DE3711608A1 - Thermoplastic moulding compositions based on polyphenylene ether - Google Patents

Abstract

Thermoplastic moulding compositions essentially containing A) from 4 to 96 parts by weight, based on the sum of components A and B, of an SAN, ABS and/or ASA polymer and B) from 4 to 96 parts by weight, based on the sum of components A and B, of a modified polyphenylene ether prepared in the melt from b1) from 90 to 99.95% by weight, based on B, of a polymer component containing at least 20% by weight, based on b1, of polyphenylene ether and at most 80% by weight, based on b1, of a vinylaromatic polymer, and b2) from 0.05 to 10% by weight, based on B, of b21) an amide group-containing monomer containing a polymerisable double bond, b22) a lactam group-containing monomer containing a polymerisable double bond, and/or b23) an alpha , beta -unsaturated dicarbonyl compound, and b3) from 0 to 50% by weight, based on B, of further non-vinylaromatic monomers, where the sum of A and B adds up to 100 parts by weight, and their preparation.

Description

The invention relates to thermoplastic molding compositions containing essential

• A) 4 to 96 parts by weight, based on the sum of components A and B, a SAN, ABS and / or ASA polymer and
• B) 4 to 96 parts by weight, based on the sum of A and B, of a modified polyphenylene ether, produced in the melt from
  • b₁) 50 to 99.95% by weight, based on B, of a polymer component which contains at least 20% by weight, based on b₁, polyphenylene ether and at most 80% by weight, based on b₁, of a vinyl aromatic polymer, and
  • b₂) 0.05 to 10% by weight, based on B,
    • b₂₁) an amide group-containing monomer with a polymerizable double bond,
    • b₂₂) of a lactam group-containing monomer with a polymerizable double bond and / or
    • b₂₃) an α, β- unsaturated dicarbonyl compound and
  • b₃) 0 to 40 wt .-%, based on B, further non-vinyl aromatic monomers, the sum of components A and B giving 100 parts by weight.

This invention further relates to the production of these molding compositions.

Thermoplastic molding compounds, the styrene polymers and polyphenylene ethers (PPE) are included, for. B. from US Pat. Nos. 33 83 435, 41 28 602 and 41 28 603 known. Such molding compositions are suitable for the production of Molded parts that have better heat resistance than such Moldings that do not contain polyphenylene ether.

It has been proposed in U.S. Patent 4,360,618 Styrene polymers which copolymerize 2 to 8% by weight of acrylonitrile included to use for the production of molded parts. It was found however, that even at higher acrylonitrile contents, which are over 8.5% by weight lie, an incompatibility with the polyphenylene ether occurs, so that Moldings with poor mechanical properties from such mixtures  be preserved. Molding compounds, the PPE and styrene-acrylonitrile copolymers with higher levels of acrylonitrile (SAN), which may be impact resistant have therefore not yet been modified.

In US Patent 43 87 189 copolymers of styrene and Acid, acid anhydride or acid chloride comonomers, optionally May contain acrylonitrile, implemented with PPE. The disadvantage is that insufficient mechanical stability of the moldings, especially if the copolymers contain acrylonitrile, which is believed to be in the minor Reactivity of the comonomers to the PPE is justified.

In EP's 156 990, 170 946 and EP-A-86 105 796.0 there are special Graft copolymers made from PPE and styrene-acrylonitrile copolymers with special monomer components with the help of special ones Coupling agents have been described. However, are unfavorable the not yet satisfactory mechanical properties of the resulting manufactured molded parts or the technically complex production of Molding compounds on the production of special copolymers and subsequent coupling reaction in organic solvents.

The flame retardant of thermoplastic materials is made from Vogel,
"Flame-proofing of plastics", Hüthig-Verlag, Heidelberg (1966), pages 94 to 102
Troitzsch, "Fire behavior of plastics", Hanser-Verlag, Munich (1982), pages 1 to 65
Hirschler, "Developments in Polymer Stabilization", Volume 5,
Editor G. Scott, Applied Science Publishers, London (1982), pages 107 to 151
known. When using relatively large amounts of halogen-containing flame retardants and with the simultaneous use of synergists, thermoplastics do not burn off after being flamed with a hot flame and extinguish on their own. This effect of self-extinguishing only occurs without the use of a synergist after the addition of a much larger amount Halogen-containing flame retardants. Molding compositions equipped in this way have disadvantages that the processor cannot usually tolerate. Characteristic are e.g. B. the discoloration of the molding compounds and the corrosion of processing machines.

Without the use of synergists, the amount of flame retardant must be increased become, which severely affects the equipment equipped with it Thermoplastics and due to a significant decrease in heat resistance leads to burning dripping. So these problems can only by reducing the amount of halogen-containing flame retardants be solved. However, the thermoplastics then often no longer reach the classification UL 94 V0 or UL 94 V1.  

In addition to the possibility mentioned above, thermoplastics to equip them with halogen-containing flame retardants Possibility of halogen-free flame protection. So are from the DE-OS 34 32 749, DE-OS 34 32 750 and the German patent application No. 35 26 549.3 self-extinguishing, halogen-free molding compounds based on PPE and styrene-acrylonitrile polymers are known. Are unfavorable however the still unsatisfactory mechanical properties of the Molding compounds and the molded parts made from them or the technical elaborate production of the molding compounds through the production of the special Copolymers and the subsequent coupling reaction in organic Solvents.

The present invention was therefore based on the object To provide polyphenylene ether thermoplastic molding compositions, the described Avoid disadvantages, are easy to manufacture and molded can be processed with good mechanical properties.

This object was achieved according to the invention by the ones defined at the outset thermoplastic molding compounds.

In addition, special designs of the molding compositions were in accordance with the Subclaims and a process for their production found.

The molding compositions are described in detail below.

It goes without saying that for self-extinguishing halogen-free thermoplastic molding compounds only those components come into question that in turn halogen free, d. H. are free of halogen except for traces.

A SAN, ABS and / or ASA polymer is used as component A.

The polymers can be used individually or as a polymer mixture, if appropriate mixed with conventional auxiliaries used in usual amounts. Mixtures of 40 to 60, in particular 45 to 55% by weight are preferred. of the SAN polymer and 40 to 60, in particular 45 to 55 wt .-%, each based on the mixture of the ABS and / or ASA polymer. Such Mixtures are made by known methods, e.g. B. by coextrusion, manufactured and are commercially available.

For the purposes of this invention, a SAN polymer is a styrene-acrylonitrile copolymer Roger that.  

This copolymer consists of at least 50% by weight, based on the copolymer, of a vinyl aromatic monomer having 8 to 12 carbon atoms, such as α -methylstyrene, para-methylstyrene or, in particular, styrene itself and an nitrile group-containing, ethylenically unsaturated monomer containing 3 to 6 carbon atoms, especially acrylonitrile or methacrylonitrile. It preferably contains 15 to 40, in particular 20 to 38% by weight, based on the copolymer, of the copolymerized nitrile monomers. It can also up to 20 wt.%, Based on the copolymer, monomers such as methacrylic acid, z. B. methyl methacrylate or ethyl methacrylate, butyl acrylate or 2 ethylhexyl acrylate and methacrylamides or mixtures of these compounds in copolymerized form.

These SAN copolymers are known per se and are commercially available. They become continuous in the usual way in solution, emulsion or mass or produced discontinuously. The average molecular weights (Weight average _w ), determined by gel permeation chromatography generally between 10,000 and 1 million.

An ABS or ASA polymer in the sense of this invention is a Graft copolymer from a butadiene or acrylate rubber as Graft base and a SAN copolymer understood as a graft shell.

These impact-modified SAN copolymers are known per se, for. B. from Ullmann's "Encyclopedia of Technical Chemistry", 4th edition, Vol. 19, 1980, pp. 277 to 295 and commercially available.

The grafted butadiene rubber known per se adjusts Graft copolymer from a butadiene polymer as an elastomer Graft base that has a glass temperature of below 0 ° C (according to K. H. Illers and H. Breuer, Kolloid Zeitschrift 176 (1961) 110), and one Graft cover.

Examples of suitable rubber are: polybutadiene (cf. DE-OS 14 20 775 and DE-OS 14 95 089), as well as copolymers predominantly butadiene and styrene with comonomers such as isoprene, acrylonitrile or vinyl methyl ether.

As a graft base comes from the European itself Patent application No. 8 61 05 520.0 known acrylic ester polymer in question, whose glass temperature is below 0 ° C, preferably below -30 ° C. These  Mainly, polymers can be built up from alkyl acrylates with 1 to 8 carbon atoms in the alkyl radical such as n-butyl acrylate or 2-ethylhexyl acrylate, in addition also from up to 50, in particular 10 to 20% by weight, based on the polymer, further copolymerizable monomers such as Butadiene, isoprene, styrene, acrylonitrile or vinyl methyl ether or Mixtures of these. These acrylic ester polymers are preferably crosslinked. In in this case they contain 0.1 to 5, preferably 1 to 4% by weight, based on the polymer, a multifunctional monomer such as divinylbenzene or Di-hydro-di-cyclopentadienyl acrylate.

The graft copolymer is generally composed of 20 to 70 preferably 40 to 70, in particular 55 to 65% by weight of the graft base and 30 to 80, preferably 30 to 60, in particular 35 to 45% by weight in each case based on the graft copolymer, the graft shell. This contains in turn, about 60 to 80% by weight of a vinyl aromatic monomer such as Styrene and about 20 to 40% by weight, in each case based on the graft shell, of another ethylenically unsaturated monomer such as acrylonitrile polymerized in, the acrylonitrile also by half Methyl methacrylate can be replaced.

Both the rubbers and the graft copolymers are Usually made in emulsion or solution, the grafting can also be done in a known manner in several stages. Arise Graft copolymers in which the graft shell in which the expert known limits is grafted onto the elastomeric base.

The particle sizes of the graft copolymers can meet the requirements be determined and adjusted according to known methods, e.g. B. in emulsion polymerization using a seed latex or through a subsequent agglomeration step. Usually the middle one Particle size (d₅₀ value of the integral mass distribution, determined according to the method described in DE-AS 24 27 960 between 0.1 and 1 µm) Graft copolymers prepared in a known manner in emulsion were, or between 0.5 and 10 microns for products that are known Were prepared in solution.

Component A is used in amounts of 4 to 96, preferably 10 to 90 parts by weight, based on 100 parts by weight of the sum of Components A and B used. In halogen-free, self-extinguishing Molding compositions have proven to be particularly favorable, 10 to 70 parts by weight based on 100 parts by weight of the sum of A and B. use.  

4 to 96 parts by weight, preferably 10 to 90 parts by weight, based on 100 parts by weight of the sum of components A and B, at least one modified polyphenylene ether, which from the Components b₁ and b₂ is used. In halogen-free, self-extinguishing molding compounds have proven to be particularly favorable proven 30 to 90 parts by weight based on 100 parts by weight of Sum A and B to use. Under "modified" one should by Implementation in the melt of components b₁, b₂ and optionally b₃ caused change in the polyphenylene ether can be understood.

Component b 1 is a polymer component which at least 20, preferably more than 50, in particular more than 60% by weight, based on b₁, polyphenylene ether and at most 80, preferably less than 50, in particular less than 40% by weight, based on b 1, of a vinyl aromatic Contains polymers. For halogen-free, phosphorus-containing It is particularly advantageous for molding compositions to contain more than 90% by weight of PPE and less than 10 wt .-%, each based on b₁, of the vinyl aromatic To use polymers.

Polyphenylene ether is known per se, for example by oxidative coupling made from phenols disubstituted in the o-position will. Such polyphenylene ethers are preferably used, which with compatible with vinyl aromatic polymers, i.e. H. wholly or largely in these polymers are soluble (cf. A. Noshay, Block Copolymers, pp. 8 to 10, Academic Press, 1977 and O. Olabisi, Polymer-Polymer Miscibility, 1979, pp. 117 to 189).

The polyphenylene ethers used generally have a relative Viscosity from 0.3 to 0.8 dl / g, measured in 1% by weight solution in Chloroform at 25 ° C.

For example, some polyphenylene ethers, such as those mentioned in O. Olabisi, lc, pp. 224 to 230 and 245, are listed here
Poly (2,6-diethyl-1,4-phenylene) oxide,
Poly (2-methyl-6-ethyl-1,4-phenylene) oxide,
Poly (2-methyl-6-propyl-1,4-phenylene) oxide,
Poly (2,6-dipropyl-1,4-phenylene) oxide,
Poly (2-ethyl-6-propyl-1,4-phenylene) oxide, preferred
Poly (2,6-dimethyl-1,4-phenylene) oxide or
Copolymers, such as those containing 2,3,6-trimethylphenol, also polymer blends. However, poly (2,6-dimethyl-1,4-phenylene) oxide is particularly preferred.

The vinyl aromatic polymer is preferably used with the Compatible with polyphenylene ether. The molecular weight of these polymers is generally in the range of 1500 to 2,000,000, preferably in the range from 70,000 to 1,000,000.

Examples of preferred vinyl aromatic polymers compatible with polyphenylene ethers can be found in the already mentioned monograph by Olabisi, pp. 224 to 230 and 245. Vinyl aromatic polymers made from styrene, α -methylstyrene or p-methylstyrene, p-methylstyrene may only be mentioned here as examples; minor amounts (preferably not more than 20, in particular not more than 8% by weight, based on the polymers) may also involve comonomers such as (meth) acrylonitrile or (meth) acrylic esters in the structure. A particularly preferred vinyl aromatic polymer is polystyrene. It is understood that mixtures of these polymers can also be used.

Methods of making such vinyl aromatic polymers are per se known and described in the literature, so that here more details spare. Only here are examples as suitable Polymerization processes the bulk, suspension, emulsion or Solution polymerization mentioned.

The proportion of component b₁ in component B is in the range of 50 to 99.95, preferably 72 to 99.9 and in particular 95 to 99% by weight, based on B.

As an essential component b₂ contains the modified Polyphenylene ether B) at least one of the compounds b₂₁ to b₂₃. In principle, mixtures of different compounds can be b₂₁ to b₂₃ are used, but in general the use is only one of them Connection types advantageous.

The proportion of component b₂ is 0.05 to 10, preferably 0.1 to 8, in particular 1 to 5% by weight, based on component B.  

As component b₂ are amide group-containing monomers with at least a polymerizable double bond (b₂₁) suitable, preferably those of the general formulas I or II

where R¹, R², R³, R⁴, R⁵ and R⁶ are hydrogen, alkyl or cycloalkyl groups with up to 12 carbon atoms or aryl groups and Z alkylene groups with 1 to 12 C atoms and R¹ and R⁴ additionally alkoxy groups with 1 to 12 C atoms represent and n has the value 0 or 1, preferably 0.

Preferred substituents R¹, R², R³, R⁴, R⁵ and R⁶ are hydrogen, Alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with up to 8 carbon atoms or aryl groups, for example phenyl. R¹ and R⁴ are especially H or methyl.

Examples include acrylamide, N-methyl, N-ethyl, N-propyl, N-butyl, N-pentyl, N-hexyl, N-heptyl, N-octyl, N-nonyl, N- (2-ethylhexyl) - acrylamide, N-cyclohexylarylamide, N-phenylacrylamide, the corresponding N, N derivatives such as N, N-dimethylacrylamide and the corresponding Called methacrylamides and their mixtures. Acrylamide is preferred, Methacrylamide, N-phenylacrylamide and N-phenylmethacrylamide are used.

As component b₂) can also contain at least one lactam group Monomer with at least one polymerizable double bond (b₂₂) are used. Lactams are generally preferred Structure III

used, where X is a linear branched alkylene group with 2 to 15 carbon atoms and Y is the general formula

Has,
where R⁷ is a hydrogen atom, an alkyl or alkoxy group having 1 to 4 carbon atoms and R⁸ is a direct bond or a divalent substituent

where m is an integer from 1 to 4.

Preferred substituents Y are very generally vinyl, acryloyl, methacryloyl or residues with styrene basic structures, especially the Acryloyl and methacryloyl residue.

Lactam units which are polymerizable or copolymerizable to polyamides are preferred, as described in Houben-Weyl, Methods of Organ. Chemie, Volume XI / 2, pp. 511 to 587, (1958) and Volume XIV / 2, pp. 111 to 131, (1963). Examples include β- propiolactams such as 3,3'-dimethyl-3-propiolactam. Also preferred lactam units are pyrrolidone and ε- caprolactam, also 7-enantholactam, 8-capryllactam and 12-laurolactam, as described in K. Dachs, Angewandte Chemie, 74, 540 to 545, (1962). Mixtures of these compounds can also be used.

As a particularly preferred example of a component b₂₂ here only N- (meth) acryloyl- ε -caprolactam

called,
where R¹⁵ can be a hydrogen atom or a methyl group.

Component b₂₃ is α, β- unsaturated dicarbonyl compounds, preferably those of the general formula IV

in which

R⁹und R¹² hydroxyl groups, aroxy, alkoxy, aralkoxy or Cycloalkoxy groups with up to 12 carbon atoms, -NR¹³R¹⁴ or together -0- or -NR¹³- R¹⁰ and R¹¹ are hydrogen or, when R¹⁰ or R¹¹ is hydrogen, one Alkyl group with up to 12 carbon atoms, one aryl group, together one Alkylene group with 4 carbon atoms or with halogen-containing molding compounds also chlorine. R¹³ and R¹⁴ are hydrogen, alkyl, aralkyl, cycloalkyl or aryl groups with up to 12 carbon atoms, which in turn are represented by C₁-C₄ alkyl or alkoxy groups can be substituted.

The substituents must, of course, be such that they do not prevent the modification reaction. It is therefore generally α, β- unsaturated dicarboxylic acids, their anhydrides, imides, monoesters or monoamides of these dicarboxylic acids.

Examples of dicarboxylic acids are maleic acid, fumaric acid, Methyl maleic acid, butenyl succinic acid and tetrahydrophthalic acid and at halogen-containing molding compositions also called chloromaleic acid, of which Maleic acid and fumaric acid are particularly preferred.  

Examples of anhydrides are maleic anhydride, Methyl maleic anhydride and also in the case of halogen-containing molding compositions Chloromaleic anhydride.

Preferred imides are derived from maleic acid. The substituents R¹⁰, R¹¹ and R¹³ are alkyl groups with 1 to 4 carbon atoms, for example methyl, ethyl or n-, i- or t-butyl, or Phenyl groups which may be alkyl or alkoxy substituted can. As maleimides, N-methylmaleinimide is only an example, N-butyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N- (p-methylphenyl) maleimide, N- (3,5-dimethylphenyl) maleimide, N- (p-methoxyphenyl) maleimide, N-benzyl maleimide, N- (1-naphthyl) maleimide or mixtures thereof called. Of these will N-phenylmaleimide is particularly preferred.

Preferred half esters and half amides are derived from maleic acid.

The half esters are preferably derived from primary and secondary Monoalcohols, such as methanol, ethanol, n- and i-propanol, n- and i-butanol, Pentanols, hexanols, heptanols, octanols, e.g. B. 2-ethylene hexyl alcohol and higher alcohols such as dodecanols and cycloaliphatic alcohols, e.g. B. Cyclohexanol. Alcohols with aromatic are also suitable Structural units such as B. benzyl alcohol. However, alkanols are preferred with 1 to 6 carbon atoms. As amines for the preparation of the invention Half-amides used are generally secondary amines and Called N-alkylanilines. Examples of this are N-methyl or N-ethylalkylamines or N-methylaniline. In general, half-esters become the Half amids preferred.

Molding compositions which as component b₂₃) a half ester or a half amide Maleic acid often have particularly good flow properties, d. H. particularly high melt index values (MFI).

If necessary, in the manufacture of the modified Polyphenylene ether B also other non-vinyl aromatic comonomers b₃ are used, which under the manufacturing conditions with the Component b₁ react or graft on them. For example here called acrylic acid, methacrylic acid, acrylates and methacrylates, just to to list some. The proportion of these comonomers is generally 0 up to 40 and preferably not more than 20% by weight, based on B. Particularly however, molding compositions which do not contain any of these comonomers are preferred contain.  

In the production of the modified polyphenylene ether B up to 20 wt .-%, based on B, are used on radical starters.

The proportion of radical starters is usually less than the sum of used monomeric compounds b₂. In general it is an organic peroxide or an azo compound. Used can be organic peroxides with a half-life in the range of 0.1 to 3000 seconds at 200 ° C. The choice of radical starter is based after the desired reaction temperature. For example, as Radical initiators called tert-butyl peroxide and dicumyl peroxide.

Often, especially at temperatures above 265 ° C, it has proven to be proven to be advantageous without specifying radical initiators, d. H. in absence or practical absence of radical starters. this applies especially when fumaric acid is used as component b₂, because here may be undesirable when using radical starters Side reactions can occur.

To produce the modified polyphenylene ether B, the ones used Components in the melt, generally at 250 to 350 ° C, preferably 265 to 295 ° C, reacted with each other. Are suitable for this especially extruders, since they are generally also good ones Mixing of the components is achieved. The dwell times are in generally in the range of 0.5 to 30 minutes, preferably 1 to 5 minutes. Are particularly suitable for the process according to the invention Twin-screw extruder.

A particularly preferred method variant is described below.

The components are preferably metered in together and in one Melting part melted. The extruder screw in the melting part preferably contains kneading elements. The adjoins the melting zone Reaction zone, which preferably kneading elements and additional kneading elements with downstream downstream thread. Before the Product discharge is preferably a degassing zone for removal of volatile components. The melt discharged is generally granulated and the granules for the preparation of the invention Molding compounds used.

In principle, the production of the modified polyphenylene ether is also in each reaction vessel, which is a reaction of the components with each other enables, feasible.  

Sometimes it is advantageous if the molding compositions according to the invention additionally as component C an unmodified polyphenylene ether contain. This preferably corresponds to that used in component b₁ Polyphenylene ether, which is why here to the statements there suitable connections. The proportion of component C if available, is a maximum of 9 times, preferably less than 5 times, in particular less than 1.0 times the amount by weight, in which component B is used in the molding composition according to the invention.

However, it must be noted that the proportion of component A in the Molding compound does not become too small. The total weight of B and C should therefore 24 times, preferably 9 times the amount by weight of component A in the Do not exceed molding compounds.

The molding compositions according to the invention can, if appropriate, be a further constituent D. in an amount up to 4 times, preferably up to 1.0 times, in particular up to 0.5 times the amount by weight of the sum of Components B and, if present, C, vinyl aromatic polymers contain. In the case of halogen-free, self-extinguishing molding compounds, it has proven to be beneficial, lower amounts of D, namely less than that 0.3 times the amount by weight of the sum of components B and, if available, C, to use.

Vinyl aromatic compounds compatible with polyphenylene ethers are preferred Polymers as already described in component b 1. For closer Details should therefore be made to the comments on component b₁.

The vinyl aromatic polymers can also be impact modified. Such polymers are known to those skilled in the art as impact-resistant polystyrene (HIPS) known. The vinyl aromatic polymers are in the presence of a rubber-like polymers. As rubbery polymers are for example called polybutadiene and polyisoprene rubber.

The usually impact modified for the production Processes used for styrene polymers are bulk polymerization or solution, such as in US Pat. No. 2,694,692 described. The impact modified styrene polymers (HIPS) have generally a melt index (MFI (200 ° C / 5 kg) measured according to DIN 53 735) from 2 to 30, in particular from 2.5 to 20 g / 10 min.

In addition to those that may be present in components A and D, grafted rubbers, such as polybutadiene, acrylate, styrene butadiene, Polybutene rubber, hydrogenated styrene butadiene, acrylonitrile butadiene,  Ethylene propylene, polyisoprene rubber can also be ungrafted as Component E can be added. Rubber E should also be mentioned styrene-grafted ethylene-propylene rubbers, thermoplastic ethylene Propylene rubbers, thermoplastic polyester elastomers, ethylene rubbers and ionomers, including styrene-butadiene block copolymers AB, ABA, ABA smeared (taper), ABAB, ABAB smeared block Copolymers, star-block copolymers and similar, analog isoprene block polymers and in particular (partially) hydrogenated block copolymers. The Component E can be present in amounts of up to 40, preferably 1 to 20,% by weight be present on the molding compositions in the molding compositions according to the invention.

The molding compositions according to the invention can be used for flame-proofing if they are halogen-free, 1 to 40, in particular 5 to 20 wt .-%, based on the Molding compound containing a compound F containing phosphorus.

These are organic and inorganic containing phosphorus Compounds in which the phosphorus has a valence level of -3 to +5. The value level is understood to mean the term “oxidation level” as described in the textbook on inorganic chemistry by A.F. Hollemann and E. Wiberg, Walter de Gruyter and Co. (1964, 57th to 70th edition), pages 166 to 177. Phosphorus compounds valence levels -3 to +5 are derived from phosphine (-3), diphosphine (-2), phosphine oxide (-1), elemental phosphorus (± 0), hypophosphorous acid (+1), phosphorous acid (+3), hypodiphosphoric acid (+4) and phosphoric acid (+5) from.

Only a few of the large number of compounds containing phosphorus Examples mentioned.

Examples of phosphorus compounds of the phosphine class that represent the valence level -3 are aromatic phosphines, such as triphenylphosphine, Tritolylphosphine, trinonylphosphine, trinaphthylphosphine and the like. a .. special triphenylphosphine is suitable.

Examples of phosphorus compounds of the diphosphine class representing the valence level -2, are tetraphenyldiphosphine, tetranaphthyldiphosphine u. a. Tetranaphthyldiphosphine is particularly suitable.

Phosphorus compounds of valence level -1 are derived from phosphine oxide from. Examples are triphenylphosphine oxide, tritolylphosphine oxide. Trinonylphosphine oxide, Trinaphthylphosphine oxide. Triphenylphosphine oxide is preferred.  

Grade 0 phosphorus is the elemental phosphorus. In question come red and black phosphorus. Red phosphorus is preferred.

Phosphorus compounds of the "oxidation level" +1 are e.g. B. Hypophosphites. they can have a salt character or be purely organic in nature. Examples are calcium hypophosphite and magnesium hypophosphite, also double hypophosphites or complex hypophosphites, or organic hypophosphites, such as cellulose hypophosphite esters or esters of hypophosphorous acids Diols such as B. of 1,10-dodecyldiol. Also substituted phosphinic acids and their anhydrides, such as. B. diphenylphosphinic acid can be used will. Melamine hypophosphite is also suitable. Furthermore come in Question diphenylphosphinic acid, di-p-tolylphosphinic acid, di-cresylphosphinic anhydride. But there are also compounds such as hydroquinone, ethylene glycol, Propylene glycol bis (diphenylphosphinic acid) ester u. a. in question. Aryl (alkyl) phosphinamides, such as, for. B. Diphenylphosphinic dimethylamide and sulfonamidoaryl (alkyl) phosphinic acid derivatives, such as B. p-tolylsulfonamidodiphenylphosphinic acid. Prefers Hydroquinone and ethylene glycol bis (diphenylphosphinic acid) are used ester.

Phosphorus compounds with oxidation level +3 are derived from the phosphorous Acid. Cyclic phosphonates which differ from Derive pentaerythritol, neopentyl glycol or pyrocatechol. Furthermore is Phosphorus of grade +3 in triaryl (alkyl) phosphites, such as. B. Triphenyl phosphite, tris (4-decylphenyl) phosphite, tris (2,4-di-tert.- butylphenyl) phosphite or Phenyldidecylphosphit u. a. contain. Coming but also diphosphites, such as. B. propylene glycol-1,2-bis (diphosphite) or cyclic phosphites derived from pentaerythritol, neopentyl glycol or Derive catechol, in question.

Methylneopentylphosphonate (methanephosphonic acid methyl ester) is particularly preferred and phosphite and dimethylpentaerythritol diphosphonate and phosphite.

Above all come as phosphorus compounds of oxidation level +4 Hypodiphosphates, such as. B. tetraphenyl hypodiphosphate or bisneopentyl hypodiphosphate into consideration.

The phosphorus compounds with oxidation level +5 are mainly alkyl and aryl substituted phosphates. Examples are phenyl bisdodecyl phosphate, Phenylethyl hydrogen phosphate, phenyl bis (3,5,5-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyldi (tolyl) phosphate, di phenyl hydrogen phosphate, bis (2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate,  Bis (2-ethylhexyl) phenyl phosphate, di (nonyl) phenyl phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) p-tolyl phosphate, p-tolyl-bis (2,5,5- trimethylhexyl) phosphate or 2-ethylhexyl diphenyl phosphate. Especially phosphorus compounds in which each radical is an aryloxy radical are suitable is. Triphenyl phosphate is very particularly suitable.

Cyclic phosphates can also be used. Especially Diphenylpentaerythritol diphosphate and phenylneopentyl phosphate are suitable.

In addition to the low molecular weight phosphorus compounds listed above still oligomeric and polymeric phosphorus compounds in question.

Such polymeric, halogen-free organic phosphorus compounds with Phosphorus in the polymer chain is created during manufacture, for example of pentacyclic unsaturated phosphine dihalides such as is described for example in DE-OS 20 36 173. The Molecular weight, measured by vapor pressure osmometry in dimethylformamide, the polyphospholine oxides should be in the range from 500 to 7000, preferably in Range from 700 to 2000.

The phosphorus has the oxidation state -1.

Furthermore, inorganic coordination polymers of aryl (alkyl) phosphinic acids such as B. Poly [sodium (I) methylphenylphosphinate] can be used. Their manufacture is specified in DE-OS 31 40 520. The phosphor has the oxidation number +1.

Such halogen-free polymeric phosphorus compounds can also be used the reaction of a phosphonic acid chloride, such as. B. phenyl, methyl, Propyl, styryl and vinylphosphonic dichloride with bifunctional Phenols such as e.g. B. hydroquinone, resorcinol, 2,3,5-trimethylhydroquinone, Bisphenol-A or Tetramethylbisphenol-A arise.

Other halogen-free polymeric phosphorus compounds that are in the Molding compositions according to the invention can be contained by reaction of phosphorus oxide trichloride or phosphoric acid ester dichlorides with one Mixture of mono-, bi- and trifunctional phenols and others Compounds bearing hydroxyl groups prepared (cf. Houben-Weyl-Müller, Thieme-Verlag Stuttgart, Organic Phosphorus Compounds Part II (1963)). Polymeric phosphonates can also be used by transesterification reactions of phosphonic esters with bifunctional Phenols (cf. DE-OS 29 25 208) or by reactions of Phosphonic acid esters with diamines or diamides or hydrazides (cf.  US-PS 44 03 075) are produced. But that is also an option inorganic poly (ammonium phosphate).

However, oligomeric pentaerythritol phosphites, phosphates and -phosphonates according to EP-PS 8 486, e.g. B. Mobil Antiblaze®19 (registered Trademark of the company Mobil Oil) can be used.

Triphenylphosphine oxide is very particularly preferably used, Triphenyl phosphate, dimethylpentaerythritol diphosphonate, Hydroquinone bis (diphenylphosphinic acid) ester and methyl neopentyl phosphate (Methanephosphoric acid neopentyl ester) and Mobil Antiblaze 19.

In addition, the thermoplastic molding compositions according to the invention Contain usual additives and processing aids. The amount these additives are generally not more than 40, in particular not more than 20% by weight, based on the molding compound.

The usual additives are heat and light stabilizers, sliding and Mold release agents, colorants, such as dyes and pigments in conventional Called quantities. Other additives are reinforcing agents such as Glass fibers, carbon fibers, aromatic polyamide fibers and / or Fillers, gypsum fibers, synthetic calcium silicates, kaolin, calcined Kaolin, wollastonite, talc, chalk, also flame retardants halogen-containing molding compositions such. B. brominated or chlorinated organic Compounds, optionally in a mixture with antimony compounds.

The thermoplastic molding compositions according to the invention are produced expediently by mixing the components at temperatures in the Range from 200 to 320 ° C, preferably 250 to 300 ° C in usual Mixing devices, such as. B. kneaders, Banbury mixers and Single screw extruders, preferably in a twin screw extruder. Around Obtaining a molding compound that is as homogeneous as possible is an intensive process Mixing necessary, which can be achieved in a known manner. The Residence times are generally in the range from 0.5 to 30 minutes. preferably from 1 to 5 min. The order of mixing the components can be varied, two or optionally three components be premixed or all components can be mixed together will.

Individual components can be used together in the production of the molding compositions react so that no pure mixtures of the components in the end product there is more.  

This is particularly sought, for. B. mixing at increased Temperature above 250 ° C if a particularly good connection of components among themselves is required.

Under a self-extinguishing molding compound in the sense of this invention understood such a molding compound, which is described in the following Fire classes UL 94 V0, V1 or 5V can be classified.

The molding compositions according to the invention can be injection molded or Manufacture extrusion molded articles with advantageous properties.

The thermoplastic molding compositions according to the invention are particularly suitable easy, e.g. B. with finished, commercially available ABS and Produce ASA polymers.

They are characterized by good processability and Heat resistance. Other advantages are the good ones mechanical properties of the molding compound and of the products produced from it Molded bodies, also in their surface gloss.

The tests mentioned in the examples and comparative tests were carried out as carried out as follows:

• 1. The flame protection test is carried out in the vertical fire test according to Underwriter Laboratories Regulations for Classification fire classes UL 94 V0, V1, V2 or 5V.
• The classification of a flame retardant thermoplastic in the Fire class UL 94 V0 occurs if the following criteria are met: With a set of 5 samples measuring 127 × 12.7 × 3.16 mm all samples after two flames of 10 s with a Do not burn an open flame (height 19 mm) for longer than 10 s. The The sum of the afterburning times for 10 flame treatments of 5 samples is not allowed be greater than 50 s. There must be no burning dripping, complete Burn off or afterglow for longer than 30 s. The Classification in fire class UL 94 V1 requires that the Afterburn times are not longer than 30 s and that the sum of the Afterburning times of 10 flame treatments of 5 samples not greater than Is 250 s. The afterglow must never last longer than 60 s. The remaining  Criteria are identical to those mentioned above. A classification in The fire class UL 94 V2 occurs when it fulfills the other criteria for classification UL 94 V1 for burning droplets is coming.
• The fire protection class UL 94 5V is classified if the following criteria are met:
  The afterburning or afterglow time of the samples must not exceed 60 s after the last flame treatment. Each sample is flamed five times with a flame of 127 mm height and an inner blue cone of 38 mm height for 5 s.
  There is an interval of 5 s between two successive flame treatments.
  There must be no burning or non-burning droplets or complete burning.
• 2. The (notch) impact strengths were measured in accordance with DIN 53 453.

Examples 1 to 15 and Comparative Experiments 1 * to 10 * Production of modified polyphenylene ethers B

B (1) 92.5 kg of poly (2,6-dimethyl) -1,4-phenylene ether (PPE) with one relative viscosity of 0.61 (measured in 1% by weight solution in CHCl₃ at 25 ° C), 5 kg of polystyrene (PS 144 C, melt flow index MFI at 200 ° C / 5 kg load (measured according to DIN 53 735) = 24 g / 10 min) and 2.5 kg of maleic acid monoethyl ester were in a twin-screw extruder (ZSK 53; Werner & Pfleiderer) dosed, in a first part below Using Kent elements melted at 280 ° C, in one second part with kneading and using kneading elements 280 ° C implemented and then in a degassing zone Degassed 280 ° C by applying vacuum. The mean dwell time in the extruder was 3 min. The emerging melt was through passed a water bath, granulated and dried. B (2) 98 kg PPE, 5 kg polystyrene (both as for B (1)) and 2 kg Fumaric acid was reacted as in the preparation of B (1). B (1V) For comparison, a graft polymer according to EP-170 946 was selected PPE and a styrene acrylonitrile polymer.  100 g of the PPE used in B (1) was mixed with dimethyldichlorosilane in toluene using tributylamine as an acid scavenger implemented. The reaction product then became 100 g a styrene acrylonitrile polymer (consisting of 62% by weight Styrene, 35% by weight acrylonitrile and 3% by weight hydroxybutyl acrylate, with a weight average molecular weight of 65,000 by continuous polymerization) using Tributylamine metered in as an acid scavenger. It became as usual worked up. B (2V) As B (2V) a graft copolymer made of PPE and a Styrene copolymer prepared according to DE-OS 34 32 749. 100 g of the PPE used in B (1) was mixed with dimethyldichlorosilane in toluene using tributylamine as an acid scavenger implemented. The reaction product then became 100 g a styrene copolymer (consisting of 72% by weight styrene, 25% Acrylonitrile and 3 wt.% Hydroxibutylacrylat, with a _w  = 60,000, produced by continuous polymerization) Toluene using tributylamine as an acid scavenger in Run for 20 minutes. The graft polymer (copolymers from Main and side chains) was removed by removing the solvent receive. B (3V) As B (3V) a graft copolymer made of PPE and a Styrene copolymer according to the German patent application P 35 26 549.3.
By continuous copolymerization of 60% by weight styrene, 35% by weight acrylonitrile, 3% by weight chloromethylstyrene and 2% by weight p-Chloromethylstyrene was added with the addition of 60 parts by weight Ethylbenzene, based on 100 parts by weight of monomers, at 140 ° C and 9 bar with 6 h residence time a copolymer with statistical Distribution of the monomers and with _w  = 39,000 produced. The Copolymer was degassed via an extruder and as granules won. 50 g of the dried copolymer was 1000 g Toluene and then 50 g of PPE (according to B (1)) and heated to 90 ° C. After cooling to 30 ° C, 50 g was added immediately a 50% by weight aqueous sodium hydroxide solution with vigorous stirring. After 5 minutes, 5 g of tetrabutylammonium hydrogen sulfate were added. It was stirred for 4 h at room temperature and warmed to 60 ° C. in 1 h, the reaction was held at 60 ° C for 1 h and then 500 g of toluene added. It was worked up as usual.

The following products were used as components A, C, D, E and F:  

Component A

A (1) 50 kg of a SAN copolymer of 65% by weight styrene and 35% by weight Acrylonitrile with a weight average molecular weight of 90,000 g / mol were mixed with 50 kg of an emulsion graft copolymer with an average particle diameter of 0.5 µm (d₅₀ value of the integral mass distribution), built up from 60% by weight, based on the emulsion graft copolymer, one Polybutadiene with a freezing temperature below 0 ° C (Graft base) and 40% by weight, based on the emulsion graft copolymer a copolymer of 65% by weight Styrene and 35% by weight acrylonitrile as a graft shell, manufactured by 95 ° C with subsequent precipitation and drying, in the usual way mixed. A (2) 50 kg of a SAN copolymer of 65% by weight styrene and 35% by weight Acrylonitrile with a weight average molecular weight of 90,000 g / mol were mixed with 50 kg of an emulsion graft copolymer with an average particle diameter of 0.49 µm (d₅₀ value of the integral mass distribution), built up from 60% by weight, based on the emulsion graft copolymer, one cross-linked acrylate rubber (98% by weight N-butyl acrylate and 2% by weight di-hydro-di-cyclopentadienyl acrylate) as a graft base and 40% by weight, based on the emulsion graft copolymer, a copolymer of 65% by weight styrene and 35% by weight Acrylonitrile as a graft shell, mixed in the usual way.

Component C

Poly (2,6-dimethyl-1,4-phenylene) ether with a relative viscosity of 0.61 (measured in 1% by weight solution in CHCl₃ at 25 ° C).

Component D

High impact polystyrene (HIPS) containing 8% by weight butadiene and a melt index (200 ° C / 5.0 kg) of 15 g / 10 min (Buna®CB NX 529 C, (® = registered trademark of Bayer) made anionically).

Component E

E (1) styrene-butadiene-styrene triblock copolymer with a styrene content of 30% by weight (Cariflex®TR 1102) (® = registered trademark from Shell), weight average molecular weight _w  = 80,000  E (2) styrene-butadiene (hydrogenated) -styrene triblock copolymer with one Styrene content of 40% by weight (Kraton®G 1650 (® = registered Trademark of Shell)).

Component F

F (1) triphenylphosphine oxide F (2) triphenyl phosphate

Tables 1 and 2 below are examples and comparative tests of thermoplastic molding compositions listed. The molding compounds were through Melt and mix the specified components in the specified Amounts in a twin-screw extruder at 280 ° C and 3 minutes residence time and subsequent granulation.  

Table 1

Claims (10)

1. Thermoplastic molding compositions containing essentially

• A) 4 to 96 parts by weight, based on the sum of components A and B, of a SAN, ABS and / or ASA polymer and
• B) 4 to 96 parts by weight, based on the sum of components A and B, of a modified polyphenylene ether, produced in the melt from
  • b₁) 50 to 99.95% by weight, based on B, of a polymer component which contains at least 20% by weight, based on b₁ polyphenylene ether and at most 80% by weight, based on b₁, of a vinyl aromatic polymer, and
  • b₂) 0.05 to 10% by weight, based on B,
    • b₂₁) an amide group-containing monomer with a polymerizable double bond,
    • b₂₂) of a lactam group-containing monomer with a polymerizable double bond and / or
    • b₂₃) an α, β- unsaturated dicarbonyl compound, and
  • b₃) 0 to 40% by weight, based on B, of further non-vinyl aromatic monomers, the sum of components A and B giving 100 parts by weight.

2. Thermoplastic molding compositions according to claim 1, characterized in that one can modify b₁ in the absence or more practical Absence of radical starters in the melt. 3. Thermoplastic molding compositions according to claims 1 and 2, characterized characterized that they as component C up to 9 times the Amount by weight of B of an unmodified polyphenylene ether included, the sum of B and C not more than 24 times Weight amount of A may be. 4. Thermoplastic molding compositions according to claims 1 to 3, characterized characterized that they as component D up to 4 times the Weight amount of the sum of B and, if available, C, one of A. various vinyl aromatic polymers.   5. Thermoplastic molding compositions according to claims 1 to 4, characterized characterized in that they contain up to 40% by weight, based on the molding composition of an impact modified rubber E. 6. Self-extinguishing thermoplastic molding compositions according to claims 1 to 5, characterized in that they do not contain halogen and 1 to 40% by weight, based on the molding composition of a phosphorus-containing Compound F included. 7. Thermoplastic molding compositions according to claims 1 to 6, characterized in that component b₂₁ is a compound of general formula I or II where R¹, R², R³, R⁴, R⁵ and R⁶ are hydrogen, alkyl or cycloalkyl groups with up to 12 C atoms or aryl groups and Z alkylene groups with 1 to 12 C atoms and R¹ and R⁴ additionally alkoxy groups with 1 to 12 C atoms represent and n has the value 0 or 1. 8. Thermoplastic molding compositions according to claims 1 to 7, characterized in that component b₂₂ is a compound of general formula III where X represents a linear branched alkylene group with 2 to 15 carbon atoms and Y the general formula Has,
where R⁷ is hydrogen, an alkyl or alkoxy group having 1 to 4 carbon atoms and R⁸ is a direct bond or one of the following divalent radicals where m is an integer from 1 to 4. 9. Thermoplastic molding compositions according to claims 1 to 8, characterized in that component b₂₃ is a compound of general formula IV in which
R⁹ and R¹² hydroxyl groups, aroxy, alkoxy, aralkoxy or cycloalkoxy groups with up to 12 C atoms, -NR¹³R¹⁴ or together -0- or -NR¹³-, R¹⁰ and R¹¹hydrogen or, if R¹⁰ or R¹¹ is hydrogen, chlorine, an alkyl group with up to 12 C atoms, an aryl group or together an alkylene group with 4 C atoms, R¹³ and R¹⁴hydrogen, alkyl, cycloalkyl, aralkyl or aryl groups with up to 12 C atoms, which in turn are represented by C₁-C₄-alkyl - Or -alkoxy groups can be substituted. 10. Process for the production of thermoplastic molding compositions according to the Claims 1 to 9 by mixing the components at one temperature in the range of 200 to 320 ° C and a residence time between 0.5 and 30 minutes.