DE3239213A1 - GRAPHITE FLUORIDE COATED WITH ORGANIC POLYMER AND METHOD FOR THE PRODUCTION THEREOF - Google Patents

Description

The invention relates to a modified graphite fluoride, which consists of graphite fluoride particles with a organic polymers are coated, furthermore a method for producing such a modified Graphite fluoride. The invention, with polymers coated graphite fluoride can either be in powder form, e.g. as a solid lubricant, or in compacted form, optionally with the addition of a synthetic resin, e.g. used as bearings or sealing elements.

Graphite fluoride is a solid material in the form of a white or gray powder, which is produced by a reaction between graphite or carbon in different forms and fluorine. Typical examples of graphite fluoride are (CF) _n and (G ^) as stable and technically usable polymeric compounds. In general, graphite fluoride has remarkably high lubricating properties and water and oil repelling properties, and is excellent in resistance to various chemicals. Therefore, graphite fluoride has been used as a solid lubricant in some fields and is still used for non-stick purposes, water- or oil-repellent purposes and anti-contamination purposes. Furthermore, it is known to be used for the production of a solid body for a specific application, for example as an electrode for electrolytic cells, by compression molding of a mixture which contains graphite fluoride as the main component

In practical applications, however, they are very important pronounced properties of the water and oil repellency of graphite fluoride, resulting in the exceptionally low surface energy Often disadvantages or difficulties in various respects are ascribed to this material. This material can hardly be dispersed in water and has very little miscibility with organic materials and has poor deformability.

Look at you. For the "use of graphite fluoride as a solid lubricant, it is ideal that fine particles of pure graphite fluoride provide an endless and dense contact film on the surface provided therewith, and for this reason it is often desirable to disperse graphite fluoride in water without the use of an auxiliary material. Indeed however, graphite fluoride has practically no wettability by water, which is shown by the fact that the contact angle of (CF) _n for water is 14-5 °, which is a very large value compared to the contact angle of 100-110 ° for polytetrafluoroethylene (PTEE), which is used as a solid lubricant, and therefore it is practically impossible to disperse pure graphite fluoride in water.

To solve this problem, it has been proposed to put together a dispersant such as colloidal silica to use with graphite fluoride. Although the use of such a dispersant for the preparation an aqueous dispersion can be effective, another problem arises in that the content of graphite fluoride cannot be adjusted as high as desired in the dispersed solid phase; the graphite fluoride content must be restricted to a maximum of about 60% by weight. Hence, it becomes impossible to use the beneficial properties of Graphite fluoride, which due to the low interfacial energy, this material are given to be fully exploited. Furthermore, it has already been proposed that particles of graphite fluoride with a binding material such as a wax or a mixture of a binding material and a surfactant to coat. In in practice, however, it is very difficult to uniformly coat the graphite fluoride particles through use to achieve a sufficiently small amount of such a coating material that the coated Graphite fluoride can sufficiently retain its characteristic properties. White

furthermore, such a coating is among the various Conditions of use of a graphite fluoride coated in this way not always stable, as the coating is only brought about by adsorption or adhesion, i.e., by physically bonding the binding material on the surfaces of the graphite fluoride particles.

In case of preparing it is already known an electrode of a primary cell using graphite fluoride as a typical example for compacting graphite fluoride containing as a main component mixtures, a mixture of graphite fluoride and PTi to mold ¹ e. The mixture is usually prepared using an aqueous dispersion of PTI ¹ E obtained by emulsion polymerization of tetrafluoroethylene. Since graphite fluoride is highly water-repellent, there is a need to suspend graphite fluoride particles in an organic solvent with a strong affinity for water before adding the graphite fluoride to the aqueous dispersion of the PTS ¹ E, and it is still necessary to use a considerably large amount of organic solvent to completely wet the graphite fluoride particles. However, the use of such a large amount of an organic solvent causes the coagulation of PTI ¹ E particles during the mixing of the graphite fluoride suspended in the solvent with the aqueous dispersion of the ΡΤΪΕ, so that the formation of undesirable large agglomerates is the result when mixed and a uniformly mixed powdery mixture is not obtained. In addition, the large agglomerates are very sticky and therefore it is difficult to pulverize them thoroughly. If the mixture containing large agglomerates is subjected to compression molding in a non-crushed state, it is very difficult to obtain a molded article of good quality because the presence of the agglomerates is a significant hindrance.

nis for a uniform transfer of the applied Is pressure and therefore defects are likely to be formed in the deformed body.

The object of the present invention is to provide a modified graphite fluoride composed of graphite fluoride particles which are coated with an organic polymer, this product being an essential better ability of dispersion in water and organic media, miscibility with organic media Materials and also the deformability should have and yet the cheap ones that are characteristic of graphite fluoride Properties is intended to be retained in order to thereby overcome the problems in practical use described above overcome by graphite fluoride.

Another object of the invention is to provide a method for producing such a modified one or graphite fluoride coated with polymer, as well as the provision of a solid body coated with polymers by compacting one Graphite fluoride, optionally with the addition of a synthetic resin, was formed.

The inventive, modified graphite fluoride, which consists essentially of fine particles of graphite fluoride. is made, polygons are coated with a vinyl-like polymer, which is an the surfaces of the graphite fluoride particles is bonded by graft polymerization.

The graphite fluoride used in the present invention is preferred either (CF) or (C ^ F), or a mixture of (CF) and (C ~ F). Preferred examples of the vinyl type Polymers are polymethyl acrylate, polymethyl methacrylate, Polystyrene and polyacrylonitrile. Preferably the content of the vinyl type polymer is the modified one

- 11-graphite fluoride in the range from 0.5 to 50 wt .-? <?.

The process of the present invention for preparing the modified graphite fluoride includes the steps of mixing of graphite fluoride in the form of fine particles with at least one vinyl-like monomer that is free radical polymerization or free radical Can experience copolymerization, the mixing being carried out in the presence of V / water, and the addition of a Polymerization initiator for the monomer or monomers to the mixture prepared in the previous stage, whereby the monomer or monomers can undergo polymerization and bond with the surfaces of the Experienced graphite fluoride particles by graft polymerization.

In most cases it will be advantageous to carry out the initial stage of mixing the graphite fluoride with the or the vinyl-like monomers by dispersing these materials in water with the addition of either a water-soluble, organic solvent or a surfactant To carry out means of continuing to use a water-soluble polymerization initiator, although it is also possible to use a semi-dry process in which only an almost negligible one small amount of water is used. The inventive method for graft polymerization can be carried out at room temperature, but it is advantageous to increase the rate of polymerization, the reaction system heat up to a temperature of about 70 ° 0 to be supplied.

A dispersion of graphite fluoride in water becomes acidic and shows a pH of around 2-3, and most Polymerization initiators for vinyl type monomers are acidic. The graft polymerization process according to the invention can under acidic conditions, which by the

Given the acidity of the graphite fluoride and the initiator are carried out, however, it is preferred to adjust the pH of the reaction system to 5 to 9 before a substantial Increase the course of the polymerization reaction, since such an adjustment of the pH is a surprising great increase in the effectiveness of the graft polymerization of the vinyl-like compound on the surfaces of the Graphite fluoride particles results. The adjustment of the pH is done by adding an alkaline compound the reaction system containing the polymerization initiator. Alternatively, graphite fluoride can be used with a alkaline solution or an alkaline gas prior to mixing the graphite fluoride with the vinyl-like monomer or the vinyl type monomers.

It is an essential feature of the modified or polymer-coated graphite fluoride according to FIG Invention that the coating of vinyl-like polymer chemically adheres to the surfaces of the graphite fluoride particles is bound by graft polymerization. In contrast to conventional coatings, which through mere adsorption or physical adhesion have been produced, has the polymer coating produced according to the invention such a high bond strength that the coating cannot be removed in a simple manner even by solvent extraction. Therefore it is possible to have a uniform and very strong coating on each particle of the treated graphite fluoride without an undesirably large amount of coating material should be used. It is therefore permissible to use the polymer-coated coating according to the invention Graphite fluoride as "microencapsulated graphite fluoride" describe. However, the present invention is not strictly limited to graphite fluoride particles, whichever are completely coated with vinyl-like polymer. Even if the polymer coating is as it is in accordance with the invention is produced is incomplete, so that

the surfaces of the graphite fluoride particles are partially exposed, the invention nevertheless encompasses that with polymer coated graphite fluoride and the manufacturing method given above.

The polymer-coated graphite fluoride of the invention can be easily dispersed in water or various organic liquids and remains in for a long time a well-dispersed state. Furthermore, such a polymer-coated graphite fluoride is excellent Deformability and is easily miscible with various synthetic resins, making it easy is possible to polymerize solid bodies by press molding this Graphite fluoride or a powdery mixture of this material and a synthetic one Resin with uniform "distribution of the coated graphite fluoride particles in each molded article.

The polymer-coated graphite fluoride according to the invention retains the favorable properties of graphite fluoride, as given by its high lubricity, completely at. Therefore, the polymer-coated according to the invention Graphite fluoride can be widely used in various fields. For example Such a polymer-coated graphite fluoride can be used very advantageously as an additive to lubricating oils and greases and to various rubbers and plastics "use, furthermore it is used for compression molding self-lubricating bearings and packings or suitable for electrodes of certain batteries.

Furthermore, it has been found that the graft polymerization coating method of the present invention is applicable to various powdery materials useful as solid lubricants, e.g., graphite, molybdenum disulf id, boron nitride, tungsten disulfide, mica, talc and polytetrafluoroethylene, the effect being that the dispersion of these materials in various

Media and the deformability of these materials are improved.

The invention is explained in more detail with reference to the drawing; in the drawing are:

Fig. 1 is a photomicrograph of a powdered

Graphite fluoride, as used in an example will;

Figure 2 is a photomicrograph of one containing polymer

coated graphite fluoride, which in this Example was made;

3 is a photomicrograph of another graphite fluoride; that was used in a further example;

Figure 4 is a photomicrograph of the polymer coated graphite fluoride used in this example was produced;

Fig. 5 is a diagram of the IR spectrum of an organic Substance, polygons when performing benzene extraction of polymer-coated graphite fluoride according to Fig. 2 was obtained;

Fig. 6 is a diagram of the IR absorption spectrum of the

undissolved residue from benzene extraction;

7 is a photomicrograph showing a section of a represents solid body formed by press molding the polymer-coated graphite fluoride from Fig. 2; "

8 is a photomicrograph of a section of a

solid body made by compression molding of the not

treated graphite fluoride according to i'ig. 1 received became;

J'ig. 9 is a photomicrograph of a polymer coated Graphite fluoride, which in another Example of the invention was prepared with the pH of the polymerization reaction system adjusted became;

Figure 10 is a photomicrograph of a polymer: coated Graphite fluoride produced in the same example without adjusting the pH became.

In the present invention, the two graphite fluorides which can be represented by (CF) _n and (Cp ^ n are almost equally useful, and it is possible to use a mixture of these two kinds of graphite fluorides in any proportion it possible to use graphite fluoride of another different type, generally indicated by the formula (CP "), where χ in the case of

-K η

range from about 0.1 to about 1.5 and the technical accessibility of this material is not always given is. In either case it is advantageous if the graphite fluoride is in the form of fine particles, e.g. Particles with an average particle size of less than 100 μm.

Regarding the material for the polymer coating can be almost any choice among vinyl-like monomers that undergo radical polymerization, be taken, and if necessary it is possible to jointly to use two or more kinds of vinyl-like monomers which undergo radical copolymerization. Examples of useful compounds with a vinyl type bond are acrylic acid, methacrylic acid, Acrylates, methacrylates, acrylic esters, methacrylic esters, acrylic

nitrile, N-methylo 1 acryl amide, vinyl chloride, vinyl acetate, Styrene, divinylbenzene and vinylidene fluoride.

In the polymer-coated graphite fluoride, the content of vinyl-like polymer should be at least 0.5% by weight, to achieve a substantial improvement in the dispersion properties. In theory there aren't any sharp upper limit for the polymer content in the coated graphite fluoride, but in practice it is It is important that the coated graphite fluoride has the desired Exhibits properties of graphite fluoride sufficiently, therefore the preferable upper limit is for the polymer content in the coated graphite fluoride 50% by weight. The polymer content can be within these limits in the coated graphite fluoride can be set as desired by the proportion of vinyl-like monomers to the graphite fluoride is adjusted.

In the method according to the invention for producing the polymer-coated graphite fluoride described above a common way is to disperse graphite fluoride and vinyl-like monomer in either a mixture of water and an organic, water-soluble solvent or a mixture of water and a surfactant Middle. The organic solvent can, for example, from alcohols, e.g. methanol and ethanol, ketones, e.g. acetone, ethers and amines can be selected. The most preferred solvent is ethanol, especially since the use of ethanol is effective for increasing grafting power, this being that Weight ratio of the graphite fluoride by graft polymerization bonded vinyl-type polymers to the vinyl-type which has been subjected to the polymerization reaction Is monomers. The organic solvent is used in an amount sufficient for good dispersion of the graphite fluoride is used in the obtained aqueous medium, however, an excessively large amount is used

organic solvent not advantageous, as cies results in a decrease in grafting capacity. In the case of Ethanol, the preferred range of the ratio of water / water to ethanol is 0.1: 1 to 2.3: 1, expressed by weight. The surfactant may or may not be anionic, cationic, or nonionic is a mixture of surfactants of different types Types act.

A water-soluble initiator such as sulfur dioxide, an aqueous solution of sulfurous acid, an aqueous solution of a hydrogen sulfite, potassium persulfate, azobiscyanovaleric acid or 2,2'-azobis (2-amidinopropane) dihydrochloride is advantageously used as the polymerization initiator for the selected vinyl-like conomer. Advantageously, an aqueous dispersion system is created by adding 1 to 100 parts by weight of graphite fluoride and 0.1 to 100 parts by weight of vinyl-like monomer in a mixture of 100 parts by weight of water and either 1 to 100 parts by weight of organic Solvent or 1 to 50 parts by weight of surfactant and thoroughly stirring the resulting mixture. A polymerization initiator is then added to the aqueous dispersion and stirring is continued. It is sufficient if the amount of polymerization initiator, 0.01 to 20 wt -.% Constitutes the vinyl-type monomer.

After the addition of the polymerization initiator, the vinyl-like monomer in the aqueous dispersion undergoes radical polymerization and graft polymerization with the graphite fluoride, even at room temperature. However, it is advantageous to keep the reaction system at an appropriately elevated temperature, such as about 50 ^° C. to 70 ^° C., in order to thereby increase the rate of polymerization and to complete the polymerization reaction in a shorter period of time. According to this process, a high degree of polymerisation can be achieved in a relatively

tively short reaction times such as 1 to 5 hours can be achieved.

ITacn, the completion of the polymerization reaction will be the reacted slurry to separate the solid component filtered, this being a polymer-coated graphite fluoride in powder form, and the polymer-coated Graphite fluoride is thoroughly washed with water and dried. This is how the manufacture of the polymer-coated graphite fluoride according to the invention achieved by simple operations, and, it it is easily possible to regulate the proportion of reactants and the reaction conditions in the desired manner.

In the process of the present invention, it is particularly preferred to adjust the pH of the polymerization reaction system to 5 to 9 after the addition of the polymerization initiator, since such an adjustment of the pH has the effect of greatly increasing the grafting ability. Numerically, the grafting capacity becomes more than 90 % and in some cases close to 100%. When graphite fluoride is dispersed in water with the aid of an organic solvent or a surfactant as previously described, the dispersion becomes acidic and exhibits a pH of about 2- to 4-, probably due to the presence of a small amount of ascribed to free fluorine on the surfaces of the graphite fluoride particles. In addition, the above-described polymerization initiators preferred according to the invention are acidic materials. Without adjustment of the pH it would be natural that the polymerization reaction would proceed under acidic conditions, represented by a pH above 2 but below 5. The production of polymer-coated graphite fluoride according to the invention is completely possible in practice even under such acidic conditions, but in such a case it is difficult to increase the grafting rate above values of 70 ° .

Probably the reason for increasing the grafting capacity by adjusting the pH of the reaction system to 5 to 9 using an alkaline compound is that the neutralization of the free fluorine as the source of acidity by the attack of the alkaline compound on the surfaces of the graphite fluoride particles causes numerous active points to appear on these surfaces. In an experiment on an aqueous dispersion of graphite fluoride (CF) _n with a pH of about 5, the addition of an alkaline compound to raise the pH of the dispersion to about 8 caused the initially white color of the dispersion to turn brown Color changed so that a neutralization phenomenon on the surfaces of the graphite fluoride can be understood.

The range of the adjusted pH value of the reaction system is 5 to 9, initially because of the effect of a such setting remains inadequate at a set pH value below 5 and continues at If the pH value exceeds 9, there is the possibility of graphite fluoride decomposing. The setting the pH value can be adjusted by adding an alkaline material such as an alkali metal hydroxide, alkali metal carbonate, aqueous ammonia, ammonia gas or an ammonium salt to the polymerization reaction system can be achieved after the addition of the polymerization initiator. Alternatively, the same purpose is achieved if Graphite fluoride with an alkaline solution or an alkaline gas before preparing the polymerization reaction system is treated »

In the case of carrying out the polymerization reaction after the semi-dry process described above, only very small amounts of water and organic Solvent used so that the graphite fluoride and

the vinyl monomer is only wetted with the liquid medium instead of being dispersed therein. When such a semi-dry process is provided, suitable ratios of the materials can be used in the method of the invention are indicated as follows: 0.1 to 600 parts by weight are advantageously used per 100 parts by weight of graphite fluoride Water, 0.1 to 300 parts by weight of an organic, water-soluble solvent or 0.1 to 150 parts by weight of a surfactant, 0.1 to 100 parts by weight vinyl-like monomer or vinyl-like monomers and a polymerization initiator in an amount of from 0.01 to 20 % By weight, based on the vinyl-like monomer (s), used.

In the semi-dry process, there is no need to filter the reaction system after the completion of the Polymerization reaction, and the polymer-coated graphite fluoride is sprayed by thoroughly washing the reaction with water and drying the washed Product received. The semi-dry process has advantages such as the possibility of treating a large Amount of graphite fluoride in a reaction vessel with a relatively small capacity, a large decrease the consumption of organic solvent and / or the elimination of a process for dissolving · ■ resource recovery as well as a simplification of the work processes for the recovery of the product. However that is Grafting capacity in the semi-dry process is lower than in the normal process using an aqueous dispersion if there is no other difference in others Factors of response there.

Further, in the case of the semi-dry process, it is very preferable to adjust the pH of the reaction system to 5 to 9 to adjust. In such a case it is advantageous to treat the graphite fluoride with an alkaline compound before mixing with vinyl-like momomer

- ^. j -

■ and water to carry out. Palls the setting 'of the pH value after the preparation of the polymerization reaction system if desired, the use of a gaseous alkaline compound such as ammonia gas is advantageous.

The polymer-coated graphite fluoride according to the invention shows good dispersion properties in various liquid media and has a very high affinity or Miscibility with various organic, powdery materials such as rubber (rubber) and synthetic Resins. Furthermore, such a polymer-coated graphite fluoride is very strong and almost ideal Polymer coating produced, even if the proportion of polymer to graphite fluoride is very low. Therefore such a polymer-coated graphite fluoride can die excellent lubricating properties or the others desired properties of graphite fluoride completely have, and by using such a material it is possible to produce a continuous lubricating film, which can practically be regarded as consisting of pure graphite fluoride powder.

Furthermore, such a polymer-coated graphite fluoride has good deformability, so that it is possible to do so Material alone into a solid body of a desired shape by the application of adequate pressure and heat to contact. The good dispersing properties of the polymer-coated graphite fluoride are also found in Compression molding this material so that the molded body has a dense and cohesive structure.

Using a mixture of the polymer-coated graphite fluoride and a suitable powder of a synthetic Resin or plastic, it is easier to press-molded To manufacture bodies of various shapes and

to increase the strength of the moldings. Various resins or plastics can be used for this purpose, as will be described later, and phenolic resins, polymethyl methacrylate resin, polyacetal resin and ABS resin can be cited as preferred examples. In principle there is no strict limit on the Amount of resin or plastic to be added, however it is from the point of view of fully exploiting the favorable properties of graphite fluoride it is preferred to limit the amount of resin such that the total weight of the polymer coating on the graphite fluoride particles and the resin added for compression molding does not include the weight of the graphite fluoride in the resulting mixture exceeds.

The press molding of the mixture of polymer-coated graphite fluoride and a selected resin in powder form is carried out by a conventional method, and a metal mold can be used here. With regard to the Preßformbedingungen it is usually sufficient to apply a pressure of 14-7-4-4-1 bar (150-4-50 kg / cm), while the mixture is kept heated at 100-250 ⁰ C, while the most suitable pressures and temperatures depending on the kind of the vinyl type polymer coated on the graphite fluoride and that with the. coated graphite fluoride mixed resin are variable.

In terms of good dispersing property and affinity for resins, compression molding gives the polymer-coated one Graphite fluoride to which a resin is added became, a dense, compacted, solid body, in which is the polymer-coated graphite fluoride particles are very evenly distributed. The compression molded bodies have excellent physical properties, and it is even possible to manufacture intricately shaped bodies. In case the graphite fluoride on the surface

-θάβε compression-molded body exposed v / should be grounded so that the surface the unique properties of graphite fluoride shows in a pronounced manner, this can be achieved by grinding the surface of the compression molded body which removes the resin from the surface, or alternatively the surface can be coated with a suitable organic solvents for dissolving the resin present on the surface. When a greater interest in the exploitation of the properties of graphite fluoride than in the physical Given the strength of the molded body, advantageously only a small amount of resin is added to it polymer-coated graphite fluoride added, or it becomes graphite fluoride coated with polymer alone compression molded.

Although this is not essential, it is possible to add any auxiliary material consisting of conventional, additives and / or inorganic materials used in the compression molding of synthetic plastics is selected to be a mixture of the polymer-coated Graphite fluoride and a selected plastic.

The polymer-coated graphite fluoride according to the invention, either in powder form or in compacted form, has greatly increased application possibilities compared to untreated graphite fluoride or graphite fluoride which has been treated according to the previously proposed procedures. Typical examples of the wide range of possible applications are summarized below:
(1) Manufacture of composite materials: A variety of composite materials can be made by mixing the polymer-coated graphite fluoride with natural or synthetic rubber, synthetic plastics, fiberglass, ceramic products, graphite or

other carbonaceous materials, asphalt, tar and / or pitch. Molded body from such composite materials are useful as self-lubricating bearings and sealing elements such as packings and seals, it is also possible to convert some of these composite materials into fiber form. Since the polymer coating according to the invention is strongly bonded to the graphite fluoride particles, at With the use of these composite materials, a very stable lubricating film is formed on the sliding contact surface are, and therefore the moldings have a very low wear rate and can strong heats, which by large values of the product of the applied pressure by the speed of the Relative movement of the moldings are given, withstand.

Examples of synthetic rubbers for this application are styrene rubber, butadiene rubber, Chloroprene rubber, butyl rubber, nitrile rubber, ethylene propylene rubber, chlorinated and sulfonated Polyethylene (trade name Hypalone) or chlorosulfonated Polyethylene rubber, acrylic rubber, Urethane rubber, fluororubber, silicone rubber, Thiokol and ethylene vinyl acetate rubber.

Examples of synthetic plastics for this use are phenolic resin, urea resin, melamine resin, Aniline resin, unsaturated polyester resin, diallyl phthalate, epoxy resin, alkyd resin, polyimido resins, Silicone resin, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyacrylonitrile, polyvinyl butyral, Polyamide, ABS resin, polycarbonate, polyacetals, Polyethylene terephthalates, polyphenylene oxide resins, polyphenylene sulfide resins, polysulfones, polyurethanes, Ionomer resins, fluororesins and cellulosic plastics.

(2) Addition to lubricating oils or greases:

The powdered polymer-coated graphite fluoride is used in various lubricating oils and greases for use as gear oil, spindle oil, cooling machine oil, Dynamo oil, turbine oil, machine oil, cylinder oil, lubricating oil for piston engines, especially for aircraft, Marine machine oil, stringy Stauffer grease, Stauffer grease, glass fiber grease, bearing grease for motor vehicles and ball bearing grease added.

Purely the aforementioned lubricating oils are polyolefins, Glycols, carboxylic acid esters, phosphoric acid esters, silicones, perfluorocarbons and chlorinated aromatics Compounds listed as useful materials. Purely the aforementioned lubricating greases are calcium soap grease, Sodium soap fat, aluminum soap fat, Barium soap fat, Pett mixed soaps, calcium complex soap fat, Barium complex soap fat and non-soap Pette, which non-soap materials like Bento.nit or fine silica as viscosity modifiers use, given as examples.

(3) Application for the formation of dry films for lubrication:

The polymer-coated graphite fluoride in powder form either alone or together with an organic one or inorganic binder is used on sliding contact surfaces of various apparatus in one such It is applied in a way that a dry and lubricating material is piled up, which is used for permanent lubrication, is used for running-in in an initial stage of operation or for loosening.

(4) Use as a non-stick agent or dissolving gown: The polymer-coated grophite fluoride in powder form is used as a lubricant and non-stick agent in forging and compression molding operations e.g. bodies made of sintered alloys, plastic molded bodies or rubber molded bodies. For this use, the polymer-coated graphite fluoride powder can be in a liquid or a Gas can be dispersed for spraying on the intended surfaces.

(5) Use in the processing of metals:

In metalworking operations such as cutting, The polymer-coated graphite fluoride is in powder form by rolling, drawing, pressing, grinding and polishing to the cutting oil, rolling oil, forming oil, grinding oil and the polishing liquid for the purpose of increasing the Lubricating effect of these oils or liquids added.

It should be noted that the uses listed above are only exemplary, and that the polymer-coated graphite fluoride according to the invention in the entire field of application of graphite fluoride is advantageous and in almost spring case numerous advantages over the use of untreated Graphite fluoride offers.

The invention is explained in more detail using the following examples:

example Λ

A. ■ 1 1 three-necked flask was immersed in a constant temperature bath at 60 ⁰ C and there were ml of water, 200 ml ethanol, 100 g of graphite fluoride (CF) _n and filled 25 g Methylmethacrylatmonomeres into the flask. The graphite fluoride was in the form of fine particles,

ORIGINAL BATHROOM

which had been obtained by pulverization in a jet mill and now passed through a sieve with a mesh size of 0.053. Figure 1 is a photomicrograph of the graphite fluoride particles used in this example. While stirring the mixture in the flask, 20 ml of a 6% aqueous solution of sulfurous acid was added to initiate the polymerization of the methyl methacrylate. At this stage, the pH of the aqueous reaction system was about 2. The stirring of the reaction system was continued for 4 hours after the addition of the sulfurous acid solution. Then, the solid component of the reacted slurry was separated from the liquid by filtration, washed thoroughly with water and then dried at 80 ⁰ C in vacuum to give 117j8 g powdery product was obtained.

Fig. 2 is a photomicrograph of the graphite fluoride thus treated. Like from this photomicrograph As can be seen, it could be confirmed that the graphite fluoride particles well with polymerized methyl methacrylate are coated without the presence of methacrylate polymer independently of the graphite fluoride particles can be observed. The polymer-coated graphite fluoride was subjected to benzene extraction during 48 hours and both the extract and the solid remaining undissolved in the benzene were subjected subjected to the IR absorption tip spectral analysis. The fig. shows the IR absorption spectrum of the extract and FIG. 6 shows that of the undissolved solid. By this analysis confirmed that the extract was a homopolymer of polymethyl methacrylate, furthermore confirms that the absorption spectrum of the undissolved solid matches the spectrum of polymethyl methacrylate agreed. These facts show the training a graft bond of the polymethyl methacrylate to the Surfaces of the graphite fluoride particles. The polymer-coated graphite fluoride was a thermogravimetri-

See analysis (TGA), this showed that the content of the polymethyl methacrylate in the coated graphite fluoride, calculated from the weight loss 15.1 wt% was.

In the following examples, microscopic observation was the IR absorption spectrum analysis and the thermogravimetric analysis according to those previously made Information given to the graft bond of the to confirm vinyl-like polymers on the graphite fluoride and determine the polymer content in the coated graphite fluoride.

Example 2

In this example, 330 ml of water, 150 ml Graph.itfluorid (CPF) _n were ^unc * ^ O g Methylmetacrylatmonomeres into a 1 1 three-necked flask immersed in a constant temperature bath of 60 ⁰ C filled. The graphite fluoride was in the form of fine particles obtained by pulverization in a jet mill and passed through a sieve with a mesh size of 0.062 mm. Figure 3 is a photomicrograph of this graphite fluoride. While stirring the mixture in the flask, 20 ml of a 6% strength aqueous solution of sulfurous acid were added to initiate the polymerization of the methyl methacrylate. At this stage, the pH of the aqueous reaction system was about 2. The stirring of the reaction system was continued for 3 hours after the addition of the sulfurous acid solution. Then, the unreacted slurry was filtered to separate the solid component, this was thoroughly washed with water and dried in vacuo at 80 ⁰ G. Figure 4- is a photomicrograph of the polymer-coated graphite fluoride obtained by this procedure.

The polymer coated graphite fluoride possessed when dry State a total weight of 124-.7 g and contained 19, G Weight percent polymethyl methacrylate.

Example 3

In this example, 100 ml of water, 150 ml of ethanol, 100 g of graphite fluoride particles (Cj?), As used in Example 1, and 30 g of methyl acrylate monomer were poured into a 1 l three-necked flask which was placed in a bath with a constant temperature of 60 ° C was immersed. While stirring the mixture in the flask, 20 ml of a 6% aqueous solution of sulfurous acid was added to initiate the polymerization of the methyl acrylate. At this stage, the pH of the aqueous reaction system was about 2. The stirring of the reaction system was continued for 3 hours after the addition of the sulfurous acid solution. The converted slurry was then filtered to separate off the solid component, this was washed thoroughly with water and dried ^{at 70 ° C. in vacuo.}

The polymer-coated graphite fluoride obtained by this procedure weighed 121.2 g in the dry state and contained 17.5 wt% polymethyl acrylate.

Example 4-

Using the same apparatus as in the preceding Examples were 285 ml of water, 200 ml of methanol, 100 g of graphite fluoride particles (Cp), as used in Example 2, and 20 g of diethyl acrylate monomer Stir mixed while maintaining the constant temperature bath at 60 ° C. While stirring continuously 15 ml of 6% aqueous solution of sulfurous acid was added to the mixture in the flask to initiate polymerization of methyl acrylate added. At this stage, the pH of the aqueous reaction system was about 3 · Das The reaction system was stirred 4 hours after the feed

continued administration of the solution of the sulphurous acid. Then the reacted slurry was filtered to separate the solid component, this was thoroughly washed with water and dried in vacuo at JOC.

The graphite fluoride obtained by this procedure, polymer coated weighed 111.8 g in the dry state, and contained 10.8 wt -.% Polymethyl methacrylate.

Example 5

Using the same apparatus as in the previous examples, 4-70 ml of water, 10 ml of polyoxyethylene alkyl ether, which was used as a nonionic surface-active agent, 100 g of the graphite fluoride particles (Oi ¹ ) described in Example 1, and 30 g Methyl methacrylate monomer mixed with stirring while the bath was kept ^{at 50 0 C with constant temperature.} With continued stirring, 20 ml of 6% aqueous solution of sulfurous acid was added to the mixture in the flask to initiate the polymerization reaction. At this stage, the pH of the aqueous reaction system was about 3. Stirring of the reaction system was continued for 4 hours after the addition of the sulfurous acid solution. The converted slurry was then filtered to separate off the solid component, this was washed thoroughly with water and dried ^{at 70 ° C. in vacuo.}

The polymer-coated graphite fluoride obtained by this procedure weighed 120.1 g in the dry state and contained 17.4% by weight polymethyl methacrylate.

Example 6

Using the same apparatus as in the previous examples, 280 ml of water, 200 ml of ethanol, 100 g of graphite fluoride (Ci ¹ ), as used in Example 1, and 30 g of acrylonitrile monomer were added with stirring

mixes while the bath was kept ^{at 60 0 C with constant temperature.} With continued stirring, 20 ml of 10 µl aqueous solution of 2.2 ^{liters of} azobis (2-amidinopropane) dihydrochloride was added to the mixture in the flask to initiate the polymer oxidation reaction. At this stage, the pH of the aqueous reaction system was about 3. Stirring of the reaction system was continued for 3 hours after the addition of the polymerization initiator solution. Then the reacted slurry was filtered to separate the solid component, this was washed thoroughly with water and dried in vacuo at 80.degree.

The polymer-coated graphite fluoride obtained by this procedure weighed 123.9 g in the dry state and contained 19.3% by weight polyacrylonitrile.

Example 7

Using the same apparatus as in the previous examples, 280 ml of water, 200 ml of ethanol, 100 g of the graphite fluoride (CP) _n used in Example 1, 15 g of methyl methacrylate monomer and 15 S of styrene monomer were mixed with stirring while the constant temperature bath was heated to 60 ⁰ C was kept. With continued stirring, 20 ml of 6% aqueous solution of sulfurous acid was added to the mixture to initiate the copolymerization reaction. At this stage, the pH of the aqueous reaction system was about 3. Stirring of the reaction system was continued for 3 hours after the addition of the sulfurous acid solution. The converted slurry was then filtered to separate off the solid component, this was washed thoroughly with water and dried ^{at 80 ° C. in vacuo.}

The polymer-coated graphite fluoride obtained by this procedure weighed 122.5 g in the dry state and contained 18.8% by weight of the copolymer of styrene and Methyl methacrylate.

Example 8

Using the same flask as in the previous examples, 280 ml of water, 200 ml of acetone, 100 g. of the graphite fluoride (CF) _n used in Example 1 and 10 g of methyl methacrylate monomer mixed with stirring at room temperature. While stirring was continued, 10 ml of 6% strength aqueous solution of sulfurous acid were added to initiate the polymerization reaction. At this stage, the pH of the aqueous reaction system was about 3. Stirring of the reaction system was continued for 5 hours after the addition of the sulfurous acid solution. The converted slurry was then filtered to separate off the solid component, this was washed thoroughly with water and dried ^{at 70 ° C. in vacuo.}

The polymer-coated graphite fluoride obtained by this procedure weighed 105 g in the dry state and contained 4.8 wt% polymethyl methacrylate.

To determine the dispersing properties of this polymer-coated Graphite fluorides in oil became 1 part by weight of the coated graphite fluoride at 100 parts by weight Turbine oil No. 40 added at room temperature, and that Mixing was carried out using a homogenizer operated at 10,000 rpm for 10 minutes. Then the mixture was treated in a centrifuge separator operating at 3000 rpm for 5 minutes, thereafter the mixture was left to stand at room temperature. After 60 minutes, the remained coated graphite fluoride particles still almost completely dispersed in the oil, although sedimentation of a small part of the graphite fluoride particles was established.

For comparison, the untreated graphite fluoride used as starting material in this Example 8

particles in the same turbine oil using the same procedure dispersed. Upon removal from the centrifuge separator, the graphite fluoride particles experienced almost complete sedimentation in the oil within a period of 15 minutes.

Example ^

The graft polymerization process of Example 8 was in generally repeated in the same way, with j'edoch the amount of methyl methacrylate reduced to 5 U and the polymerization reaction time was shortened to 3 hours.

As a result, there became a polymer-coated graphite fluoride obtained, which weighed 101.2 g in the dry state and contained 1.2% by weight of polymethyl methacrylate.

Example 10

The polymer-coated graphite fluoride prepared in Example 1 became a solid, cylindrical Body deformed using a metal tool. No other materials were added to the coated one Graphite fluoride was added and press molding was performed at

180 C while applying a pressure of 24-5 bar (250 kg / cm) carried out for 10 minutes. The press molding was easy to accomplish.

The compression molded body was subjected to a flexural strength test, which gave an average flexural strength value of 30.4 N / mm ^2. Fig. 7 is a photomicrograph showing a section of the compression molded body made in this example. As can be seen from this photomicrograph, the polymer coated graphite fluoride particles were very uniformly distributed in the compression molded body.

Furthermore, those in Examples 2, 4-, 6, 7, 8 and 9 manufactured, polymer-coated graphite fluoride individually subjected to the press molding described above under the same press molding conditions. In every pail it was very easy to accomplish compression molding, and the polymer-coated graphite fluoride particles were uniform in distributed over the molded bodies. The following Table 1 shows the flexural strength values of the compression molding these polymer-coated graphite fluorides produced, solid body. In the table, PHT1A means polymethyl methacrylate and PMA polymethyl acrylate.

Comparative example A.

For comparison, non-treated graphite fluorides (CI ¹⁾ were used as starting materials in Examples 1 and 2, subjected to press molding as described in Example 10 and (CoF) _n. Before compression molding, each of these untreated graphite fluorides was mixed in the dry state with the resin which corresponded to the polymer coatings produced in Examples 1, 2, 4, 6, 7, 8 or 9 in such a way that the resin content in the mixture obtained was mixed with the polymer content in the polymer-coated graphite fluorides of Examples 1, 2, 4-, 6, 7 »8 or 9 matched.

In either case, however, it was not possible to do so To achieve compression molding under the molding conditions described in Example 10 or the compression molded Body was too weak and brittle to determine its flexural strength.

Comparative example B

Furthermore, for comparison, the untreated graphite fluoride (CF) used in Example 1 was compared with powdered Polymethyl methacrylate mixed in a weight ratio of 1: 1, and the resulting mixture became a solid, cylindrical body after

same method and under the same molding conditions as Compression molded in Example 10. In this case, compression molding was possible, and the flexural strength of the compression molding Body was determined to be 1.67 N / mm ^ as from table evident. Fig. 8 is a photomicrograph showing a section of this press molded body. As can be seen from this photomicrograph, the distribution of graphite fluoride particles is in the press molded Body not uniform at all.

Table 1

Graphite fluoride

Example 1 coated (CF)

_{Ex. 2} it coats ^ 2 -O ₁

E.g. 4 it coats (C ₂ F) ₁

Example 6 coated es (CF) _n

Example 7 coated

Example 8 it coats (CF)

Ex. 9 coated (CF) _n

Content of

Tightened form- flexural strengthens it

g g

grafted sites bar- keit ^

Polymer resin speed (E '/ ram2) / (kg / cm ^<i ) (% by weight)

15.1

(PTIMA)

Well

30.4

o1O

19.8
(PMiA) - Well 34.1 348 10.8
(PI-IA) - Well 22.1 225 19.3
(Polyacryl
nitrile) - Well 31.2 318 18.8
(PMMA-styrene) - Well 28.0 285 4.8
(PMMA) - Well 8.34 85 1.2
(PMMA) PMMA
5g Well 2.55 26th - bad 1.67 17th

"Comparative Example B untreated (GF),

Example 11

The polymer-coated graphite fluoride produced in Example 1 was shaped into a solid, cylindrical body by the compression molding method described in Example 10 and under the deformation conditions mentioned there, and test pieces each in the form of a rectangular plate of 10 mm × 30 mm and 2 mm thick were made cut out of the compression molded body. The test pieces were divided into four groups, which were subjected to the following four kinds of treatments. On each of the treated test pieces, the contact angle of the polymer-coated and compacted graphite fluoride for water at 25 ° C. was measured by the usual droplet method for a surface perpendicular to the direction of pressing during compression molding.
Treatment A: The area of measurement of the test piece became

washed off with ethanol.

Treatment B: In a closed glass container, the test piece was immersed in about 50 ml of water, and the glass container was shaken at about 200 cycles per minute for one hour and then washed the measuring surface of the test piece with ethanol.

Treatment G: The area of measurement of the test piece was made lightly with emery paper ► of fineness polished and then the surface was washed with ethanol.

Treatment D: The test piece was given treatment C first and then treatment B was carried out.

The results of the measurements of the contact angle are summarized in Table 2 below.

Comparative example C

For comparison, test pieces were made with those in Example 11 mentioned dimensions from the compression molded body of the Comparative example B (mixture of untreated Graphite fluoride and polymethyl methacrylate) cut out and subjected to the treatments and measurements described in Example 11. Table 2 contains the values for the contact angle obtained by measuring the test pieces of Comparative Example C.

Tabel A. 2 C. D. 115 ° 130 ° 128 ° 131 ° * 110 ° 89 ° BEFORE APPLICATION Contact angle Example 11 B. Comparison ex. C. 115 ° 105 °

* The surface of the test piece was not smooth and had considerable corrugations.

The samples of Example 11 in both pretreatment C and pretreatment D gave greater values of des Contact angle in comparison with the values obtained after pretreatment A or pretreatment B. The reason for this is believed to be that partial or local peeling off of the polymethyl methacrylate coating by polishing while exposing graphite fluoride surfaces Auftr $ t.Im EaIl of the sample of Comparative Example C, which the pretreatment D subjected it is believed that the very small value of the contact angle is due to the separation of some graphite fluoride particles is caused by the treated surface of the test piece.

The following Examples 12 and 13 show the addition of one Powder of a synthetic resin or synthetic plastic to a polymer-coated graphite fluoride

• »ι '■> - · f ■ -

according to the invention in compression molding of the graphite fluoride to a solid body.

Example 12

Each of the examples 1, 2, 4, 6, 7i, 8 and 9 herge Asked, polymer-coated graphite fluoride was in the dry state with a powdery synthetic Synthetic resin selected from polymethyl methacrylate (IWlA), phenolic resin, polyacetal resin and ABS resin in the the proportions given in Table 3 below. Any mixture of coated graphite fluoride and plastic powder became a cylindrical solid body with a diameter of 50 mm using a Shaped metal shape. The compression molding was carried out at 180 ° C. while applying a pressure of 24-5 bar (250 kg / cm). Each mixture showed good moldability so that compression molding was easy to do, and there was no difficulty in releasing the molded body from the metal tool. The molded body were subjected to the flexural strength test, the results of these are listed in Table 3. Furthermore, it was determined by microscopic observation, that the polymer-coated graphite fluoride particles are solid in each molded in this example Bodies were uniformly distributed in the molded body.

Comparative Example D.

For comparison, that used in Example 1 was untreated Graphite fluoride (CF) with any of the in the example 12 plastic powders used mixed in the proportions given in Table 3, and that Untreated graphite fluoride (CUF) used in Example 2 was mixed with polymethyl methacrylate powder, as shown in Table 3 as well. The compression molding procedure described in Example 12 was followed by all these mixtures repeated. However, in some cases it was impossible to achieve the desired deformation,

and in each case of successful compression molding, it was found that the distribution of graphite fluoride particles in each molded article was significantly non-uniform. The shaped in this experiment, the solid bodies were subjected to the test for flexural strength, the results are also listed j in Table ⁷ below.

• ·

-40-Table 3

Graphite fluoride

Content of grafted polymer (wt .-%) added Verforin resin to 10g availability
Graphite fluoride

Flexural strength

(N / mm ² ) (kg / cm ² )

Example 1, coated (CF) ₁

Ex.1, coated. ()

Example 2, coated ( ^C 2 ^F ) _n

Example 4, coated (CF) _n

Example 6, coated (OT)

E.g. 71 coating
tetes ( ^{c: F} )

Example 8, coating
tetes ()

Example 8, coating
tetes (OT)

9, coated
tetes (OT) _n

Ex. 9, coating
tetes' (CFl

19.8

(PI-MA)

10.8 (PMA)

, 19.3 (polyacrylonitrile)

18.8 (EHMA-styrene)

4.8 (PMlA)

1.2

(PMMA) PMMA
1.0 g

Phenolic resin
3.0 g

Phenolic resin
7.5 g

Phenolic resin

3.0 g

Phenolic resin
■ 7.5 g

Acetal resin

2.1 g

SECTION
1.0 g

EMMA
1.0 g

PM-LA
0.1 g

SECTION
6.0 g

Well
Well
Well

Well
Well

Well

Well
Well
Well

32.9 335 34.3 350 39.0 398

33.4 37.8

28.9 30.4 4.41 35.3

340 385

320

295 310

45 360

See Ex. D.
.not treated
deltes (CF) _n PM'IA
1.5 g not possible,
to defor
men - 17th See Ex. D.
η i.t behan
deltes (C ₂ ¹ O _n PtIMA
3.0 g ti - 21 See Ex. D.
untreated
tes (CF) _n PMMA
5.0 g bad 1.67 28 ti _ Phenolic resin
5.0 g ir 2.06 18th Il _ Acetal resin
7.0 g ti 2.75 Il SECTION
5.0 κ Il 1.77

Example 15

The polymer-coated graphite fluoride prepared in Example 8 was mixed in the dry state with a pulverized ABS resin, phenolic resin or polyacetal resin, each in the proportions shown in Table 4 below. Each mixture was press molded in a metal die to produce a solid, cylindrical body. Press molding was carried out at 100-180 ⁰ C (measured at the surface of the metal die) by applying a pressure of 14-7-197 "bar (150-200 kg / cm" ¹⁾ carried out for about 10 minutes.

The moldings were subjected to an abrasion test at which each sample is subject to a relative movement with a Speed of 1000 m / min under a pressure of 29.4 bar (30 kg / cm) was forced. In the table the results of this test are listed.

Comparative example E.

For comparison, the untreated graphite fluoride used in Example 8 was used in a dry state with each of the three kinds of plastics mentioned in Example 13 were mixed, and each mixture was mixed with that in Example 13 subjected to the compression molding process. The molded bodies were subjected to the aforementioned abrasion test, the results of this are given in Table 4.

It 9 1

ff * »

-42 table

Graphite fluoride

Added resin and weight ratio of resin to graphite flaoride

Abrasion (mg / cm .h)

Example 13 coated
(OP) _n
(Ex. 8) Phenolic resin
6.50: 100 2.0 Il Polyacetal resin
6.30: 100 17.1 ABS resin
6.50: 100 18.6 Cf. not treated
deltes (CF) _n Phenolic resin
50:50 19.3 E.g. Il Polyacetal resin
70:30 80.5 Il ABS resin
50:50 91.1

The following examples show the effect of adjusting the pH of the aqueous reaction system to 5-9 the graft polymerization stage according to the invention.

Example 14

This example is a modification of the graft polymerization in view of the pH of the reaction system only Procedure of Example 1.

In the apparatus described in Example 1 and at the temperature mentioned there, the mixing of 100 g of powdered graphite fluoride (Ci ¹ ), 280 ml of water, 200 ml of ethanol and 25 g of methyl methacrylate monomer and the addition of the 20 ml of 6% aqueous solution of sulphurous Acid carried out according to the information in Example 1. At this time, the pH of the reaction system in the state of aqueous dispersion was about

When the sulfurous acid solution had been added, the pH of the aqueous dispersion was raised to 7.7 by adding sodium hydroxide. The stirring of the extraction system was continued for 4 hours after the pH adjustment, then the reaction system was filtered to separate the solid component, which was washed and dried in the same manner as in Example 1.

In this way, 122.5 g of dry product in powder form was obtained. It was confirmed by microscopic observation that the individual graphite fluoride particles were well coated with polymer. In this product, neither graphite fluoride free of polymer nor polymer free of graphite fluoride particles could be observed. The polymer-coated graphite fluoride was subjected to benzene extraction for 4-8 hours, and both the extract and the undissolved solid were subjected to infrared absorption spectrum analysis, which gave the same results as in Example 1. Therefore, the polymethyl methacrylate grafted on the surfaces of the graphite fluoride particles out of question. The content of polymethyl methacrylate was 18.4 wt .- certain herein to% by thermogravimetric analysis of the polymer coated graphite fluoride In Example 1, the polymer content of 15 * 1 ^c / ° '-A-IIS was that value of the polymer content was 90% the Pfropfvermögen calculated, given by the proportion of the polymer grafted on the graphite fluoride to the monomer initially charged in the polymerization reaction vessel «. For comparison, it should be noted that in the case of Example 1, the grafting capacity was calculated to be 71 % .

Example 15

Using the same apparatus as in the previous examples, 250 ml of water, 200 ml of ethanol, 100 g of the graphite fluoride mentioned in Example 2 ( ^C 2 ^F ^ n

and 30 g of methyl methacrylate monomer mixed with stirring while a constant temperature of 60 ^° C. was maintained in the bath. With continued stirring, 50 ml of 4% aqueous solution of 2.2 ^L azobis (2-amidinopropane) dihydrochloride was added to the mixture as a polymerization initiator. At this time, the pH of the aqueous reaction system was about 3. Soon after the addition of the polymerization initiator, sodium hydroxide was added to adjust the pH of the reaction system to 7-0. After adjusting the pK value, the reaction system was further stirred for 3 hours. Then, the unreacted slurry was filtered to separate the solid component, this was washed thoroughly with water and .getrocknet in "vacuo at 80 ⁰ C.

The polymer-coated graphite fluoride obtained by this procedure weighed 128.5 g in the dry state and contained 22.2% by weight polymethyl methacrylate. With this one Procedure, the grafting capacity was calculated to be 95%.

For comparison, this procedure was repeated except that the addition of sodium hydroxide was omitted xrarde. This means that the pH of the aqueous Reaction system remained at about 3.

The polymer-coated graphite fluoride obtained in this case weighed 118.3% in the dry state and contained 15.5% by weight of polymethyl methacrylate, so that the grafting capacity was calculated to be 61 % .

Example 16

Using the same apparatus as in the previous examples, 250 ml of water, 250 ml of ethanol, 100 g of the graphite fluoride ( ⁰ F) _n used in Example 1 and 30 g of methyl acrylate monomer were mixed with stirring while the constant temperature bath was kept ^{at 60 ° C} became. With continued stirring, 20 ml of 6% strength

'_ _h ^ _ 32392Ί3

aqueous solution of sulfurous acid was added to the mixture in the flask. At this time, the pH of the aqueous reaction system was about 2. Soon after the addition of the sulfurous acid solution, an aqueous solution of potassium hydroxide was added to adjust the pH of the reaction system to 6.5. After adjusting the pH, stirring of the reaction system was continued for 3 hours. The converted slurry was then filtered to separate off the solid component, this was washed thoroughly with water and dried ^{at 70 ° C. in vacuo.}

Figs. 9 is a photomicrograph of the graphite fluoride obtained by this "procedure, polymer-coated The product weighed in the dry state 129, *.) - g and contained 22.7 wt .-% polymethyl acrylate, so that the Pfropfvermögen was calculated to be 98%.

For comparison, the procedure was repeated except that the addition of potassium hydroxide solution was omitted became. This means that the pH of the aqueous reaction system was left at about 2.

The graphite fluoride obtained in this case, polymer-coated weighed in the dry state 115 3 B ^an d contained 13 ·> 3 wt -.% Polymethyl acrylate, so that the Pfropfvermögen to 51 ° / ° calculated. Fig. 10 is a photomicrograph of the polymer-coated graphite fluoride obtained in this case.

Example 17

Using the same apparatus as in the previous examples, 250 ml of water, 200 ml of methanol, 100 g of the graphite fluoride used in Example 15 (CpF) and 20 g of methyl acrylate monomer mixed with stirring, while the bath was kept at a constant temperature of 60 ° C. With continued stirring were

50 ml of 4% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride was added to the mixture as a polymerization initiator. At this time, the pH of the aqueous reaction system was about 3 times. Soon after the addition of the initiator, the pH of the reaction system was adjusted to 5 »4- by adding an aqueous sodium hydroxide solution. After adjusting the pH, stirring of the reaction system was continued for 4 hours. The converted slurry was then filtered to separate off the solid component, this was washed thoroughly with water and dried ^{at 70 ° C. in vacuo.}

The polymer-coated graphite fluoride thus obtained weighed 118.0 g in the dry state and contained 15.3 wt% polymethyl acrylate. In this case it was Grafting capacity 90%.

For comparison, the procedure with the exception repeated that the addition of the sodium hydroxide was omitted. This means that the pH of the aqueous Reaction system was left at about 3. The polymer-coated graphite fluoride obtained in this EaIl weighed 109.4 g in the dry state and contained 8.6% by weight of polymethyl acrylate, so that the graft could be 47% was.

Example 18

Using the same apparatus as in the previous examples, 250 ml of water, 200 ml of methanol, 100 g of the graphite fluoride (C]?) Used in Example 14 and 20 g of methyl methacrylate monomer were mixed with stirring while the constant temperature bath was kept ^{at 60 ° C} became. While stirring was continued, 50 ml of a 4% aqueous solution of the polymerization initiator used in Example 17 was added to the mixture in the flask. At that point it was

the pH of the aqueous reaction system about 3 · Soon after the addition of the polymerization initiator, the pH of the reaction system became through. Addition of sodium hydroxide adjusted to 8.5. Thereafter, stirring of the reaction system was continued for 4 hours. The converted slurry was then filtered to separate off the solid component, this was washed with water and dried ^{at 70 ° C. in vacuo.}

The graphite fluoride obtained in this manner, polymer coated weighed in the dry state S 119.4 and contained 16.2 wt -.% Polymethyl methacrylate. In this case, the grafting capacity was 97%

For comparison, the procedure was repeated except that the addition of sodium hydroxide was omitted became. This means that the pH of the aqueous reaction system was kept at about 3. This in polymer-coated graphite fluoride obtained in this case weighed 110.8 g in the dry state and contained 9.7% by weight of polymethyl methacrylate so that the grafting capacity was 54%.

Example 1 ^

Using the same apparatus as in the preceding examples, 200 ml of water, 200 ml ethanol, 100 of the graphite fluoride used in Example 14 (C ¹⁾ g and 30 g of acrylonitrile monomer with stirring mixed while the bath was maintained at a constant temperature of 60 ⁰ C . While stirring was continued, 50 ml of a 4% aqueous solution of the polymerization initiator used in Example was added to the mixture in the flask. At this time, the pH of the aqueous reaction system was about 3. Soon after the addition of the polymerization initiator, the pH of the reaction system was adjusted to 7> 1 by adding sodium hydroxide. Thereafter, the reaction system was stirred

continued for 3 hours. The converted slurry was then filtered to separate off the solid component, this was washed with water and dried ^{at 80 ° C. in vacuo.}

The polymer-coated graphite fluoride obtained in this case weighed 127.0 g when dry and contained 21.3% by weight polyacrylonitrile. In this case, the grafting capacity was 90%.

For comparison, the procedure was repeated except that the addition of the sodium hydroxide was omitted. This means that the pH of the reaction system was kept at about 3. The polymer-coated graphite fluoride obtained in this case weighed 118.0 g and contained 15.3% by weight of polyacrylonitrile, so that the grafting capacity was 60 % .

Example 20

Using the same apparatus as in the previous examples, 250 ml of water, 200 ml of ethanol, 100 g of the graphite fluoride (CI ¹ ) used in Example 14 and 20 g of styrene monomer were mixed with stirring while the bath was kept ^{at 60 ° C. at a constant temperature} . While stirring was continued, 50 ml of 4% aqueous solution of the polymerization initiator used in Example 17 was added to the mixture in the flask. At that time, the pH of the aqueous reaction system was about 3. Soon after the addition of the polymerization initiator, the pH of the reaction system was adjusted to 7.1 with the addition of sodium hydroxide. Thereafter, stirring of the reaction system was continued for 3 hours. The converted slurry was then filtered to separate off the solid component, this was washed thoroughly with water and dried ^{at 80 ° C. in vacuo.}

The polymer-coated graphite fluoride obtained in this way weighed 118.2 g in the dry state and contained 15% _. 4% by weight polystyrene. In this case the potato capacity was 91%

For comparison, this procedure was repeated with the exception that the adjustment of the pH with the addition of sodium hydroxide was omitted. The polymer-coated graphite fluoride obtained in this case weighed 111.0 g and contained 9.9% by weight of polystyrene, so that the grafting capacity was 55 ° / ° .

Example 21

Using the same apparatus as in the previous examples, 280 ml of water, 200 ml of ethanol, 100 g of graphite fluoride (CF) used in Example 14 and 6 g of methyl methacrylate monomer were mixed with stirring while maintaining the constant temperature bath at 60 ° C. While stirring was continued, 20 ml of a 4% aqueous solution of the polymerization initiator used in Example 17 was added to the mixture in the flask. At this time, the pH of the aqueous reaction system was about 3. Soon after the addition of the polymerization initiator, the pH of the reaction system was adjusted to 7-5 with the addition of sodium hydroxide. Thereafter, stirring of the reaction system was continued for 5 hours. The converted slurry was then filtered to separate off the solid component, this was washed thoroughly with water and dried ^{at 70 ° C. in vacuo.}

The polymer-coated graphite fluoride obtained in this way weighed 105.4 g in the dry state and contained 5 »1% by weight of polymethyl methacrylate. In this case, the grafting ability was 90 %.

* i * 5 * ö- *

For comparison, this procedure was repeated with the exception that the adjustment of the pH by adding sodium hydroxide was omitted. The polymer-coated graphite fluoride obtained in this case weighed 102.7 g in the dry state and contained 2.6% by weight of polymethyl methacrylate, so that the graft ν enable was 4-5 % .

Example 22

As a pretreatment, 110 g of the graphite fluoride (CE) used in Example 1 were dispersed in a mixture of 200 ml of ithanol and 300 ml of water, followed by the addition of sodium hydroxide to adjust the pH of the mixture to about 10, and the result was The mixture was stirred for 30 minutes. The graphite fluoride was then obtained, washed with water and dried ^{at 80 ° C. in vacuo.}

Using the same apparatus as in the previous examples, 250 ml of water, 200 ml of ethanol, 100 g of the alkali treated graphite fluoride and 20 g Methyl methacrylate monomer mixed with stirring while maintaining the constant temperature bath at 65 ° C became. While stirring was continued, 50 ml of a 6% aqueous solution of SOp to the mixture in Piston added. At this time, the pH of the aqueous reaction system was about 5. Thereafter, became stirring of the reaction system was continued for 4 hours. Then, the reacted slurry was filtered to separate the solid component, which became thoroughly washed with water and dried in vacuo at 80.degree.

The polymer-coated graphite fluoride obtained in this way weighed 118.2 g in the dry state and contained 15.4% by weight polymethyl methacrylate. In this Fall, the grafting capacity was 91%.

Example 25

Those in Examples 14, 15, 17, 19, 20 and 21 through Adjustment of the pH of the polymerization reaction E; systems The polymer-coated graphite fluorides produced were individually as described in Example 10 Compression molding process without adding any other Materials subject. In feather jail it was easy to carry out compression molding, and the polymer-coated graphite fluoride particles were uniform in that molded body distributed. The molded body were subjected to the flexural strength test, the results of which are shown in Table 5 below. For comparison, those in the same Examples without adjusting the pH of the polymerization reaction systems produced, polymer-coated graphite fluoride individually the same compression molding process subjected. In these cases too, the polymer-coated graphite fluoride particles were uniform in each Molded body distributed. Table 5 shows the results of the flexural strength test on the molded body of these polymer-coated graphite fluorides.

Table 5

Polymer-coated with adjustment of the pH

Polymer coated without adjusting the pH

Graphite fluor id

Content of grafted polymer (% by weight)

Flexural strength _o
(kg / cnT)

Content of grafted polymer (% by weight)

Flexural Strength (N / mm ^) (kg / cm ² )

Example 14,
tetes ( coating 18.4
(PMMA) 37.1 378 12.1 27.5 280 ■ ·
• q
I. . . Example 15,
tetes ( coating 22.2
(PMMA) 38.3 390 15.5 31.2 318 \ η * *
ro :. *.
': · ..- Example 17.
tetes ( coating (PMA) 31.5 319 8.6 19.9 203 • ·
• β · ·
* <*
W «
* * / ■ J
• · · Example 19,
tetes (
Example 20,
tetes ( coating
coating , 21.3
(Polyacryl
nitrile;
, 15.4
(Polystyrene) 34.4
22.9 351
235 15.3
9.9 27.0
21.5 275
219 • J rf Example 21,
tetes ( coating (PMMA) 8.85 90 2.6 4.61 47 CjO
hO
CjO
co
ro

Example 24

The in Example 21 by adjusting the pH-Verter »des Polymerization reaction system manufactured, polymer-coated Graphite fluoride was in the dry state with a powdery polymethyl methacrylate resin, Phenolic resin, ABS resin or polyacetal resin in each case in the proportions given in Table 6 below mixed and each mixture became a solid, cylindrical body under the same molding conditions compression molded as in Examples 10 and 23. In each Case, the compression deformation was easily achieved, and it there was no difficulty in releasing the molding from the metal tool. Through microscopic It was confirmed that the polymer-coated graphite fluoride particles were uniform in each molded body were distributed. The results of the flexural strength test on the molded bodies are also given in Table 6.

Table 6

Graphite resin content, tensile bending

fluoride grafted adds to 10g strength ρ

Graphite (R / mm) Polymers (kg / cm)

(Wt%) fluoride

E.g. 21, coating
tetes ( ^Ci 0 _n (PMKA) PMIiA
1.0 g 29.4 300 Il Il PMHA
7.5 g 36, p 375 Il Il Phenolic resin
3.0 g 32.4 330 II Il SECTION
6.0 g 35.3 360 II Il Acetal resin
3.0 g 31.9 325

The following Examples 25 to 27 show the preparation of polymer-coated graphite fluoride according to the invention in a semi-dry process, which by an extremely small amount of liquid medium is characterized in the graft polymerization process.

Example 25

As a pretreatment, 500 g of the graphite fluoride ( ⁰ ^) described in Example 1 were dispersed in a mixture of 15 g water and 1000 g ethanol, which were present in a 5 l beaker, followed by the addition of 10% aqueous solution of Sodium hydroxide to adjust the pH of the mixture to 9 while stirring the mixture continuously. When the pH decreased below 9 as a result of the consumption of the added sodium hydroxide in a neutralization reaction, further sodium hydroxide solution was added to raise the pH to 9. This procedure was repeated until the pH of the mixture almost remained unchanged from 9, and stirring was then continued for a further 50 minutes. Then, the mixture in the form of a slurry was filtered to separate the graphite fluoride particles, these were washed with water and dried. About 500 g of alkali-treated graphite fluoride (CF) _{n were} obtained in this treatment.

100 g of the alkali-treated graphite fluoride were poured into a 1 liter three-necked flask immersed in a bath at a constant temperature of 65.degree. Then 0.6 g of water and 0.4 g of ethanol were added to the graphite fluoride in the flask with vigorous stirring. AX Next, 10 ml of 6% sulfurous acid solution and 10 g of methyl methacrylate monomer were added to the mixture in the flask. Thereafter, stirring of the obtained reaction system was continued for 4 hours to complete the polymerization reaction. The product of the polymerization reaction was ^{dried in vacuo at 80 °} C. for 6 hours.

The product of this treatment weighed 105.0 g in a dry state, and it was confirmed to be a polymer-coated one Graphite fluoride with a content of 4.8 wt .-% polymethyl methacrylate, which is on the surfaces of the graphite

fluoride particles was grafted, acted. -The "Ffropfverwurde calculated at 50 / ό.

The graft polymerization process of this example was repeated with the exception that the Kengen were reduced at solution of sulfurous acid and HethylmethacrylatmonomereEi to 5 ^m l or 5 E. The polymer-coated graphite fluoride obtained in this case weighed 102.5 g in the dry state and contained 2.2% by weight of polymethyl methacrylate, so that the graft ratio was 46 % .

Example 26

The alkali treatment of graphite fluoride (ClO _n) described in Example 25 was repeated except that an increased amount of sodium hydroxide was used to adjust the pH of the treated system to 11.

Using 100 g of the treated in this way Graphite fluoride became the graft polymerization process of Example 25 carried out in the same way, except that 2 g of 2,2'-azobis (2-amidinopropane) dihydrochloride were used in place of the sulfurous acid solution and the amount of methyl methacrylate monomer increased to 30 g became.

The graphite fluoride obtained in this manner, polymer coated weighed 109.7 g in the dry state, and contained 8.8 wt -. ° / o polymethylmethacrylate. The graft ν enable was 32 %.

The graft polymerization process of this example is shown repeated again, but with 10 ml of the solution of sulfurous acid as the polymerization initiator and 10 g Acrylonitrile monomer instead of methyl methacrylate monomer were used. The polymer-coated graphite fluoride obtained in this case weighed in the dry

stood 104.4 g and contained 4.2% by weight of polyacrylonitrile, so that the grafting capacity was 44 % .

Example 27

A 3 1 three-necked flask was kept in a constant temperature bath of 40 ⁰ C, and 500 g of Graphitfluoridε (CgIO described in Example 2 _n to the flask filled ammonia gas was blown into the flask for 30 minutes under stirring of the graphite fluoride in a. An amount of 100 ml / min was blown in. The temperature of the bath ^{was then increased to 130 °} C. and this temperature was then maintained for 1 hour The graphite fluoride treated in this way was washed with water and dried.

Using "100 g of the ammonia treated Graphite fluoride became the graft polymerization process of Example 25 using 10 ml of solution of sulfurous acid and 10 g of methyl methacrylate monomer identical repeated.

The Graph.itfluorid obtained in this Pail, polymer coated weighed 105.4 g in the dry state, and contained 5.1 wt -.% Polymethyl methacrylate. In this case the grafting capacity was 5 ^%

Example 28

Using 100 g of the untreated graphite fluoride (CF) _n described in Example 1 instead of the alkali-treated graphite fluoride used in Example 26, the graft polymerization process of Example 26 for the polymerization of methyl methacrylate was carried out under otherwise identical conditions.

The polymer-coated graphite fluoride obtained in this case weighed 102.1 g when dry and contained

2.1 Gevv '.- / o polymethyl methacrylate, so that the grafting capacity 7%.

Beis-QJel 29

Using 100 g of the described in Example 2, Untreated graphite fluoride (C ~ F) instead of the ammonia-treated graphite fluoride used in Example 27 was used the graft polymerization process of Example 27 was carried out under otherwise identical conditions.

The polymer-coated graphite fluoride obtained in this case weighed 101.2 g when dry and contained

1.2% by weight of polymethyl methacrylate. The grafting capacity was 12%.

As previously described, is the graft polymerization coating method according to the invention not only on graphite fluoride, but also on numerous other materials, which are useful as solid lubricants are applicable. The following examples show the application of the invention to typical solid lubricants.

example 30th

A Λ 1 three-necked flask was kept in a constant temperature bath at 60 ^° C., and 250 ml of water, 200 ml of ethanol, 100 g of powdered molybdenum disulfide and 12 g of methyl acrylate monomer were mixed in the flask with stirring. While stirring was continued, 50 ml of a 4% aqueous solution of 2,2'-azobis- (2-amidinoproparO-dihydrochloride was added to the mixture. At this time, the pH of the aqueous reaction system was about 2. Then, the The pH of the reaction system was adjusted to 8.5 with the addition of an aqueous sodium hydroxide solution. Thereafter, the stirring of the reaction system was stopped for 4 hours to complete the polymer

sation reaction continued. The converted slurry was then filtered to separate off the solid component, this was washed thoroughly with water and dried ^{at 80 ° C. in vacuo.}

The powdery product of this treatment weighed dry Condition 111.6 g, and it was confirmed that it contained 10.4% by weight of polymethyl acrylate grafted to were bonded to the surfaces of the iolybdenum disulfide particles. In this case, the grafting capacity was 97%

The procedure described above was repeated with the exception that the pH was adjusted to 70 by reducing the amount of sodium hydroxide used for the adjustment. The polymer-coated molybdenum disulfide obtained in this case weighed 118.4 g in the dry state and contained 15.5% by weight of polymethyl acrylate. The grafting capacity was 92 %.

The procedure of this example was repeated again with the exception that the adjustment of the pH was omitted. This means that the pH of the aqueous reaction system was left at about 2. The molybdenum disulfide obtained in this case, polymer-coated weighed 106.4 g in the dry state, and contained 6.0 wt -. ° / o polymethylacrylate. The graft ν enable was 53%.

Example 31

Using the same equipment as in Example 30 became 480 ml of water, 100 g of powdered graphite from a natural source and 20 g of methyl acrylate monomer mixed with stirring. While stirring was continued, 20 ml of a 6 oil aqueous solution of sulfurous acid was added to the mixture in the flask. To this The time the pH of the aqueous reaction system was about 2. Then the pH of the reaction system was

systems adjusted to 7-3 by adding an aqueous sodium hydroxide solution. Thereafter, stirring of the reaction system was continued for 4 hours to complete the polymerization reaction. The converted slurry was then filtered to separate off the solid component, this was washed thoroughly with water and dried ^{at BO 0 C in vacuo.}

The powdery product of this treatment weighed 119.2 g when dry and was found to contain 16.1% by weight of polymethyl acrylate which was grafted to the surfaces of the graphite particles. In this case, the grafting capacity was 96 %.

The procedure described above was repeated with the exception that the addition of the sodium hydroxide to adjust the pH was omitted. The polymer-coated graphite obtained in this case weighed 111.8 g in the dry state and contained 10.6% by weight of polymethyl acrylate, so that the grafting capacity was 59 % .

Claims (1)

Claims 1. Modified graphite fluoride comprising fine particles of graphite fluoride, which with a vinyl-like polymer, which is bonded to the surfaces of the graphite fluoride particles by graft polymerization are coated. 2. Modified graphite fluoride according to claim 1, characterized characterized in that the content of the polymer in the modified graphite fluoride is at least 0.5% by weight . 3. Modified graphite fluoride according to claim 2, characterized characterized in that the content of the polymer in the modified graphite fluoride is not greater than 50% by weight is. -f.- 4. Modified graphite fluoride according to one of the claims 1 to 3, characterized in that the polymer polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, Polyacrylonitrile, poly-N-methylolacrylamide, Polyvinyl chloride, polyvinyl acetate, polystyrene, polyvinylbenzene, Is polyvinylidene fluoride or a copolymer thereof. 5 · Codified graphite fluoride according to claim 4, characterized characterized in that the polymer polymethyl acrylate, Polymethyl methacrylate, polyacrylonitrile, polystyrene or is a copolymer of styrene and acrylonitrile. 6. Modified graphite fluoride according to one of claims 1 to 5> characterized in that the graphite fluoride is (C ₂ F) _n or a mixture thereof. 7 · Modified graphite fluoride according to one of the preceding Claims, characterized in that the graphite fluoride particles coated with the polymers are compacted to form a solid body. 8. Modified graphite fluoride according to claim 7, characterized characterized in that the solid body further comprises a synthetic resin which together with the modified Graphite fluoride is compacted. 9. Modified graphite fluoride according to claim 8, characterized characterized in that the total weight of the synthetic resin and the polymer is not greater than the weight of graphite fluoride are in the solid body. 10. Modified graphite fluoride according to claim 9, characterized characterized in that the synthetic resin is made from polymethyl methacrylate, phenolic resins, polyacetal resins and ABS resins is selected. 11. Process for the preparation of a modified graphite fluoride according to claim 1, characterized in that it includes the steps of mixing the graphite fluoride in Form of fine particles with at least one vinyl-like monomer which leads to a radical Polymerization or a radical copolymerization is capable of comprising, the mixing in the presence is carried out by water, and that a polymerization initiator for the vinyl-type Monomers is added to the mixture obtained in the previous stage, so that the vinylarti- ~ The monomers undergo polymerization or copolymerization and adhere to the surfaces of the graphite fluoride particles be bound by graft polymerization. 12. The method according to claim 11, characterized in that the pH of the polymerization reaction system is adjusted to a value in the range from 5 to 9 after the addition of the initiator. 13 · The method according to claim 12, characterized in that the pH of the reaction system by adding a alkaline compound is adjusted to the reaction system. 14. The method according to claim 12, characterized in that the pH of the reaction system by treatment of graphite fluoride with an alkaline compound is adjusted prior to the step of mixing the graphite fluoride with the vinyl type monomer or monomers. 15 · The method according to any one of claims 11 to 14, characterized characterized in that the mixing stage by dispersing the graphite fluoride and the vinyl-type Monomers carried out in a mixture of water and an organic, water-soluble solvent will. 16. The method according to claim 15 »characterized in that that alcohols, ketones, ethers or amines are used as organic solvents. 17. The method according to claim 16, characterized in that that ethyl alcohol is used as the organic solvent, the weight ratio of the water to ethyl alcohol in the range from 0.1: 1 to 2.3: 1. 18. The method according to claim 16, characterized in that 1 to 100 parts by weight of the graphite fluoride and 0.1 to 100 parts by weight of the vinyl-like monomer or monomers in a mixture of 100 parts by weight of water and 1 to 100 parts by weight of the organic solvent are dispersed. 19 · The method according to any one of claims 11 to 14, characterized characterized in that the mixing step is carried out by dispersing the graphite fluoride and the vinyl type monomer (s) is carried out in a mixture of water and a surfactant. 20. The method according to claim 19, characterized in that that 1 to 100 parts by weight of graphite fluoride and 0.1 to 100 parts by weight of the vinyl-like monomer or monomers dispersed in a mixture of 100 parts by weight of water and 1 to 50 parts by weight of the surfactant will. 21. The method according to any one of claims 11 to 14, characterized characterized in that the mixing stage is carried out by wetting the graphite fluoride and the vinyl-like monomer or monomers is performed with a relatively small amount of water. 22. The method according to claim 21, characterized in that the water with an organic, water-soluble solvent is mixed. 25. The method according to any one of claims 11 to 14, characterized characterized in that 100 parts by weight of graphite fluoride with 0.1 to 100 parts by weight of the vinyl type monomer or monomers in the presence of a mixture of 0.1 to 100 parts by weight of water and 0.1 to 300 parts by weight of one organic, water-soluble solvents are mixed. 24. The method according to any one of claims 11 to 14, characterized characterized in that 100 parts by weight of graphite fluoride with 0.1 to 100 parts by weight of the vinyl-like monomer (s) in the presence of a mixture of 0.1 to 600 parts Parts by weight of water and 0.1 to 150 parts by weight of one surfactants are mixed. 25. The method as claimed in claim 20, 23 or 24, characterized in that that the amount of the polymerization initiator in the range of 0.01 to 20 wt .-%, based on the or the vinyl type monomers. 26. The method according to any one of claims 11 to 25 , characterized in that the vinyl-like monomer or vinyl-like monomers used is acrylic acid, methacrylic acid, acrylates, methacrylates, acrylic esters, methacrylic esters, acrylonitrile, H-methylolacrylamide, vinyl chloride, vinyl acetate, styrene, vinylidene fluoride or divinylbenzene . 27. The method according to claim 26, characterized in that the polymerization initiator is sulfur dioxide, sulphurous Acid, hydrogen sulfites, potassium persulfate, azobiscyanovaleric acid or 2,2'-azobis (2-amidinopropane) dihydrochloride is used. 28. The method according to any one of claims 11 to 27, characterized in that the graphite fluoride (CP), (C2? ') or a mixture thereof is used. 29 · The method according to any one of claims 11 to 28, characterized in that the polymerization reaction at a Temperature in the range from room temperature to 70 ° C is carried out. 30. A method for producing a solid body which contains a modified graphite fluoride which, according to the method according to claim 11, wherein the method of molding comprises the steps of blending the modified graphite fluoride in powder form with a synthetic resin in powder form and applying pressure to the mixture of modified graphite fluoride. and synthetic resin at an elevated temperature. 31. The method according to claim 3O _5, characterized in that such an amount of synthetic resin is used that the total weight of the synthetic resin and the polymer in the modified graphite fluoride is not greater than the weight of the graphite fluoride in the modified graphite fluoride. 32. The method according to claim 31 *, characterized in that as synthetic resin polymethyl methacrylate, phenolic resin, Polyacetyl resin or ABS resin is used. Characterized 33 · The method of any of claims 30 to 32, that the pressure in the range of 147-44-1 bar (15O-45O kg / cm), and the elevated temperature is in the range from 100 ⁰ C to 250 ⁰ C. lies.