EP0000726A1 - Polyolefine masses containing alkaline-earth metal carbonates, and a process for their production - Google Patents

Abstract

In the case of polyolefins filled with alkaline earth carbonates, very good compatibility between the hydrophilic filler and the hydrophobic polymer matrix is achieved if certain organophosphorus compounds are used as adhesion promoters. Improved mechanical properties are obtained in the plastic articles produced from such polyolefin molding compositions.

Description

As is known, the mechanical, electrical and thermal properties of plastics can be improved by adding inorganic fillers. However, due to their hydrophilic properties, these fillers are only slightly compatible with the mostly hydrophobic polymers. In the case of polymers filled with inorganic substances, this leads to a deterioration in some mechanical properties.

It is known to treat natural calcium carbonates with surfactants in order to improve their distributability in plastics. These substances include medium and high molecular weight saturated and unsaturated fatty acids. e.g. Butyric acid, lauric acid, oleic acid, stearic acid (cf. DE-PS 958 830).

It is also known to use a calcium carbonate treated with stearic acid as an impact-resistant component in the production of impact-resistant, plasticizer-free form bodies based on polyvinyl chloride (cf. DE-AS 1 469 886).

It is also known to combine calcium carbonate with compounds which contain an ethylene bond in the molecule and free radical initiators (cf. DE-OS 1 794 310, DE-OS 20 61 180).

Finally, it is also known to react alkaline earth carbonates with at least one unsaturated carboxylic acid with stirring in the absence of liquid water in the powdery inorganic material. Substances that form free radicals can be present. (see DE-AS 22 62 126).

However, it has been shown that the improvements in mechanical properties achieved with the use of modified alkaline earth metal carbonates are not yet sufficient, particularly in the case of polyolefins.

It has now been found that very good compatibility is achieved between the hydrophilic filler and the hydrophobic polymer matrix, which leads to improved mechanical properties of plastic articles produced therefrom if certain organophosphorus compounds are used as adhesion promoters.

• 90 bis 20 Gewichtsteilen eines Polyolefins
• 10 bis 80 Gewichtsteilen eines Erdalkalicarbonats üblichen Zusatzstoffen sowie 0,1 bis 10 Gew.-%, bezogen auf' den Füllstoff, eines Haftvermittlers, dadurch gekennzeichnet, daß sie als Haftvermittler eine phosphororganische Verbindung der Formel
  
  worin R¹ einen Alkylrest mit 1 bis 18.Kohlenstoffatomen, einen Alkenylrest mit 2 bis 18 Kohlenstoffatomen, einen Aralkylrest mit 7 bis 13 Kohlenstoffatomen, dessen Alkylkette 1 bis 3 Kohlenstoffatome aufweist, oder einen Aralken^ylrest mit 8 bis 13 Kohlenstoffatomen, dessen Alkenylkette 2 oder 3 Kohlenstoffatome aufweist, und R² und R³ gleich oder verschieden sind und Wasserstoff, einen Alkylrest mit 1 bis 8 Kohlenstoffatomen, einen Arylrest mit 6 bis 10 Kohlenstoffatomen, einen Aralkylrest mit 7 bis 13 Kohlenstoffatomen, dessen Alkylkette 1 bis 3 Kohlenstoffatomen aufweist, oder einen Alkenylrest mit 3 bis 5 Kohlenstoffatomen bedeuten, enthält.

The invention relates to a filler-containing plastic molding composition consisting of

• 90 to 20 parts by weight of a polyolefin
• 10 to 80 parts by weight of an additive customary in alkaline earth metal carbonate and 0.1 to 10% by weight, based on the filler, of an adhesion promoter, characterized in that they act as an adhesion promoter, an organophosphorus compound of the formula
  
  wherein R ¹ is alkyl of 1 to 18.Kohlenstoffatomen, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, whose alkyl chain has from 1 to 3 carbon atoms, or an aralkene ^y lrest having 8 to 13 carbon atoms, whose alkenyl chain 2 or has 3 carbon atoms, and R ² and R ^{3 are} identical or different and are hydrogen, an alkyl radical with 1 to 8 carbon atoms, an aryl radical with 6 to 10 carbon atoms, an aralkyl radical with 7 to 13 carbon atoms, the alkyl chain of which has 1 to 3 carbon atoms, or represents an alkenyl radical having 3 to 5 carbon atoms.

The organophosphorus compounds of the formula (I) to be used according to the invention are phosphonic acids and their esters. In formula (I), R represents an aralkyl radical having 1 to 18, preferably 3 to 8, in particular 2 to 6 carbon atoms. The alkyl radical can be straight-chain or branched or ring-shaped. R ^{1 also} denotes an alkenyl radical having 2 to 18, preferably 2 to 12 carbon atoms, or an aralkyl radical having 7 to 13, preferably 7 to 10, in particular 7 to 9 carbon atoms, the alkyl chain of which has 1 to 3, preferably 1 or 2, carbon atoms, or an aralkenyl radical having 8 to 13, preferably 8 to 10, in particular 8 to 9 carbon atoms, the alkenyl chain of which has 2 or 3 carbon atoms. The aromatic radical is a carbocyclic nucleus with 6 or 10 ring carbon atoms, which optionally carries side chains. R ² and R ³ are the same or different and each represents hydrogen, an unbranched or branched or cyclic alkyl radical having 1 to 8, preferably 2 to 8 carbon atoms, an aryl radical having 6 to 10, preferably 6 to 8 carbon atoms, an aralkyl radical having 7 to 13, preferably 7 to 10 carbon atoms, the alkyl chain of which has 1 to 3, preferably 1 or 2 carbon atoms, or an alkenyl radical with 3 to 5, preferably 3 or 4 carbon atoms. Aromatic residues are preferably carbocyclic nuclei with 6 or to ring carbon atoms, which can optionally carry side chains.

The phosphonic acids and phosphonic acid esters to be used according to the invention can be prepared by known methods.

For example, the phosphonic acids can be prepared from their tetra- or dihalides by reaction with water, by saponification of the corresponding esters, by disproportionation of phosphonic acids or by addition of phosphorous acid to olefinic double bonds; the phosphonic acid esters by reacting the phosphonic acid tetra- or dihalides with alcohols or from esters of phosphorous acid with alkyl halides (Kosolapoff, Organophosphorus Compounds, Wiley and Sons, New York, 1950; Houben-Weyl, Vol. XII / 1, Thieme Verlag Stuttgart ).

Suitable phosphonic acids are, for example, methanephosphonic acid, ethanephosphonic acid, propanephosphonic acid, butanephosphonic acid, n-hexanephosphonic acid, cyclohexanephosphonic acid, 2,3-dimethylbutanephosphonic acid, octanephosphonic acid, decanephosphonic acid, dodecanephosphonic acid, octadecanephosphonic acid, phenylmethanephosphonic acid, 1-phenylphosphonic acid, 1-phthalophosphonic acid, 1-phthalylphosphonic acid, 1, 2-phenyl-vinylphosphonic acid-1, 2,4-dimethyl-4-methylpentane-phosphonic acid, dimethyl-2-methylpropane-phosphonic acid and 2,4-dimethyl-butane-phosphonic acid. Vinylphosphonic acid, propanephosphonic acid, hexanephosphonic acid, octanephosphonic acid, dodecanephosphonic acid, 2,4-dimethyl-4-methylpentanephosphonic acid, dimethyl-2-methylpropanephosphonic acid and 2,4-dimethylbutanephosphonic acid are preferably used.

Suitable phosphonic acid esters are, for example, Methanphosphonsäurediäthylester, ethanephosphonic acid diethyl ester, ethanephosphonic acid dibutyl, Butanphosphonsäure dibutyl, n-Hexanphosphonsäurediäthylester, n-hexanephosphonic diphenyl, Octanphosphonsäurediäthylester, dodecanephosphonic acid dimethyl ester, Octadecanphosphonsäure acid diethyl ester, vinylphosphonic acid, vinylphosphonic acid diethyl ester, vinyl phosphonic acid-di- (2 -ethyl-hexyl) -ester, vinylphosphonic acid dioctyl ester, vinylphosphonic acid diallyl ester, allylphosphonic acid diallyl ester, allylphosphonic acid dimethallyl ester, phenylmethane-phosphonic acid monoethyl ester, methanephosphonic acid ethylhexyl ester. Dibutyl butanephosphonate, diallyl vinylphosphonate, dimethyl vinylphosphonate and dioctyl vinylphosphonate are preferably used.

The phosphonic acids and phosphonic acid esters to be used according to the invention are added to the molding composition in an amount of 0.1-10% by weight, preferably 0.5-2% by weight, based on the filler. Mixtures of different phosphonic acids or phosphonic acid esters, or mixtures of phosphonic acid with phosphonic acid esters can also be used.

The filler can be a natural or synthetic, i.e. precipitated alkaline earth carbonate. Suitable carbonates are, for example, limestone powder, chalk, precipitated calcium carbonate, natural magnesite, natural hydromagnesite, synthetic basic magnesium carbonate, calcium magnesium carbonate, dolomite. Calcium carbonates are preferably used. The invention. alkaline earth carbonates to be used have an average particle diameter of 0.1 to 50 µm, preferably 1 to 10 µm. Mixtures of different alkaline earth carbonates can also be used.

The phosphonic acid or the phosphonic acid ester can be introduced into the molding composition in various ways.

So you can suspend the filler in an organic solvent, alcohols such as methanol, ethanol, butanol, hydrocarbons such as hexane, benzene, toluene, ethers such as diethyl ether, di-isopropyl ether or ketones such as acetone, diethyl ketone serve as the solvent. You can also add the coupling agent directly or dissolved in a suitable solvent, stir the mixture well at room temperature or elevated temperature, distill off the solvent and dry the residue. The filler can also be mixed with the coupling agent in a mixer at room temperature or at elevated temperature, the temperature possibly being above the melting point of the coupling agent.

If the adhesion promoter is liquid, it can be added directly to the filler or diluted with a suitable solvent in a high-speed mixer or sprayed onto the filler in the form of a mist in the form of a mist. In this way, solid adhesion promoters can also be applied to the filler dissolved in a suitable solvent.

Alternatively, the adhesion promoter can be mixed with the polymer in a mixer and then the untreated filler can be added, or all three components, namely the polymer, the filler and the adhesion promoter can be mixed at the same time. This simultaneous mixing can take place in a premixer, but also in the granulating extruder.

The filler is preferably first treated with the adhesion promoter.

Polymeren verwendet. Besonders bevorzugt wird Polyäthylen verwendet.Suitable base polymers for the plastic molding compositions according to the invention are 1-olefin homo- and copolymers, for example high-density and low-density polyethylene, polypropylene, 1-polybutene, 1-poly- (4-methyl) -phthaline, 1-olefin copolymers, such as ethylene Propylene copolymers and ethylene-butene copolymers, mixtures of these polymers and mixtures of these polymers with

Polymers used. Polyethylene is particularly preferably used.

vorzugsweise bis 30 Gew.-%.The polymer content of the molding compositions is 90 to 20,

preferably up to 30% by weight.

Zusatzstoffe enthalten. Als solche sind zu

Licht- und Wärmestabilisatoren, Antioxidantien,

udgl. sowie Farbpigmente, Flammsehutzmittel. Die erste Gruppe ist in den Formmassen im allgemeinen in einer Menge von 0,01 bis 5 Gewichtsprozent,

auf die Menge Polymer plus Füllstoff, enthalten. Farbpigmente und Flammschutzmittel werden in einer Menge entsprechend den Bedürfnissen eingesetzt.The molding compositions according to the invention can have the usual properties which facilitate processing and the physical properties

Contain additives. As such are too

Light and heat stabilizers, antioxidants,

etc. as well as color pigments, flame retardants. The first group is in the molding compositions generally in an amount of 0.01 to 5 percent by weight,

on the amount of polymer plus filler. Color pigments and flame retardants are used in an amount according to needs.

0,05 bis 4 Gew.-Teilen eines phenolischen Stabilisat

gegebenenfalls 0,01 bis 4 Gew.-Teilen eines

haltigen Costabilisators, sowie gegebenenfalls

3 Gew.-Teilen einer basischen oder neutralen

wie z.B. Calciumstearat oder Zinkstearat, sowie gebenenfalls 0,1 bis 4 ^Gew.-Teilen eines Phosphits und gebenenfalls 0,01 bis _{4 Gew}.-Teilen eines bekannten UV-

aus der Gruppe der Alkoxyhydroxybenzophenone, Hydroxyphenylbenzotriazole, Benzylidenmalonsäuremonotrilester oder der sog. Quencher (z.B. Nickelchelate).An effective Stabilisat combination of _poly-1-n olefination e, such as high, middle, and Niederdruckpolymerisate of _C2 - to C ₄ -1-olefins, especially polyethylene and polypropylene, or of polymers such 1-olefins, for example, consist, in each case based on 100 parts by weight of polymer,

0.05 to 4 parts by weight of a phenolic stabilizer

optionally 0.01 to 4 parts by weight of one

containing costabilizer, and optionally

3 parts by weight of a basic or neutral

such as calcium stearate or zinc stearate, and optionally 0.1 to 4 parts ^{by weight of} a phosphite and optionally 0.01 to ₄ parts _{by weight of} a known UV

from the Group of the alkoxyhydroxybenzophenones, hydroxyphenylbenzotriazoles, benzylidene malonic acid monotrilesters or the so-called quencher (for example nickel chelates).

If an olefinically unsaturated phosphonic acid or a corresponding ester is used as a modifying agent, a polymerization initiator, for example benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, tert-butyl peroctoate, azobisisobutyronitrile in an amount of 0.01 to 1 percent by weight, based on the amount of unsaturated phosphonic acid or phosphonic acid esters can be added.

Molded parts made from the thermoplastic molding composition according to the invention have very good impact strength and impact strength, which makes them particularly suitable for the production of technical articles.

Another advantage of the adhesion promoters to be used according to the invention is that they have a favorable influence on the flow behavior of the polymer melt during injection molding and, for example, facilitate the filling of the mold in the production of complicated injection molded parts.

The subject matter of the invention is illustrated by the examples below.

Example 1:

450 parts of calcium carbonate of the calcite type with an average particle diameter of 5 microns and a specific surface area according to the BET method (Brunauer, Emmet, Teller, J. Am. Chem. Soc. 60, 309) of 1 m ² / g are in 2,000 parts of acetone suspended. With good stirring, 50 parts of vinylphosphonic acid are added dropwise within 30 minutes. The suspension is stirred for 2 hours at room temperature, then the acetone is distilled off in vacuo. and the residue dried at 40 ° C in a vacuum drying cabinet.

450 parts of the calcium carbonate thus treated are mixed with 1050 parts of polyethylene (density 0.96 g / cm ³ , melt index 23 g / 10 min. Containing 0.42% by weight of a phenolic stabilizer and 2.5% by weight of a sulfur-containing costabilizer ) well mixed in a plow blade mixer. The mixture obtained is extruded into a strand in a twin-screw extruder, which is then granulated in a cutting machine. Test specimens are produced from the granules using an injection molding machine.

In a comparative example, 450 parts of untreated calcium carbonate are mixed with 1050 parts of polyethylene in the same way. The mixture is processed as described above.

The properties of the test specimens are listed in Table I. A 1/2 standard rod is used as a test specimen.

Elongation and tensile strength are determined according to DIN 53 455, impact strength according to DIN 53 453 (30 mm jaw spacing, transverse position) impact strength according to DIN 53 448, ball indentation hardness according to DIN 52 456 and the modulus of elasticity according to DIN 53 457.

Examples 2-14:

The same calcium carbonate as in Example 1 is treated with different phosphonic acids or phosphonic acid esters in different concentrations, based on the amounts of calcium carbonate. 300 parts of the calcium carbonate thus treated are mixed with 700 parts of the same polyethylene and the mixture is processed as described in Example 1. The properties of the test specimens are listed in Table II.

Example 15:

500 parts of calcium carbonate of the calcite type with an average particle diameter of 5 _/ um and a specific surface area (BET) of 1 m ² / g and 7.5 parts of octanephosphonic acid are mixed in a high-speed mixer at 800 rpm. mixed at 80 ° C for 30 minutes.

450 parts of the calcium carbonate treated in this way are mixed well with 1,050 parts of polyethylene (density 0.96 g / cm ³ , melt index 23 g / 10 min) in a plow blade mixer. The mixture is further processed as described in Example 1. The properties of the test specimens are listed in Table III.

Example 16:

Example 15 is repeated, except that 3 parts of dodecanephosphonic acid are used instead of octanephosphonic acid to modify the calcium carbonate. The properties of the test specimens are listed in Table III.

Example 17:

A solution of 5 parts of octadecanephosphonic acid in 50 parts of acetone is added in 30 minutes in a high-speed mixer from an atomizer to 500 parts of calcium carbonate of calcite type with an average particle diameter of 5 _μm and a specific surface area (BET) of 1 m ² / g 1,200 rpm sprayed.

450 parts of the calcium carbonate treated in this way are mixed with 1,050 parts of polyethylene (density 0.96 g / cm ³ , melting point 23 g / 10 min, containing 0.42% by weight of a phenolic stabilizer and 2.5% by weight of a sulfur-containing costabilizer ) well mixed in a plow blade mixer. The mixture is further processed as described in Example 1. The properties of the test specimens are listed in Table III.

Example 18:

Example 17 is repeated, except that 5 parts of vinylphosphonic acid bis (2-ethylhexyl) ester are used without solvent instead of octadecanephosphonic acid. The mixture is further processed as described in Example 1. The properties of the test specimens are listed in Table III.

Example 19:

Example 17 is repeated, except that 10 parts of vinylphosphonic acid are used instead of octadecanephosphonic acid become. The mixture is further processed as described in Example 1. The properties of the test specimens are listed in Table III. As a comparison, a mixture of untreated calcium carbonate and polyethylene is produced in accordance with Example 15.

Example 20:

500 parts of calcium carbonate of calcite type having a mean particle diameter of 1.5 _/ um and a specifi _- see surface area (BET) of 7 m ² / are suspended in 2500 parts of n-hexane g. With good stirring, 12.5 parts of vinylphosphonic acid are added dropwise within 30 minutes. The suspension is stirred for 3 hours at room temperature, then the hexane is distilled off in vacuo and the residue is dried at 40 ^° C. in a vacuum drying cabinet. 450 parts of the calcium carbonate treated in this way are mixed with 1,050 parts of polyethylene (density 0.96 g / cm ³ , melt index 23 g / 10 min. Containing 0.42% by weight of a phenolic stabilizer and 2.5% by weight of a sulfur-containing costabilizer ), well mixed in a plow blade mixer. The mixture obtained is extruded into a strand in a twin-screw extruder, which is then granulated in a cutting machine. Test granules are produced from the granules using an injection molding machine. In a comparative example, 450 parts of untreated calcium carbonate are mixed with 1,050 parts of polyethylene in the same way and processed further.

The properties of the test specimens are listed in Table IV.

Example 21:

500 parts of precipitated calcium carbonate with an average particle diameter of 0.2 μm and a specific surface area (BET) of 9 m ² / g are suspended in 2,500 parts of acetone. 5 parts of vinylphosphonic acid are added dropwise with thorough stirring in the course of 30 minutes.

Working up, mixing with polyethylene and testing are carried out as described in Example 20.

A comparison sample with unmodified, precipitated calcium carbonate is also produced here.

The properties of the test specimens are listed in Table IV.

Example 22:

Example 21 is repeated with the proviso that instead of acetone, methanol is used as the solvent and octanephosphonic acid is used as the modifier for precipitated calcium carbonate instead of vinylphosphonic acid. The properties of the test specimens are listed in Table IV.

Example 23:

To 1,100 parts of polyethylene with a density of 0.96 g / cm ³ and a melt index of 23 g / 10 min. a solution of 4.7 parts of vinylphosphonic acid in 4.7 parts of water in a high-speed mixer at 1200 rpm from a sputtering device. sprayed within 20 minutes. 1,050 parts of the polyethylene treated in this way are mixed well in a plow blade mixer with 450 parts of calcium carbonate (average particle diameter .mu.m, specific surface area 1 m ² / g).

The mixture is further processed as described in Example 1. The properties of the test specimens are listed in Table V.

Example 24:

Example 23 is repeated, an additional 0.04 part of tert-butylhydroxyperoxide being added in the high-speed mixer.

The mixture is further processed as described in Example 1. The properties of the test specimens are listed in Table V.

Example 25:

1,100 parts of polyethylene (density 0.96 g / cm ³ , melt index 23 g / 10 min. Stabilized as in Example 1) and 7 parts of octanephosphonic acid are mixed in a high-speed mixer at 80 ° C. for 20 minutes.

1,050 parts of the polyethylene treated in this way are mixed well in a plow blade mixer with 450 parts of calcium carbonate (average particle diameter 5 μm, specific surface area 1 m ² / g).

The mixture is further processed as described in Example 1. The properties of the test specimens are listed in Table V.

Example 26:

Example 25 is repeated with the change that dodecanephosphonic acid is used instead of octanephosphonic acid. The properties of the test specimens are listed in Table V.

Example 27:

1,050 parts of polyethylene (density 0.96 g / cm ³ , melt index 23 g / 10 min., Stabilized as in Example 1), 450 parts of calcium carbonate (average particle diameter 5 μm, specific surface area 1 m ² / g) and 4.5 parts Oetanephosphonic acid are mixed at 80 ° C in a high-speed mixer for 30 minutes. The extrusion and testing are carried out as described in Example 1.

The properties of the test specimens are listed in Table V.

Examples 28-35:

Made from 70% by weight polyethylene (density 0.96 g / cm ³ , melt index 23 g / 10 min., Stabilized as in Example 1) and 20% by weight calcium carbonate (average particle size 5 _/ um, specific surface area 1 m ² / g) which had been treated with various modifiers according to Example 1, polyolefin molding compositions are produced,

The test specimens are examined for impact strength. The results are shown in Table VI.

Example 36:

500 parts of calcium carbonate with an average particle diameter of 2.5 μm and a specific surface area (BET) of 2 m ² / g are suspended in 2,000 parts of acetone.

0.5 parts of vinylphosphonic acid are added with thorough stirring. The suspension is stirred for 3 hours at room temperature, then the acetone is distilled off in vacuo and the residue is dried at 40 ° C. in a vacuum drying cabinet.

450 parts of the calcium carbonate treated in this way are mixed with 1,050 parts of polyethylene (density 0.96 g / cm ³ , melt index 23 g / 10 min. Containing 0.42% by weight of a phenolic stabilizer and 2.5% by weight of a sulfur-containing costabilizer ) well mixed in a plow blade mixer.

The test specimens are produced and tested as described in Example 1.

As a comparison, 450 parts of untreated calcium carbonate are mixed with 1,050 parts of polyethylene in the same way and processed as described above.

The properties of the test specimens are shown in Table VII.

Example 37:

500 parts of calcium carbonate with an average particle diameter of 2.5 microns and a specific surface area (BET) of 2 m ² / g and 2.5 parts of octanephosphonic acid are mixed in a high-speed mixer at 1200 rpm. mixed at 80 ° C for 20 minutes. 450 parts of the calcium carbonate treated in this way are stabilized with 1,050 parts of polyethylene (density 0.96 g / cm ³ , melting point 23 g / 10 min., As in Example 36) in a plow shovel Mixer well mixed.

The test specimens are produced and examined as described in Example 1.

The properties of the test specimens are shown in Table VII.

Example 38:

500 parts of calcium carbonate with an average particle diameter of 5 _/ um and a specific surface area (BET) of 1 m ² / g and 5 parts of dodecanephosphonic acid are mixed in a high-speed mixer at 1200 rpm. mixed at 80 ° C for 20 minutes.

450 parts of the calcium carbonate treated in this way are combined with 1,050 parts of polypropylene (density 0.905 g / cm ³ melt index 7 g / 10 min, containing 0.5% by weight of a phenolic stabilizer and 1.75% by weight of a sulfur-containing costabilizer) Plow blade mixer mixed well.

For a comparison test, 450 parts of untreated calcium carbonate are mixed with 1,050 parts of polypropylene in the same way.

The further processing of the mixtures, the production of the test specimens and the testing are carried out as described in Example 1.

The properties of the test specimens are shown in Table VIII.

Examples 39-45:

As described in Example 15, the same polyethylene is mixed with further amounts of the same calcium carbonate, which was modified with 1 percent by weight octanephosphonic acid, based on the amount by weight of filler, and processed further. For this purpose, mixtures with untreated calcium carbonate are produced as a comparison.

The properties of the test specimens are shown in Table IX.

Claims (3)

1. Plastic molding compound containing filler consisting of 90 to 20 parts by weight of a polyolefin, 10 to 80 parts by weight of an additive customary in alkaline earth metal carbonate, and 0.1 to 10% by weight, based on the filler of an adhesion promoter, characterized in that they act as an adhesion promoter, an organophosphorus compound of the formula

wherein R ^{1 is} an alkyl group with 1 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, an aralkyl group with 7 to 13 carbon atoms, the alkyl chain of which has 1 to 3 carbon atoms, or an aralkenyl group with 8 to 13 carbon atoms, the alkenyl chain is 2 or 3 carbon atoms and R and R ^{3 are the} same or different and are hydrogen, an alkyl radical having 1 to 8 carbon atoms, an aryl radical having 6 to 10 carbon atoms, an aralkyl radical having 7 to 13 carbon atoms, the alkyl chain of which has 1 to 3 carbon atoms, or an alkenyl radical 3 to 5 carbon atoms. 2. Plastic molding compound containing filler consisting of 90 to 20 parts by weight of a polyethylene 10 to 80 parts by weight of an additive customary in alkaline earth metal carbonate and 0.1 to 10% by weight, based on the filler, of an adhesion promoter, characterized in that they act as an organophosphorus compound of the formula

wherein R ^{1 is} an alkyl radical

18 carbon atoms, an alkylene radical. with 2 to 18 carbon atoms, an aralkyl radical with 7 to 13 carbon atoms, the alkyl chain of which has 1 to 3 x-carbon atoms, or an aralkenyl radical with 8 to 13 carbon atoms, the alkylene chain has 2 or 3 carbon atoms, and R ² and R ^{3 are the} same or different and Contains hydrogen, an alkyl radical with 1 to 8 carbon atoms, an aryl radical with 6 to 10 carbon atoms, an aralkyl radical with 7 to 13 carbon atoms, the alkyl chain of which has 1 to 3 carbon atoms, or an alkenyl radical with 3 to 5 carbon atoms. 3. Process for the production of a plastic molding compound containing filler consisting of 90 to 20 parts by weight of a polyolefin, 10 to 80 parts by weight of an additive customary in alkaline earth metal carbonate and 0.1 to 10% by weight, based on the filler, of an adhesion promoter, by mixing the constituents, characterized in that an organophosphorus compound of the formula is used as the adhesion promoter

wherein R ^{1 is} an alkyl group with 1 to 18 carbon atoms, an alkanyl group with 2 to 4 carbon atoms, an aralkyl group with 7 to 13 carbon atoms, the

Has 1 to 3 carbon atoms, or one

having 8 to 14 carbon atoms, the alkeryl chain of which has 2 or 3 carbon atoms, and R ² and R ^{3 are} identical or different and

an alkyl radical with 1 to 8 carbon atoms, an aryl radical with 6 to 10 carbon atoms, an aralkyl radical with 7 to 13 carbon atoms, the alkyl chain of which has 1 to 3 carbon atoms, or an alkenyl radical with 3 to 5 carbon atoms

is used.