, preferably from 2 to 20 wt .-%, based on the sum of components A to F.

Especially phosphoric acid esters of phenols, bisphenols or poly phenols or their mixtures come as component E in Be dress.  

For example, phosphates such as triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethyl phosphate or tri- (isopropyl phenyl) phosphate can be used.

Further examples of suitable halogen-free phosphorus compounds are

or

Mean in it
R², R³, R⁴ and R⁵ are identical or different aryl radicals substituted by C₁-C₄-alkyl or aralkyl groups such as, for example, phenyl-C₁-C₆-alkyl,
R⁶ is a simple carbon / carbon bond, -O-, -S-, SO₂-, -CO-, -CH₂-, -C (CH₃) ₂- or a carbon atom, to the biradical cyclo hexyl or 3.3 , 5-trimethylcyclohexyl groups are bound, and
m is an integer from 0 to 10.

Examples of phosphorus compounds of the formula III and IV are Phosphoric acid ester of 1,4-dihydroxy-benzene (hydroquinone), 1,3-dihydroxy-benzene (resorcinol), 4,4'-dihydroxydiphenyl,  Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane (Bisphenol A) and 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Likewise, phosphoric acid esters of the general formula V

can be used as component E
wherein
R⁷ is hydrogen or alkyl of 1 to 8 carbon atoms, preferably methyl,
R⁸

R⁹ phenyl, which can be substituted by alkyl having 1 to 4 carbon atoms, aryl such as phenyl or aralkyl or mixtures of phenyl and aralkyl, for example benzyl or 2-phenyl ethyl,
u an integer from zero to 12 and
v is an integer from zero to 5,
wherein the core number of the polyphenol molecule, ie the number of benzene rings of the compound V, is not higher than 12 without the radicals R⁹ to R höher.

Examples of phosphoric acid esters according to formula V are phosphorus acid esters of novolaks. Suitable novolaks are condensation products from formaldehyde and phenols of the general formula VI

wherein R¹⁰, R¹¹ and R¹² are optionally hydrogen, halogen or C₁-C₂₀-alkyl, C₄-C₇-cycloalkyl, C₆-C₁₀-aryl groups such as phenyl or can be naphthyl or wherein R₁₁ denotes hydrogen and R¹⁰, R¹² and R¹³ are the same as R oben or R⁸ could be.

Typical examples of phenols are phenol, o-cresol, m-cresol, p-cresol, 2,5-dimethyl, 3,5-dimethyl, 2,3,5-trimethyl, 3,4,5-trimethyl, p-t-butyl, p-n-octyl, p-stearyl, p-phenyl, p- (1-phenylethyl) -, 1-phenylethyl, o-isopropyl, p-isopropyl or m-isopropylphenol. Phenol is preferably used, o-cresol, m-cresol, p-cresol, p-t-butylphenol, o-t-butylphenyl.

However, mixtures of these phenols can also be used the. Novolaks used with preference are phenol / formaldehyde novo lak, o-cresol / formaldehyde novolak, m-cresol / formaldehyde novolak, p-cresol / formaldehyde novolak, t-butylphenol / formaldehyde novolak or o-octylphenol / formaldehyde novolak. Is particularly preferred the p-cresol / formaldehyde novolak.

Further examples of suitable phosphoric acid esters are phosphoric acid re-bis-phenyl- (4-phenylphenyl) ester, phosphoric acid-phenyl- bis- (4-phenylphenyl) ester, phosphoric acid tris- (4-phenyl- phenyl) ester, phosphoric acid bis-phenyl (benzylphenyl) ester, Phosphoric acid phenyl bis (benzylphenyl) ester, phosphoric acid tris (benzylphenyl) ester, phosphoric acid bis-phenyl- (1-phenyl- ethyl) phenyl) ester, phosphoric acid-phenyl-bis ((1-phenyl- ethyl) phenyl ester, phosphoric acid tris - ((1-phenyl- ethyl) phenyl) ester, phosphoric acid bis-phenyl - ((1-methyl-1-phenyl- ethyl) phenyl ester, phosphoric acid-phenyl-bis- (1-methyl-1-phenyl- ethyl) phenyl ester, phosphoric acid tris - ((1-methyl-1-phenyl-  ethyl) phenyl ester, phosphoric acid phenyl-bis- (4- (1-phenyl- ethyl) -2,6-dimethylphenyl) ester, phosphoric acid bis-phenyl-2,4-di benzylphenyl ester, phosphoric acid bis-phenyl-2,4-di- (1-phenyl- ethyl) phenyl ester and phosphoric acid bis-phe nyl-2,4-di- (1-methyl-1-phenylethyl) phenyl ester.

The phosphoric acid-phenyl-bis- (4-phenyl- phenyl) ester, phosphoric acid bis-phenyl - ((1-phenyl- ethyl) -phenyl) ester, phosphoric acid-phenyl-bis - (((1-phenyl- ethyl) -phenyl) ester, phosphoric acid bis-phe nyl - ((1-methyl-1-phenylethyl) phenyl) ester, phosphoric acid phenyl bis - ((1-methyl-1-phenylethyl) phenyl) ester, phosphoric acid tris ((1-methyl-1-phenylethyl) ester, phosphoric acid phenyl bis- (benzylphenyl) ester and the phosphoric acid bis-phe nyl-2,4-di- (1-methyl-1-phenylethyl) phenyl ester and their Mixtures.

Regarding the particularly preferred halogen-free phosphorus compounds F counts triphenylphosphine oxide.

The halogen-free phosphorus compounds are known per se or can be produced by methods known per se. So can for example novolaks with triaryl esters of phosphorus acid, preferably triphenyl phosphate, are transesterified. It can but also novolaks with phenols in the presence of phosphorus oxychlor rides can be implemented. Here, for. B. one to two equiva lente of a novolake with one mole of triphenyl phosphate or Phosphoric acid trichloride are implemented.

Of course, mixtures of different halo gene-free phosphorus compounds can be used as component E.

Component F

As component F, the molding compositions according to the invention can have 0 to 50 wt .-%, preferably from 0.1 to 45 wt .-%, based on the Sum of components A to F, additives included.

According to the invention, additives are fibrous or particulate shaped fillers, processing aids, stabilizers or Antistatic agents understood. Those that come into consideration according to the invention Additives are essentially halogen-free.  

The processing aids and stabilizers are generally mine used in amounts of 0.01 to 5 wt .-%, reinforcement medium, however, usually in amounts of 5 to 40 wt .-%, each Weil based on the sum of components A to F.

Carbon or glass are particularly preferred as component F. fibers.

The glass fibers used can be made of E, A or C glass and are preferably with a size, e.g. B. based on epoxy resin and an adhesion promoter, based on functionalized silanes equipped. Their diameter is generally between 6 and 20 µm. Both continuous fibers (rovings) and cuts can be made glass fibers with a length of 1 to 10 mm, preferably of 3 up to 6 mm.

Furthermore, fillers or reinforcing materials, such as glass balls, Mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder or wollastonite can be added.

In addition, metal flakes, metal powder, metal fibers, metal coated fillers (e.g. nickel-coated glass fibers) like this like other aggregates that shield electromagnetic waves called men. Aluminum comes in particular for the latter purpose flakes into consideration; further mixing this mass with additional Chen carbon fibers, carbon black or nickel-coated C fibers.

The molding compositions according to the invention can also further addition contain substances for polycarbonates, SAN polymers and Graft copolymers based on ASA or ABS or their Mixtures are typical and common. As such additives may be mentioned, for example: dyes, pigments, antistatic agents, Antioxidants and especially the lubricants that are used for the Further processing of the molding compounds, e.g. B. in the manufacture of Moldings or molded parts are required. Among the preferred Lubricants include ethylene oxide / propylene oxide copolymers, high molecular multi-component esters and polyethylene waxes.

The production of the thermoplastic mold according to the invention mass is made by mixing the components. It can be beneficial be to premix individual components. Even mixing the Components in solution and removal of the solvent is possible Lich.  

Suitable organic solvents for components A to E. and the soluble group F additives are, for example, chlorine benzene, mixtures of chlorobenzene and methylene chloride or Gemi cal from chlorobenzene and aromatic hydrocarbons, e.g. B. Toluene.

Evaporation of the solvent mixtures can, for example, in Evaporation extruders take place.

Mixing the z. B. dry components A, B, C, D, E and ge if necessary, F can be carried out using a wide variety of methods. However, components A, B are preferably mixed, C, D, E and optionally F at temperatures of 200 to 320 ° C by extruding, kneading or rolling the compo together nenten, where necessary the components previously from the at the solution obtained from the polymerization or from the aqueous dis persion have been isolated.

Component E can also e.g. B. as a powder or in the form of a aqueous solution directly into the melt of components A, B, C, D and, if necessary, F can be introduced. In case of insertion in the form of an aqueous solution, the water is discharged solution unit from the mixing device, preferably an extruder, away. Component E is preferably in the melt Component C introduced.

As mixing units for the implementation of the invention Processes are, for example, tumble mixers or agitators to call mixers.

Suitable units for melt compounding are examples wise discontinuous, heated internal kneader with or without stamp, continuous working kneader, screws kneader with axially oscillating screws. Twin-screw extruder like this like mixing rolls with heated rolls.

For melt extrusion there are, for example, one or two shaft extruder particularly suitable.

The thermoplastic molding compositions according to the invention can processed the known methods of thermoplastic processing become, e.g. B. by extrusion, injection molding, calendering, Blow molding, pressing or sintering.

The molding compositions according to the invention are essentially halogen free, but are characterized by the fact that they do not burn tending to drip. They can be processed thermoplastically  and have good mechanical properties. The fiction Modern thermoplastic molding compositions are suitable for production of moldings, foils or fibers.

Examples

The mean particle size and the particle size distribution were determined from the integral mass distribution. In the middle ren particle sizes is in all cases Weight average of the particle sizes, as determined with the help of an analy table ultracentrifuge using the method of W. Scholtan and H. Lange, Kolloid-Z, and Z.-Polymer 250 (1972), pages 782 to 796. The ultracentrifuge measurement delivers that integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than certain sizes. The average particle diameter, which is also the d₅₀ value of the inte grail mass distribution is referred to as the Particle diameter defined at which 50 wt .-% of the particles have a smaller diameter than the diameter that the d₅₀ value corresponds. Likewise then have 50 wt .-% of the particles a larger diameter than the d₅₀ value. For characterization the width of the particle size distribution of the rubber particles in addition to the d₅₀ value (average particle diameter) resulting from the integral mass distribution d₁₀ and d₉₀ values used. The d₁₀ or d₉₀ value of the integral masses Distribution is defined according to the d₅₀ value with the Difference that they related to 10 or 90 wt .-% of the particles are. The quotient Q = (d₉₀-d₁₀) / d₅₀ represents a measure of the Particle size distribution.

The average molecular weights (weight average M _w ) were each determined by gel permeation chromatography against a polystyrene calibration curve.

The following components were used:

Component A1

A commercial polycarbonate based on bisphenol A with a relative solution viscosity η _rel of 1.3 ml / g, measured on a 0.5 wt .-% solution in methylene chloride at 23 ° C.

Component B1

A fine-particle graft polymer made from
β₁₁) 16 g butyl acrylate and 0.4 g tricyclodecenyl acrylate, which in 150 g water with the addition of 1 g of the sodium salt of a C₁₂-C₁₈ paraffin sulfonic acid, 0.3 g potassium persulfate, 0.3 g sodium hydrogen carbonate and 0.15 g sodium pyro phosphate Stirring were heated to 60 ° C. 10 minutes after the start of the polymerization reaction, a mixture of 82 g of butyl acrylate and 1.6 g of tricyclodecenyl acrylate was added over the course of 3 hours. After the monomer addition was complete, stirring was continued for an hour. The latex of the crosslinked butyl acrylate polymer obtained had a solids content of 40% by weight, the average particle size (weight average) was found to be 76 nm and the particle size distribution was narrow (quotient Q = 0.29).
β₁₂) 150 g of the polybutyl acrylate latex obtained according to β₁₁) were mixed with 40 g of a mixture of styrene and acrylonitrile (weight ratio 75:25) and 60 g of water and with stirring after the addition of a further 0.03 g of potassium per sulfate and 0.05 g Lauroyl peroxide heated to 65 ° C for 4 hours. After the graft copolymerization had ended, the polymerization product was precipitated from the dispersion using calcium chloride solution at 95 ° C., washed with water and dried in a warm air stream. The degree of grafting of the graft polymer B1 was 35% and the particle size was 91 nm.

Component B2

A coarse-particle graft polymer that was produced as follows:
β₂₁) To a template from 1.5 g of the latex prepared according to β₁₁) were after the addition of 50 g of water and 0.1 g of potassium persulfate in the course of 3 hours on the one hand a mixture of 49 g of butyl acrylate and 1 g of tricyclodecenyl acrylate and on the other hand a solution 0.5 g of the sodium salt of a C₁₂-C₁₈ paraffin sulfonic acid in 25 g of water at 60 ° C. Polymerization was then carried out for 2 hours. The latex of the crosslinked butyl acrylate polymer obtained had a solids content of 40%. The mean particle size (weight average of the La tex) was determined to be 430 nm, the particle size distribution was narrow (Q = 0.1).
β₂₂) 150 g of the latex prepared according to β₂₁) were mixed with 20 g of styrene and 60 g of water and heated with stirring after addition of a further 0.03 g of potassium persulfate and 0.05 g of lauroyl peroxide to 65 ° C. for 3 hours. The dispersion obtained in this graft copolymerization was then polymerized with 20 g of a mixture of styrene and acrylonitrile in a weight ratio of 75:25 for a further 4 hours. The reaction product was then precipitated from the dispersion by means of a calcium chloride solution at 95 ° C., separated off, washed with water and dried in a warm air stream. The degree of grafting of the graft polymer B2 was determined to be 35%; the average particle size of the latex particles was 510 nm.

Component B3

A graft polymer prepared by polymerizing 60 g Butadiene in the presence of a solution of 0.6 g t-dodecyl mercaptan, 0.7 g of C₁₄ Na alkyl sulfonate as an emulsifier, 0.2 g of potassium peroxodisul fat and 0.2 g sodium pyrophosphate in 80 g water at 65 ° C. After The polymerization autoclave was terminated tense. The turnover was 98%.

A polybutadiene latex was obtained, the middle one Particle size was 0.1 microns. This was achieved by adding 25 g an emulsion of a copolymer of 96 g of ethyl acrylate and 4 g of nethacrylic acid amide with a solids content of 10 weight share agglomerated, with a polybutadiene latex with a mitt leren particle size of 0.35 µm was created. After adding 40 g Water, 0.4 g of Na-C₁₄ alkyl sulfonate and 0.2 part of potassium peroxodi 40 g of a mixture of styrene and acrylonitrile in the sulfate Weight ratio of 70:30 fed within 4 hours. The polymerization was carried out while stirring the batch at 75 ° C. The turnover based on styrene-acrylonitrile was practically quanti tative. The graft rubber dispersion obtained was by means of Calcium chloride solution precipitated and the separated graft polymer washed with distilled water.  

Component C1

A copolymer of styrene and acrylonitrile in a weight ratio of 75:25, produced by continuous solution polymerization. The average molecular weight M _w was 157,000 g / mol.

Component C2

A copolymer of styrene and acrylonitrile in a weight ratio of 80:20, produced by continuous solution polymerization. The average molecular weight M _w was 160,000 g / mol.

Components D1 to D3

Copolymers of styrene and acrylonitrile, each with a weight ratio of 75:25, produced by emulsion polymerization and the following average molecular weights M _w .
D1: 730,000 g / mol
D2: 850,000 g / mol
D3: 1,200,000 g / mol.

Component D4

Terpolymer of styrene, acrylonitrile and hydroxyethyl acrylate in a weight ratio of 73: 24: 3, produced by emulsion polymerization. The average molecular weight M _w was 970,000 g / mol.

Component E1

Triphenyl phosphate (e.g. Disflamoll® from Bayer).

Component E2

Resorcinol diphosphate (e.g. Fyrolflex RDP from Akzo).

Component F1

High molecular weight multi-component ester based on fatty acids with one Viscosity from 110 to 150 mPa · s at 80 ° C (e.g. Loxiol® G 705 der Henkel company).  

Component T1

Polytetrafluoroethylene (e.g. Telfon-Dispersion 30N from the company DuPont).

Production of molding compounds

The respective components were in a twin-screw extruder (ZSK 30 from Werner & Pfleiderer) mixed at 250 to 280 ° C, discharged as a strand, cooled and granulated. The dried one Granules became standard small bars at 250 to 280 ° C, ISO test specimen processed as well as flat bars for the UL 94 test.

The heat resistance of the samples was determined using the Vicat-Er softening temperature determined. The Vicat softening temperature was according to DIN 53 460, with a force of 49.05 N and a Temperature increase of 50 K per hour on standard small bars averages.

To characterize the flowability of the molding compounds, the Melt volume index (HVI) according to DIN 53 735 at one temperature of 260 ° C and 5 kg load.

The impact strength (ak) was determined according to ISO 179 leA at 23 ° C Right. The flame retardancy was tested vertically Fire test according to the regulations of the Underwriter Laboratories (UL 94). The test was carried out on 5 samples of dimensions each 127 mm × 12.7 mm × 1.7 mm.

The corresponding fire classes were classified according to UL-94 according to the following criteria:

The compositions and properties of the thermoplastic Molding compositions can be found in Tables 1 and 2.  

Table 1

V: Comparative experiments

Table 2

Claims (7)

1. Molding compounds

• A) 1 to 96.5% by weight of at least one halogen-free polycarbonate,
• B) 1 to 96.5% by weight of at least one halogen-free graft polymer, built up from
  • b₁) 40 to 80 wt .-% of a graft base made of a rubber-elastic polymer with a glass transition temperature of below 0 ° C.
  • b₂) 20 to 60 wt .-% of a graft
    • b₂₁) 50 to 95 wt .-% vinyl aromatic monomer of the general formula I wherein R represents an alkyl radical with 1 to 8 carbon atoms or a hydrogen atom and R¹ represents an alkyl radical with 1 to 8 carbon atoms and n has the value 0, 1, 2 or 3 or methyl methacrylate or mixtures thereof and
    • b₂₂) 5 to 50 wt .-% acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or mixtures thereof
• C) 1 to 96.5% by weight of at least one halogen-free, thermoplastic copolymer with an average molecular weight (weight average M _w ) of less than 400,000
  • c₁) 50 to 95 wt .-% vinyl aromatic monomer of the general formula I or methyl methacrylate or mixtures thereof and
  • c₂) 5 to 50 wt .-% acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or mixtures thereof
• D) 0.5 to 30% by weight of at least one halogen-free, thermoplastic copolymer having an average molecular weight (weight average M _w ) of at least 800,000 g / mol and a broad molar mass distribution
  • d₁) 50 to 95% by weight of vinyl aromatic monomers of the general formula I or mixtures thereof,
  • d₂) 5 to 50 wt .-% acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or mixtures thereof and
  • d₃) 0 to 15% by weight of monoethylenically unsaturated monomers with at least one polar functional group,
• E) 1 to 25% by weight of at least one halogen-free phosphorus compound,
• F) 0 to 50 wt .-% additives.

2. Molding compositions according to claim 1, in which the copolymers D are composed of

• d₁) 60 to 90 wt .-% styrene and
• d₂) 10 to 40 wt .-% acrylonitrile.

3. Molding compositions according to claim 1 or 2, in which the copolymer Dates have average molecular weights (weight average M _w ) in the range from 850,000 to 1,200,000 g / mol. 4. Molding compositions according to one of claims 1 to 4, in which the copolymers D have a molecular weight distribution, expressed by the ratio of weight average M _w to number average M _n , in the range from 2 to 10. 5. Molding compositions according to one of claims 1 to 4, in which the Component E triphenyl phosphate, resorcinol diphosphate or Is hydroquinone diphosphate. 6. Use of the molding compositions according to one of claims 1 to 5 for the production of moldings, foils or fibers. 7. Moldings, foils or fibers containing molding compositions according to one of claims 1 to 5.