WO1981003144A1

WO1981003144A1 - Method for producing mixtures of thermoplastic synthetic materials and mineral or organic charge materials,apparatus for the implementation of the method and material produced thereby

Info

Publication number: WO1981003144A1
Application number: PCT/DE1981/000070
Authority: WO
Inventors: B Wessling; G Baller; H Grigull; W Schoenfelder
Original assignee: Sapco Systemanalyse & Projektc; B Wessling; G Baller; H Grigull; W Schoenfelder
Priority date: 1980-05-09
Filing date: 1981-05-07
Publication date: 1981-11-12
Also published as: DD158526A5; KR850001468A; RO86050A; GB2075353B; DE3017752C2; GR74899B; AR225809A1; RO86050B; FR2481991A1; DE3017752A1; GB2075353A; IT8121589A0; HU182749B; KR850000531B1; IT1138770B; BE888734A; BR8108590A; ZA813026B; ES502035A0; KR850000530B1

Abstract

In a method for producing mixtures of thermoplastic synthetic materials and mineral or organic charge materials, the materials are vacuum mixed and compressed. According to the invention, the mixtures of synthetic materials and charge materials are already homogeneous in a powder state. They are also resistant without granulation to disaggregation, they are stable and can be shaped as products. Moreover, the rigidity must be obviously high but without fragility. The values of the resistance must approach those of the pure synthetic material. Finally, commercial advantages must be attained. To these purposes, the charge materials must be electrically or electrostatically charged before and/or during the mixing with the synthetic materials. As an alternative, this can also be achieved with the synthetic material and even, for instance, through a continuous stirring within an electric field. The charge remains stable during a long period allowing a previous treatment and a storage of the charge material separated from the mixing operation. A combined loading and mixing reactor, together with an installation (57) for producing a strong grinding of the content, is also part of the invention.

Description

Process for the production of mixtures of thermoplastic plastics and mineral or organic fillers as well as device for carrying out the process and the material produced thereafter

Technical field

The invention relates to a process for the production of mixtures of thermoplastic plastics and mineral or organic fillers, the starting materials to be mixed being mixed under vacuum and thereby being compressed. The invention further relates to a device suitable for this purpose with a coolable vacuum container in which a mixing device is arranged, the supply of starting materials into the vacuum container and the removal of the mixture from the container via the maintenance of the vacuum serving funnels and valves. Finally, the invention also relates to a material in the form of a mixture of thermoplastics and mineral or organic fillers.

State of the art

The admixture of mineral or organic fillers to plastics is intended on the one hand to cheapen the raw material and on the other hand to achieve the desired properties of the later product. The particular difficulty here is to provide the foreman of the plastic-filler mixture with a homogeneous, transportable and stable polymer starting material against demixing if no immediate further processing of the mixture is intended. In addition, the mixture as raw material for further processing specified strength requirements are sufficient. To achieve these goals, various approaches have hitherto been followed, which more or less amount to a thermal treatment of the plastic base, which causes the thermoplastic to melt or soften.

In the known methods, the components plastic and filler are brought together and mixed by rolling, kneading, plasticizing or extruding. It is known that in order to form correspondingly large adhesive forces between plastic and filler, the pores of both components must be as free as possible from water and air, because with a smaller distance between the molecular chains between plastic and filler, the van der Waal forces increase, which are necessary for one Ensure connection of both components. If any gas or moisture shells that prevent cohesion are to be removed, the compounding is carried out under vacuum in single or twin screw extruders in which the materials are continuously conveyed, mixed and compressed. This requires the use of appropriate funnels with degassing devices for adding components.

On the basis of this knowledge, a process for the production of a plastic-filler mixture builds up, which has become known from DE-OS 23 34 189. Then the fillers are first subjected to intensive predrying, this predrying being carried out under vacuum, and then the mixing with the plastic also takes place under vacuum in order to ensure that moisture is excluded. During the mixing process, the process temperature must be controlled so that the plastic particles added in powder form gel on the surface, so that the filler particles sinter on it, whereby the resulting agglomerates can no longer separate.

The disadvantage of this process is that the procedural effort for drying the filler and for the sintering process (gelling) is not related to the adhesion between the plastic matrix and the filler particles and that the homogeneity of the mixture thus produced does not meet the usual requirements . In addition, coloring pigments must be added before the mixing process.

In another known method (DE-OS 23 32 583) plastic and filler are added to one another with constant kneading to achieve the desired mixture. Due to the heat generated during the kneading process as a result of the constant friction, which can be further increased by additional heat from the outside, the plastic particles melt and mix with the filler particles. This process is carried out until the filler has been substantially consumed by the mixing, so that no free or unmixed filler remains and the particles of the polymeric material have been used up by melting at least to the desired extent. Depending on the components used, the process must be repeated several times.

These and other known processes, which can be summarized under the generic term "thermal processes" due to their physical mode of action, have the disadvantage that the necessary mechanical systems are associated with high investment and operating costs and often only allow low throughputs. The mixtures produced with it are not homogeneous, ie the proportion of filler in the individual granules varies. This is usually accompanied by poorer properties of the mixture and of the later product due to the weak adhesive forces between the plastic matrix and filler particles. The plastic-filler mixtures tend to be brittle or have a high modulus of elasticity, at the same time with increasing proportion of filler to lower strength. Although these effects are to be overcome or at least limited by the addition of so-called adhesion promoters, this is associated with high procedural complexity and consequently high costs, so that this possibility is reserved for the manufacture of special products.

Presentation of the invention

On the basis of the prior art described, the object of the invention is to provide a process for the production of plastic-filler mixtures which are already homogeneous in the powdered state and which are stable against demixing and can be processed into commercial products even without complex granulation. In addition, the materials produced by the method according to the invention should have a significantly higher stiffness, but without the otherwise associated brittleness, and at the same time

Achieve strength values that come close to those of pure plastic materials and are not achieved by the mixtures produced by the previously known and previously described processes. Finally, the process according to the invention should be associated with lower costs than according to the prior art, so that the cost reduction associated with the saving in raw materials is not offset by excessively high process costs. Another object is to provide a suitable device for performing the method.

The solutions to these tasks according to the invention as well as advantageous refinements and developments of the same result from the content of the claims which precede this description.

In the procedure according to the invention, the filler is subjected to an electrostatic charge. Depending on the type of filler, this charge is over

Stable for months. This also enables pretreatment of the filler, including any necessary intermediate storage, which is separate from the mixing process in terms of time and location.

When the plastic and filler are mixed, the friction that occurs causes charge separation, the plastic charging with an opposite polarity to the filler. However, with regard to certain combinations of filler and plastic, depending on their position relative to one another in the electrostatic row, it may be necessary for the plastic itself to be subjected to a previous charge and thereby to receive a charge opposite to the filler.

During the mixing process, a tightly fitting layer of filler particles forms around the entire plastic grain only because of the opposite charges of the two components; sintering or gelling of the filler particles on the softened surface of the plastic particles takes place in contrast to that in State of the art processes do not take place. This can be demonstrated in that when the plastic-filler mixture is dispersed in water, the filler shell detaches from the plastic grain because the electrostatic binding forces are eliminated in the water. Subsequent electron microscopic examination of the again "naked" plastic powder grain reveals its almost undamaged surface.

The thickness of the filler shell depends on the desired filler content. The total amount of filler added is bound in the filler shell and does not form its own agglomerates or agglomerations that are separated from the plastic or easily separated from it. As a result, the filler shell produced according to the procedure according to the invention is resistant to normal mechanical stress, e.g. B. insensitive to pressure, shock, shear forces or friction. In addition, the even shape of the filler shell results in good flowability of the powder, which is desired in further processing.

Brief description of the drawings

Various ways can be followed when carrying out the method according to the invention, as can be seen from the examples described below. Corresponding exemplary embodiments of devices for carrying out the method are shown in the drawing. Show it:

Fig. 1 is a schematic representation of the arrangement of units for charging the Components due to friction and their subsequent mixing,

Fig. 2 is a schematic representation of the arrangement of units for charging the components in an electrical

Field and their subsequent mixing,

3 shows a schematic diagram of a combined charging and mixing grid,

4 shows a schematic representation of the arrangement of units for the resolution of the components in an electrical field for a continuous implementation of the method,

5 shows a cut open particle of the mixture with plastic core and filler shell,

6 shows the enlargement of a section of the phase boundary in FIG. 5,

7 shows the enlargement of a section of the phase boundary in FIG. 6,

Fig. 8 bar chart with a comparison of mechanical parameters of a commercially available and the material according to the invention. Implementation of the invention in three ways

Example I

20 kg of a filler, e.g. B. chalk, talc, kaolin or mica with a moisture content of less than 3 wt .-%, are mixed under vacuum in a high-speed mixer at a pressure of 10 millibars, which leads to intense friction of the filler particles against each other and on the inner reactor parts . As a result, the particles are charged electrically, with chalk receiving a negative charge, talc, kaolin and mica a positive charge of several kV each. The loads are particularly stable when the mixture takes place at short-term (e.g. 0.5 s) peak temperatures above 200 ° C, which are caused either by frictional heat or by additional heating.

The filler pretreated in this way must then cool down again. Then the electrostatically charged filler with the desired amount of plastic, for. B. 20 to 30 kg of polyethylene, polypropylene or other powdered thermoplastics, placed in an evacuated high-speed mixer. The mass is mixed at a pressure of less than one thousand pascals, whereby a certain maximum temperature must not be exceeded, which is to be regarded as an indicator of the friction that has occurred and thus of the extent to which the filler and plastic are separated. This maximum temperature is lower than the softening temperature of the plastic and its amount depends both on the combination of plastic and filler used and on their quantity ratio, for example according to the following table:

The plastic-filler mixture now available is either stored in powder form, granulated in an extruder on request or if necessary, or fed directly to processing to an end product. Granulation and processing must be carried out under vacuum so that the intensive wetting of the filler by the thermoplastics is not impeded by the air layers adsorbed in caves or niche-like irregularities of the rough surface of the casing or bubbles enclosed there. and the adhesive forces can have a beneficial effect.

The attractive forces caused by the electrical charging lead to significantly better properties of the filled thermoplastics, in particular to good impact strength with a low modulus of elasticity.

A device as shown in FIG. 1 is suitable for carrying out the method according to Example I.

This device contains a combined charging and mixing reactor 10 with two feed hoppers 11, 12. The bottom of the reactor 10 has two outlets 13, 14, of which the outlet 14 is connected to a coolable intermediate volume 15, from which a line 16 to a cooling reactor 17 leads. A line 18 is laid back from the cooling reactor 17 to the combined charging and mixing reactor 10.

The combined charging and mixing reactor 10 consists of a reactor body 19 and a cover 20 which is electrically insulated from the reactor body 19, preferably by means of a layer 21 made of polytetrafluoroethylene. To produce the required vacuum, the reactor 10 is connected to a vacuum pump 22 via its cover 20. A pressure indicator 23 is provided on the cover 20. The cover 20 of the reactor 10 is connected to a high-voltage generator 24, which can supply voltages from 0 to 10 kV and can be regulated continuously. The reactor body 19 is grounded via an earthing line 25, to which the mixer 26 located in the reactor body 19 is also connected. The earthing of the Raaktor body including the mixer can be interrupted by a switch 27. Furthermore, the reactor body 19 is equipped with a temperature sensor 28 and a charge meter 29. Cooling coils 30 are arranged in a ring around the outside of the reactor body 19.

The feed funnels 11, 12 are also connected to the vacuum pump 22 and each provided with a pressure indicator 31, 32. Both funnels are each connected to the reactor 10 via vacuum-tight closing members 33, 34.

A line 35 leads from the outlet 14 of the combined charging and mixing reactor 10 to the coolable intermediate volume 15, which is connected to a vacuum pump 36 and has a pressure indicator 37. The intermediate volume is surrounded on the outside by annular coolant lines 38.

Coolable intermediate volume 15 and cooling reactor 17 are connected to one another via line 16. The cooling reactor 17 is also connected to the vacuum pump 36 and has a pressure indicator 39. The cooling reactor consists of a cooling reactor body 40 with a lid 41, the cooling reactor body 40 being provided on the inside with a non-conductive layer 42, preferably made of polytetrafluoroethylene. Ring-shaped coolant lines 43 are arranged on the outside around the cooling reactor body 40. Inside there is an upstanding shaft 44, on which three stirring arms 45 are attached, between which individual stirring arms are still scrapers 46.

The production of a plastic-filler mixture according to the method described in Example I proceeds as follows in the device shown in FIG. 1:

A batch of filler, e.g. B. 30 kg of chalk or similar mineral is fed via the evacuated funnel 11 and the product slide 33 into the combined charging and mixing reactor 10. Here, the filler is mixed intensively by a high-speed mixer 26, the filler heating up and electrically charging. The charge is constantly checked via the temperature sensor 28 and the charge meter 29. So that no layer of the filler to be charged is deposited on the cover of the reactor 10, the latter is in turn electrically charged by the high-voltage generator 24 from a temperature of the filler of 70 to 80 ° C., and z with an opposite sign to the charge of the filler. In contrast, the reactor body 19 and mixer 26 are grounded, and if necessary, the grounding can be interrupted via the switch 27 during the charging process, so that constant potentials can be built up.

If the filler is sufficiently charged, it is conveyed through the outlet 14 via the line 35 into the coolable intermediate volume 15. There, the filler is cooled by water flowing in the cooling coils 38 before it is conveyed further via the line 16 into the cooling reactor 17. During this cooling process, the reactor 10 is cooled by cooling water which flows in the cooling coils 30 to the extent that a new one

Charge filler can be added to the reactor 10 via the funnel 11. Here the filler is charged in the same way as described. The cooling reactor 17 has four times the volume of the reactor 10, so that four batches of filler can be cooled and stored in it. This is useful because it takes less time to charge the filler than it cools down and the subsequent mixing of filler and plastic.

If the cooling reactor 17 is filled, then the first batch of filler located at the bottom has cooled down to such an extent that part of it can be returned to the reactor 10 via the line 18 and the funnel 11. At the same time, a corresponding amount of plastic is introduced into the reactor 10 via the funnel 12. Here, in the same way as with the electrical charging of the filler, an intensive mixing of plastic and filler takes place. The temperature is constantly monitored by the temperature sensor 28. If there is sufficient charge separation during mixing, the mixing process is ended. The finished powdery compound can now either be fed to a package via the outlet 13 or to a granulating extruder or another processing machine.

Example II

In a modification of the procedure described in Example I, the filler or, if necessary, the plastic can also be charged by exposing the particles to a correspondingly strong electric field. For this purpose, a correspondingly high voltage is applied between the agitator and the outer wall of a reactor designed for this purpose. The design of the agitator as a grid with attached tips is particularly advantageous, since the so-called tip removal Charge even small voltages are sufficient to generate a strong electric field locally. The direction is therefore comparable to a capacitor, the initially electrically neutral solid-state components acting as a dielectric.

If there is a negative voltage at the tips of the agitator grid, the tips emit free electrons, which are taken up by the filler or plastic molecules. There is an excess of electrons, which negatively charges the component particles. D ^' . Particles thus become charge carriers themselves, and the live grid is virtually shifted towards the outer wall of the reactor until all of the particles are electrically charged to the desired extent. Discharge of the particles at the counter electrode, namely the outer wall, is prevented by the inner wall of the reactor vessel being lined with an electrically insulating layer.

If the particles are to be charged positively, the agitator grille and outer wall must be reversed accordingly. A strong electric field with lattice tips as a (positive) anode releases electrons from the component molecules, which leads to an electron deficit, i.e. positive charging.

in both cases, the amount of charge introduced is checked via the level of the voltage and the duration of the process. A uniform charge distribution is produced by constant, slow circulation of the material by rotating the agitator grid.

After charging, the components enter a mixing reactor and are there in the same way as in Example I executed, mixed and then used for further use.

Compared to electrical charging in a high-speed mixer according to Example I, the charging in an electrical field described above in Example II has the advantage that cooling, in particular of the filler, is no longer necessary after charging. This saves the extensive machinery for cooling the material and returning it to the mixing reactor. Furthermore, the charging process can be better controlled as a result of the selectable polarity and amount of charge, and thus a particularly good coating of the plastic grain can be achieved due to the attractive forces thus caused when the plastic and filler are mixed.

The charging of the components in an electrical field can be carried out in a device as shown schematically in FIGS. 2 and 3.

On a vacuum container 49, two reactors 50, 51 of identical design for the electric charge are placed, only one of the two reactors being described below. The reactor 50 is powered by a vacuum pump

52 evacuated, the negative pressure via the pressure indicator

53 is controllable. The reactor has a reactor body 54 and a reactor cover 55 which is electrically insulated from the body 54. The reactor body 54 is in its

Inside lined with a layer 56 of an electrically insulating material.

A stirrer cylinder 57, which consists of an electrically insulating material and a conductive core 58, is introduced into the reactor cover 55 in a vacuum-tight and electrically insulated manner. The agitator cylinder 57 only extends approximately to Half of the reactor body 54. As can be seen from FIG. 3, the conductive core 58 of the agitator cylinder has a connection to an agitator 59 which is designed as a two-armed grating 59a, in which the opposing grating surfaces are each 30 ° from the

Are tilted vertically. Short points 59b made of conductive material are attached to the intersection points of the individual grid bars forming the grid 59a perpendicular to the grid plane, only on the upper side of the grid 59a tilted by 30 ° and pointing in the direction of rotation of the grid.

A voltage between 0 and 100 kV is applied to the conductive core 58 and the outer wall 60 of the reactor body 54, which is produced by a conductive material and is generated by a continuously variable high-voltage generator 61. The voltage is transferred to the rotating conductive core 58 by means of a grinding electrode 62.

The reactor 50 is also provided with a vacuum-tight feed lock 63 and an outlet 64, the latter being connected to the vacuum-tight slide valve 33 of the "vacuum container 49. This vacuum container 49 is otherwise designed with all of its components in the same way as the mixing reactor in the example I. The coolable intermediate volume and the cooling reactor, which are not required in the process described, are missing here.

In the device described above, the process according to Example II proceeds as follows:

A batch of the required filler is fed into the reactor 50 via the vacuum-tight material lock 63. The filler is constantly changed by the agitator 59 moves and moves. Between the agitator 59 and the outer wall 60 made of conductive material there is a voltage of approximately 80 kV, which is generated by the high-voltage generator 61. The polarity of the two conductive components, the agitator and the outer wall, depends on the desired charge polarity of the filler. Under vacuum, the filler remains in the reactor while the agitator is constantly rotating until all the particles have reached the desired charge. The filler is then discharged into the vacuum container 49 via the outlet 64 and the vacuum-tight product slide 33. At the same time, an equivalent amount of plastic is placed in the vacuum container 49 via the product slide 34, wherein the plastic can also be electrically charged.

A charge separation takes place in the vacuum container 49 by rapidly mixing the two components in the same way as described in Example I, so that the desired compound is formed due to the electrostatic attractive forces.

Example III

Since the examples I and II described above are devices which only permit batchwise, that is to say batchwise, production of the desired plastic / filler mixture, the device shown in FIG. 4 is set up for a continuous production process. In this case, the charging of the components must be carried out in an electric field using the procedure described in Example II, since cooling and thus intermediate storage of the components can then be dispensed with. Accordingly, the device for the continuous production of a plastic-filler mixture according to FIG. 4 consists of a mixing column 65, on which two charging reactors 50, 51 are placed, which corresponded to the reactors described in Example II, so that the components charged therein via the locks 66 , 67 get into the mixing column 65. To produce the required vacuum, the mixing column 65 is connected to a vacuum pump 68. The pressure in the mixing column is controlled by a pressure indicator 69.

The mixing column 65 is designed as a cylinder 70, which in a funnel-shaped cone tapering downwards

71 passes. The inner wall of the cylindrical part 70 of the mixing column 65 is provided with grooves 72 rising upward in a spiral. In the interior of the mixing column, a total of three rotors 74 are arranged on a vertical drive shaft 73, one of which has a small diameter in the tip of the cone 71, while the other two have a correspondingly larger diameter at the lower end of the cylindrical part 70 of the mixing column 65 are attached. The direction of rotation of the rotors 74 is chosen so that the material is conveyed upwards in the ascending spiral. Finally, there is an outlet 75 at the base of the cone 71, which is connected to a device 76 for further processing of the plastic-filler mixture, preferably an extruder.

The procedure in the device shown in FIG. 4 is as follows:

The components charged in opposite directions in the reactors 50 and 51, as described in Example II, are metered into the evacuated mixture via the locks 66, 67

' column 65 fed. In the mixing column they meet the rotors 74 arranged at the end of the cylindrical part 70, are mixed there and conveyed upwards in the spiral attached to the inner wall of the cylinder 70. During the resulting upward migration movement, an intensive mixing of the two components, namely plastic and filler, takes place.

The upward conveyance of the material in the spiral and thus the mixing time are controlled via the

Metering the supply of components into the mixing column 65 and via the speed of the rotors 74, so that a corresponding amount of finished compounds falls into the cone 71. Here it is conveyed to the outlet 75 with constant further mixing by the rotor 74 arranged in the cone tip and continuously fed to the device which is under vacuum and intended for further processing. The total residence time in the mixing column 65 should be at least five minutes.

FIG. 5 shows an enlarged photo of an individual particle 80 of a plastic / filler mixture, which was produced according to one of the process examples described above. For better clarification, the particle 80 is cut open and opened, so that an insight into the structure of the particle with plastic core 81 and filler sleeve 82 can be obtained. The sharp dividing line 83 between the plastic core 81 and filler casing 82 is clearly recognizable. The filler particles have therefore not penetrated the plastic core or the plastic core has not melted or melted and has not mixed with the filler. This can be seen even more clearly in FIGS. 6 and 7, which show a section of the dividing line 83 between the plastic core 81 and the filler shell 82 in two different, greatly enlarged scanning electron microscope images. There are no components of plastic 85 between the individual filler particles 84, as would be the case in a sintering or gelling process between plastic and filler. The adhesion between plastic and filler is only due to the attractive forces caused by the opposite electrical charges.

Commercial usability

The plastic-filler mixture produced by the process according to the invention is stable in powder form against segregation. Typically, the mixture is either granulated if the customer so desires, or directly processed into a final product. It is of particular advantage that the end products, in contrast to the process described in the "prior art" section (DE-OS 23 34 189), can be subsequently dyed, which is particularly advantageous for fibers made from the material according to the invention. The adhesive forces between plastic and filler caused by the electrical charging of the components also result in significantly better material properties of the filled thermoplastics, which are not achieved by plastic-filler mixtures produced according to the prior art. This shows the comparison of the mechanical characteristic values from FIG. 8 commercial polypropylene mixture containing 40% by weight of talc with those of a polypropylene mixture likewise containing 40% by weight of talc, prepared by the process according to the invention. Above all, a low modulus of elasticity and significantly better tear resistance and impact strength are evident.

The features of the subject matter of the application disclosed in the patent claims, in the description and in the drawing can be essential both individually and in any combination with one another for realizing the invention in its various embodiments and embodiments.

Claims

Patent claims

1. A process for the preparation of mixtures of thermoplastic materials and mineral or organic fillers, the starting materials to be mixed being mixed under vacuum and thereby being compressed, characterized in that the fillers are electrically or electrostatically charged before and / or during the mixing with the plastics become.

2. The method according to claim 1, characterized in that the plastics are electrically or electrostatically charged before and / or during mixing with the fillers.

3. The method according to claim 1 or 2, characterized in that the charging of the starting materials is carried out with strong friction of the particles against one another and on the internal reactor parts with the resulting frictional heat and corresponding electrical or electrostatic charging.

4. The method according to any one of the preceding claims, characterized in that the fillers are charged with a moisture of less than three percent by weight and under a pressure of approximately one thousand Pascals.

5. The method according to any one of the preceding claims, characterized in that the charging takes place at brief peak temperatures above two hundred degrees Celsius, these temperatures being caused by friction and / or heating.

6. The method according to claim 5, characterized in that the starting materials are cooled after charging and before mixing.

7. The method according to claim 1-6, characterized in that the applied electrical charges are between approximately one and ten kilovolts.

8. The method according to claim 1 or 2, characterized in that the starting materials are charged in an electric field before they are mixed.

9. The method according to claim 8, characterized in that the starting materials are constantly circulated during charging for uniform charge distribution.

10. The method according to claim 8 and 9, characterized in that the amount of charge introduced over the amount of Voltage and the duration of the process is controlled

11. The method according to claim 1-3 or 8, characterized in that the mixing of the charged substances takes place under a pressure of about ten hillbars.

12. The method according to claim 1-3 or 8, characterized in that the maximum temperature occurring during the mixing of the starting materials is set lower than the softening temperature of the plastic used.

13. The method according to claim 12, characterized in that the maximum temperature depending on the type and amount of plastic and / or the filler is set at different levels. (Table on page 9).

14. The method according to at least one of the preceding claims, characterized by further processing of the mixture produced, for example granulation or spinning, under the discharge of the charge excluding or at least reducing conditions, preferably under vacuum.

15. The method according to at least one of the preceding claims, characterized in that the mixture or the product, for example the granules or the filament, is colored.

16. Device for carrying out the method according to claim 1 and one or more of the further preceding claims, with a coolable vacuum container in which a mixing device is arranged, the supply of starting materials into the vacuum container and the removal of the mixture from the container above the Maintenance of the vacuum serving funnels and valves is carried out, characterized; that a combined charging and mixing reactor (10) with device (26) for generating violent friction of the 5 parts of the reactor contents is provided, which is followed by a coolable intermediate volume (15) and this in turn a cooling reactor (17), a line (18 ) from the cooling reactor (17) in the charging and mixing reactor (10) is arranged to return.

17. The apparatus according to claim 16, characterized in that the reactor body (19) and cover (20) of the charging and mixing reactor (10) are electrically isolated from each other by a layer (21) made of non-conductive material.

18. The apparatus according to claim 17, characterized in that the cover (20) is connected to a high voltage generator (24), the output voltages is designed to be infinitely variable.

19. The apparatus according to claim 18, characterized in that the reactor body (19) and friction generator (26) are set up in isolation and are grounded via an earthing line (25) and that the earthing is to be interrupted via a switch (27).

20. The apparatus according to claim 16, characterized in that a temperature sensor (28) and a charge meter (29) are attached in the charging and mixing reactor (10).

21. The apparatus according to claim 16, characterized in that the coolable intermediate volume (15) can be evacuated and for this purpose is connected to a vacuum pump (36).

22. The apparatus according to claim 16, characterized in that the cooling reactor (17) has a multiple volume, preferably four times the volume, of the charging and mixing reactor (10).

23. The device according to claim 21 and 22, characterized in that the cooling reactor (17) is evacuated and for this purpose is connected to the vacuum pump (36).

24. The device according to claim 16, characterized in that the reactor body (40) of the cooling reactor (17) is provided in its interior with a layer (42) made of non-conductive material.

25. The device according to claim 16, characterized in that an upstanding shaft (44) rotating under the action of a drive is arranged in the cooling reactor (17) and that agitator arms (45) are fastened to the shaft, between which are strippers (46 ) are located;

26. The apparatus for carrying out the method according to claim 8, with a vacuum container in which a mixing device is arranged, wherein the supply of starting materials into the vacuum container and the removal of the mixture from the container takes place via the valves which serve to maintain the vacuum, characterized in that that the vacuum tank (49) charging reactors (50, 51) are connected upstream.

27 .. Device according to claim 26, characterized in that each charging reactor (50, 51) can be evacuated and for this purpose is connected to a vacuum pump (52).

28. The apparatus according to claim 26, characterized in that the reactor body (54) and cover (55) of the charging reactors (50, 51) are electrically insulated from one another.

29. The device according to claim 26 - 28, characterized in that the reactor body (54) consists of conductive material, but is lined in its interior with a layer (56) of electrically insulating material.

30. The apparatus according to claim 26, characterized in that an agitator cylinder (57) is arranged from the cover (55) in the reactor body (54), which consists of an electrically insulating material with a conductive core (58) and up to about half of the . Immerses reactor body (54) in this.

31. The device according to claim 30, characterized in that the conductive core (58) of the agitator cylinder (57) is connected to an agitator (59) which is also designed as a multi-arm grid (59a) which is conductive.

32. Apparatus according to claim 31, characterized in that the grid surfaces each forming a plane are tilted by approximately thirty degrees from the vertical.

33. Apparatus according to claim 32, characterized in that short tips (59b) made of conductive material are attached perpendicular to the grating planes, in each case on the upper side of the tilted grating (59a) and in the direction of rotation of the agitator (59).

34. Apparatus according to claim 29 and 30, characterized in that on the outer wall (60) of the reactor body (54) and on the conductive core (58) a voltage up to one hundred kilovolts is applied, which is generated by a continuously variable high-voltage generator (61).

35.Device according to claim 26, characterized in that the charging reactors (50, 51) with the vacuum container (49) are connected vacuum-tight via locks.

36. Apparatus according to claim 26, characterized in that the discharge (75) of the vacuum container (65) is connected directly to a further processing device (76).

37. Apparatus according to claim 36, characterized in that the vacuum container designed as a mixing column (65) consists of a cylinder (70) which tapers into a funnel-shaped lower part

(71) merges, the cylindrical part (70) on the inside with helically rising grooves

(72) is provided.

38. Apparatus according to claim 37, characterized in that a plurality of rotors (74) are attached to a vertically arranged drive shaft (73) standing in the center of the mixing column (65), of which a rotor (74) is located in the tip of the funnel ( 71) is located, while the others are arranged in the lower region of the cylindrical part (70).

39. Material in the form of a mixture of thermoplastics and mineral or organic fillers, produced by the method according to claim

1 or 2, characterized in that the mixture components (80) consist of a core (81) of thermoplastic material and a filler shell (82) formed around it.

40. Material according to claim 39, characterized in that the filler casing (82) holds onto the plastic core (81) solely on the basis of the attractive forces caused by the opposite electrical charges of plastic and filler.

41. Material according to claim 40, characterized in that the surface of the plastic core (81) is undamaged under the attached filler particles.

42. Material according to claim 40, characterized in that the filler shell (82) is mechanically stable.