FI58935B - SJAELVSMOERJANDE ANTIFRIKTIONSMATERIAL - Google Patents

Description

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Patent · och regictcrstyrataan 'Anaefcan utk | d och utUkrUtM pubiicorad 30.01.8l (32) (33) (31) Pyr »*« y «uoNmim — Bo | lnJ priorluc (71) Institut Elementoorganicheskikh Soedineny Akademii Nauk SSSR, ulitsa Vavil Moscow, USSR (SU) (72) Vasily Vladimirovich Korshak, Moscow, Irina Alexandrovna Gribova,

Moscow, Martinraelilich Kabachnik, Moscow, Alexandr Petrovich Krasnov, Moscow, Alla Nikolaevna Chumaevskaya, Moscow, Olga Vladimirovna Vinogradova, Moscow, Svetlana Vasilievna Vinogradova, Moscow,

Evgenia Semenovna Krongauz, Moscow, Alla Markovna Berlin, Moscow,

Alexandr Vasilievich Vinogradov, Moskovskaya oblast, Galina Ilinichna Gureeva, Moscow, Leonid Sergeevich Zakharov, Moscow, Vladimir Dmitrievich Vorobiev, Moscow, Irina Sergeevna Mazaeva, Moscow, Georgy Viktorovich Mamatsashvili, Moscow, Natalova Monk, Moscow, Nikolai Sergeevich Zabelnikov USSR (SU) (7 ^) Oy Kolster Ab (5 ^ +) Friction reducing self-lubricating agent - Självsmörjande antifriktions-material

The invention relates to friction-reducing self-lubricating agents which are in fact plastics.

Friction-reducing self-lubricating plastics, which combine the properties of solid lubricants and structural materials, are used in the manufacture of retaining rings, bearing fittings, gear sets used in dry friction installations, components, and the like.

Friction-reducing self-lubricating plastics provide a low coefficient of friction in the absence of conventional liquid lubricants or greases.

The friction-reducing properties of the friction-reducing self-lubricating agents are due to the fact that the whole friction component is a monolithic lubricating compound.

Substances of this type can be used in equipment where liquid lubricants cannot or should not be used, such as electric vacuum units, film projectors, parts of radiant equipment, bearings intended for use at high temperatures and outdoor conditions, and the like.

Friction-reducing self-lubricating plastics are multi-component systems bonded together with polymers with all the necessary properties, above all heat resistance and heat resistance, radiation resistance, resistance to active chemicals and easy handling.

2,58935

Friction-reducing plastics use widely known solid lubricants such as graphite, molybdenum disulfide and the like as fillers. To improve the strength of the material, the filler may contain fibrous components such as asbestos, fiberglass or asbestos fabric. The filler may also contain metallic powders such as powdered molybdenum, copper, nickel or other metals to improve the thermal and electrical conductivity, formability and strength of the friction reducing agent.

These fillers are added to the friction reducing agent either separately or in combination.

The amount of filler in the friction-reducing agent can vary within wide limits, the optimal content of which is selected in each special case on the basis of the requirements that the product made of this agent must meet.

It is known in the art to use friction reducing agents in the form of plastics based on polyimides and solid lubricating fillers such as graphite, molybdenum disulphide, etc.

It is also known in the art to use friction reducing agents in which polyimides together with polyarylates and aromatic polyamides form a binder.

Rigid chain polyacrylates or aromatic polyamides added to the polyimide-based anti-friction agent stabilize its friction properties.

It is desirable to use a friction reducing agent containing U-78 by weight # polyimide, 2-95 by weight # fillers and 1-20 by weight # polyarylates or aromatic polyamides.

One of the main disadvantages of these friction reducing agents is their insufficient heat resistance. An increase in temperature from 100 ° C to 10 ° C causes an increase in the coefficient of friction from 0.08 to 0.15. As the temperature rises to 250 ° C, the properties of the friction reducing agents progressively deteriorate, resulting in weight loss, reduced performance, and finally complete destruction.

If such substances have to be used in dry friction devices, especially plain bearings, their wear resistance must be improved.

U.S. Pat. No. 3,850,820 relates to a friction-reducing material containing a carbonaceous polymer as a binder and a friction-reducing filler (graphite, molybdenum disulfide). This material has a high heat resistance under the conditions of use. The main disadvantages of this material are insufficient strength and increased brittleness, as well as the fact that the polymeric binder -carborane-containing polymer used in considerable amounts, i.e. 10-15% by weight, is difficult to obtain.

It is an object of the present invention to overcome the above disadvantages.

Accordingly, it is an object of the present invention to provide friction-reducing self-lubricating agents which have improved abrasion resistance combined with sufficient mechanical properties that do not deteriorate at high temperatures.

3,58935

The above object is achieved by providing a friction-reducing self-lubricating agent based on a nitrogen-containing polymer and combining fillers, wherein according to the invention the nitrogen-containing polymer may be fusible polyimides or polyphenylquinoxalines used in 5 to 95% by weight of the friction-reducing agent, and the filler may be molybdenum disulfide modified with phosphorus-containing acids or phosphorus-containing esters, the phosphorus content of the modified molybdenum disulfide being between 0.01 and 2% by weight and the content of the modified molybdenum disulfide being 9 to 95% by weight, based on the molybdenum with molybdenum disulfide, wherein the molybdenum disulfide content is between 1-90% by weight of the friction-reducing self-lubricating agent.

In order to produce friction-reducing self-lubricating agents with improved abrasion resistance, the nitrogen-containing polymer according to the invention must be a fusible polyimide of the general formula -O- · "-O- -Q ^ O- * -0 * 0- -ΟλΟ-

ctb oO

n = 20-1 * 00.

According to the invention, in order to produce friction-reducing self-lubricating substances with improved abrasion resistance at temperatures of the order of 300 ° C, the nitrogen-containing polymer must have a polyphenylquinoxaline having the following chemical structure: 4,58935 kAN iTh _ _ n R "= -0-; -SO 2 ~ -CO-, or is absent;

Ar = -O-, -0-0- = -O ° -0 »c ^ ° x £ cr n = 50-300.

Phosphorus-containing acids for modifying molybdenum disulphide according to the invention are ortho- and metaphosphoric acids, phosphonic acids of the general formula

R '' - P

'NoH) ^ or phosphinic acids of the general formula r' 1 IV / <·

R OH

wherein R111 and RIV are alkyl, cycloalkyl or aryl, from C1-C6, R111 and RIV being the same or different.

Phosphorus-containing esters for modifying molybdenum disulphide according to the invention can be phenyl (1,1-dihydro-perfluoroalkyl) phosphates of the general formula J> Γ (c6H50) xp <- 0CH2 (CF2) y CFj LJ? -X 5 58935 wherein x = 1-3 and y = 0-3, or phenyl (1,1-dihydroperfluoroalkoxy) cyclotriphosphazenes of the general formula <c6h50) x'a N-) j - [^ 00¾ (CF2) y cp36 wherein x = 0-6 and y = 0-3. In addition to these esters, phosphinic acid esters of the general formula rI11 ^ - p ° can also be used.

"^ -0RV

or phosphoric acid esters of the general formula \ V (0RV) 2 wherein RV is the same as R ** 1 or RIV.

Modification of molybdenum disulfide is accomplished directly by combining phosphorus-containing acids or phosphorus-containing esters having the various chemical structures described above with the starting molybdenum disulfide during mixing.

After modification with these phosphorus-containing reactants, the molybdenum disulfide according to the invention contains 0.01 to 2% by weight of phosphorus. The phosphorus content of the molybdenum sulfide is adjusted by varying the amount of phosphorus-containing compound used for the modification.

The molybdenum disulphide modified according to the invention preferably contains 0.05 to 0.1% by weight of phosphorus.

The friction reducing agent proposed according to the invention preferably contains 10 to 80% by weight of modified molybdenum disulphide. In order to improve the thermal and electrical conductivity of the proposed friction reducing agent as well as to improve its formability and strength, this friction reducing agent preferably contains a filler according to the invention, namely metal powders such as silver, copper, molybdenum or nickel powders used together or separately from 1 to 41% by weight based on the friction reducing agent.

According to an alternative embodiment of the invention, the friction reducing agent has the following composition in% by weight: fusible polyimide, 10%; molybdenum disulfide containing 0.05% by weight of phosphorus, 80%; very fine carbon 5%; and metallic molybdenum powder 5%.

According to yet another preferred embodiment of the present invention, the friction reducing agent has the following composition in% by weight: polyphenylquinoxaline 20%; molybdenum disulfide containing 0.1% by weight of phosphorus, 43%; graphite 19%; asbestos 3%; and 15% silver powder.

The friction-reducing self-lubricating agent according to the invention is characterized by high mechanical strength, excellent workability, a constant coefficient of friction over a wide temperature range and high wear resistance.

For the sake of brevity, molybdenum disulfide modified with phosphorus-containing acids or phosphorus-containing esters is hereinafter referred to as molybdenum disulfide.

Thus, for example, a friction-reducing agent prepared by compression at a temperature of 400 ° C and a pressure of 1,000 kg / cm and consisting of 90 parts by weight of a polyimide of the formula [-ΌΟγ 0O £> - © - o -O-] .

where n = 400, and 10 parts by weight of modified molybdenum disulfide containing 0.01% by weight of phosphorus has higher abrasion resistance, microhardness and strength than the molybdenum disulfide-based material (see Tables I and II).

7 '7 58935

Table I

Friction coefficient and abrasion resistance of friction reducing agents

Molybdenum disulphide Substance with di-n-heptyl sulphide phosphinic acid modified molybdenum disulphide

Wear and tear coefficient of friction Wear and tear coefficient of friction at room temperature g_ at temperature g_ 1 hour 3 hours 1 hour 3 hours over a period during 0.0037 0.09 0.0023 0.08 0.0015 0.08 0.0007 0.06

Table II

Mechanical properties of friction reducing agents

Material type Microhardness Bending stress _kg / nrn ^ _kg / an ^ _

Using modified molybdenum disulfide 40.0 660

Using molybdenum disulfide 27.0 500

The microhardness of the substances was determined in a test in which a diamond pyramid was embedded in a test substance with a specified force and the linear magnitude of the diagonal of the penetration thus formed was measured. Microhardness is defined as a load of 2 (kg) on the side surface (mm) of the penetration, provided that the angles of penetration correspond to the angles of the pyramid.

Bending stress, as used herein, is interpreted as the stress that occurs in a specimen as it decomposes.

These friction reducing agents, based on polyphenylquinoxalines and modified molybdenum disulfide, give friction kits made from them resistance to high temperatures, and the modified molybdenum disulfide used in the material gives it improved wear resistance. Thus, tests performed on anti-friction bearing retaining rings made of a proposed anti-friction agent based on polyphenylquinoxaline of formula n where n = 80 showed that at 300 ° C a substance containing modified molybdenum disulfide the wear increased to 0.0090 g in 50 hours, while the wear of similar test pieces made of molybdenum disulfide-containing material at the same temperature and time was 0.0220 g.

Other advantages and advantages of the proposed friction-reducing self-lubricating agents will become apparent from the following detailed description of the invention.

The proposed friction-reducing self-lubricating agent, which combines the properties of solid lubricants and structural material according to the invention, is a multicomponent system in which the binder is a nitrogen-containing polymer with all required properties, above all heat resistance and heat resistance, radiation resistance, active chemical resistance and good handling.

The polyimides and polyphenylquinoxalines used in this friction-reducing self-lubricating agent meet the general requirements for a polymeric binder in a friction-reducing agent.

To prepare these friction-reducing self-lubricating agents, the nitrogen-containing polymer may be a fusible polyimide of the general formula according to the invention.

ECO CO., LTD

- R-nC; CO - »n * - -G- ° -O- '-0-c" 2-0-; \ / · -' 9 58935

OyrO

0C> 'CÖD

E'- XX> XX ° X ^. · N = 20-400.

The amount of this polymeric binder is 5-95% by weight of the friction reducing agent.

According to the invention, it is possible to use both soluble polyimides having a degree of polymerization of between 20 and 400, such as those prepared from aniline phthalene and tetracarboxylic acid anhydrides, and insoluble polyimides, e.g. one based on 3,31,4,4'- diphenyloxide tetracarboxylic acid and diaminodiphenyl oxide. The main requirement for polyimides used in the proposed friction reducing agent is adequate workability.

To prepare these friction reducing agents, the nitrogen-containing polymer may likewise be polyphenylquinoxaline according to the invention having the following chemical structure - wherein R "= -O-; -SO 2 -; -CO-; or is absent -OtO-O- '- O 0 -O-! - <x &r; n = 50-300, where it is used 50-95% by weight of the friction reducing agent.

10,58935 The polyphenylquinoxalines used in this friction reducing agent have high heat resistance and heat resistance, high resistance to active chemicals and sufficient processability. Thus, for example, a polyphenylquinoxaline prepared from 3,3 ', 4,4'-tetraaminodiphenyl ether and 1,4-bis (phenylglyoxalyl) benzene of the formula ö b „where n = 160, and which molecular weight 80,000 and modified viscosity in m-cresol 72 = 0.83 dl / g, softening point 280 ° C (determined from thermomechanical curves). Thermogravimetric testing of this polymer in air with a temperature gradient of 4.5 ° / min. gave the polymer a thermal decomposition point of 480 ° C.

In order to obtain improved abrasion resistance and better mechanical properties for friction-reducing self-lubricating plastics based on fusible polyimides and polyphenylquinoxalines, 5-95% by weight of a nitrogen-containing polymer and 95-5% by weight of a filler comprising molybdenum disulfide-modified or esters, the proportion of filler being 5-95% by weight of the friction reducing agent.

The ratio of nitrogen-containing polymer to filler in this friction reducing agent can vary over a wide range depending on the specific requirements for the product made from this friction reducing agent. Thus, the addition of a large amount of fillers in the form of solid lubricants such as graphite, molybdenum disulfide and the like reduces the coefficient of friction of the friction reducing agent. However, reducing the proportion of a nitrogen-containing polymer, e.g., polyimide, to about 5% by weight results in a reduced strength 2 (impact strength of about 1-1.5 kgcm / cm), while the imide content of 95% by weight of polyol 58935 friction The reducing agent guarantees its high 2 strength (impact strength 25 kgcm / cm).

Phosphorus-containing acids for the modification of molybdenum disulphide according to the invention can be ortho- and metaphosphoric acids? phosphonic acids of general formula

R 11, -P, N (OH) 2 such as methylphosphonic, phenylphosphonic acids and the like, and phosphinic acids of the general formula R1110

RiV OH

such as di-n-butylphosphine, di-n-heptylphosphine, di-n-octylphosphine, di-n-nonylphosphine, di-n-undecylphosphine, methylphenylphosphine, dicyclohexylphosphine, diphenylphosphine, diphenylphosphine, , ditolylphosphinic, di-styrylphosphinic and other acids.

The phosphorus-containing esters used according to the invention for the modification of molybdenum disulphide may be phenyl (1,1-dihydroperfluoro-alkyl) phosphates of the general formula

O

! /.

<C6H5 °> xP- £ 0CH2 (CF2 »yCV3-x · where x = 1-3 and y = 0-3, such as triphenyl phosphate, 1,1-dihydro-perfluoroamyldiphenyl phosphate and the like? Or phenyl (1.1 -dihydroperfluoroalkoxy) cyclotriphosphazines of the general formula 12 5 8 9 3 5 <C6H50) c <-p = N ') 3 ^ CH2 <CF2> yCP3 ^ 6-x' where x = 0-6 and y = 0-3 such as hexa (1,1-dihydroperfluorobutoxy) -cyclotriphosphazine, hexaphenoxycyclotriphosphazine, phenoxypenta- (1,1-dihydroperfluorobutoxy) -cyclotriphazazine and the like.

Together with the modified molybdenum disulfide, the filler may contain molybdenum disulfide in an amount of 1 to 90% by weight, the amount of modified molybdenum disulfide being 5 to 95% by weight of the friction reducing agent. The modified molybdenum disulfide can be used in a friction reducing agent together with the molybdenum disulfide, whereby this has a beneficial effect on the economics of production.

The finely ground polyimide or polyphenylquinoxaline is thoroughly mixed with a filler, molybdenum disulfide modified with phosphorus-containing compounds or very finely divided carbon.

To produce a friction reducing agent with improved thermal and electrical conductivity, metal powders, e.g. powdered copper, silver, molybdenum or nickel, are combined in the mixture in the mixing step of the ingredients.

The metal powders used in the friction reducing agent may differ in particle size. Thus, the particle size of colloidal silver is between 0.1 and 1.5 microns, while other metal powders may have a much larger particle size. The amount of metal powders to be combined with the friction-reducing agent depends on the specific requirements for the agent. Higher concentrations of metal powder in the friction reducing agent improve its thermal and electrical conductivity, although in some cases they degrade its friction reducing properties.

The ingredients are mixed until a homogeneous mass is formed which is used like plastic. The resulting plastic in the form of a homogeneous powder is compressed at a temperature between 250-450 ° C and a pressure between 1,000-2,500 kg / cm 2 to produce articles from this friction-reducing self-lubricating agent.

.. $ · ''> 13 58935 These parts are tested for wear resistance, thermal friction properties and other mechanical properties.

Under dry friction conditions, the polymer molecules are subjected to both thermal and mechanical stresses, so that the nitrogen-containing polymeric binder together with the molybdenum sulfide modified with phosphorus-containing acids and phosphorus-containing esters forms a stronger polymer-filler bond.

After the heat treatment, the nitrogen-containing polymer, the phosphorus-containing compound (acid or ester) and the molybdenum disulfide-filler are firmly bonded to form a combination with improved abrasion resistance.

The present invention will be better understood by reference to the following specific examples which illustrate the preparation of the friction reducing agent of the invention, together with the test results.

Example 1

The friction-reducing plastic to be tested was prepared by mixing all the ingredients in a vibrating mill. The plastic thus prepared was molded into sleeve-shaped test pieces with an outer diameter of 22 mm and an inner diameter of 12 mm. In the same manner, a control specimen containing molybdenum disulfide was prepared. The friction behavior of the test pieces was tested against the surface by friction against steel at a linear velocity of 2 m / s and 2 with a load of 2 kg / cm.

The test results are shown in the tables. The composition of the plastic was as follows, in parts by weight: 90 parts of polyimide of the formula where n = 400, 10 parts of molybdenum disulphide with a particle size between 1-2 microns and treated with di-n-heptylphosphinic acid and containing 0.01% by weight -% phosphorus.

14 58935

The plastic was compressed at 400 ° C and a specific pressure of 1,000 kg / cm 2.

Table III

The friction reducing agent if- The friction reducing agent in which sa is molybdenum disulfide is a molybdenum disulfide modified with di-n-heptylphosphinic acid

Wear and tear Friction coefficient Wear and coefficient of friction at room temperature g at 1 ° C in 1 hour 3 hours 1 hour 3 hours

Table IV

Friction Reducer Microhardness Bending Stress _kg / mm_kg / cm2_ Using Modified Molybdenum Disulfide 40.0 660 Using Molybdenum Disulfide 27.0 500

Example 2 In this example, the plastic had the following composition by weight: 95 parts of a polyimide of the formula wherein n = 400; 5 parts of molybdenum disulphide having a particle size between 1-2 microns and modified with orthophosphoric acid and containing 0.05% by weight of phosphorus. The plastic was compressed and the results were tested by repeating the methods of Example 1.

r · 'i5 58935

Table V

The friction reducing agent, if- The friction reducing agent in which sa is molybdenum disulfide is molybdenum sulfide modified with orthophosphoric acid

Wear and tear Friction coefficient Wear and coefficient of friction at room temperature g at 1 g 3 hours 1 hours 3 hours

Example 3 In this example, the plastic had the following composition by weight: 10 parts of a polyimide of formula J n where n = 100; 13 parts of molybdenum disulfide having a particle size between 1-2 microns and modified with methylphosphonic acid and containing 0.03% by weight of phosphorus; 5 parts graphite, 30 parts very fine carbon, 1 part asbestos, 40 parts metallic copper powder, and 1 part metallic silver powder.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table VI

The friction reducing agent, if- The friction reducing agent in which sa is molybdenum disulphide is molybdenum disulphide modified with methylphosphonic acid

Wear and tear friction in the room Wear and tear friction at room temperature g at a roin 1 hour 3 hours 1 hour 3 hours during_time_of_01.080 0.0133 0.085 0.0142 0.0090 0.076

Example 4 In this example, the plastic had the following composition by weight: 20 parts of a polyimide of formula 58935 16 where n = 100; 33 parts of molybdenum disulfide having a particle size between 1-2 microns and modified with dicyclohexylphosphinic acid and containing 1% by weight of phosphorus; 1 part very fine carbon, 5 parts asbestos, 40 parts metallic molybdenum powder, and 1 part metallic copper powder.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table VII

Friction reducing agent, if- Friction reducing agent in which sa is molybdenum disulphide is dicyclohexylphosphinic acid modified molybdenum disulphide

Wear and tear Friction coefficient Wear and coefficient of friction at room temperature g at 1 hour 3 hours 1 hour 3 hours over time

Example 5 In this example, the plastic had the following composition by weight: 10 parts of a polyimide of the formula · -.

L J.

where n = 400; 49 parts of molybdenum disulfide having a particle size f 17,58935 of 1-2 microns and modified with diphenylphosphinic acid and containing 0.07% by weight of phosphorus, 1 part of molybdenum metal powder, and 40 parts of nickel metal powder.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table VIII

The friction-reducing agent if- The friction-reducing agent in which sa is molybdenum disulfide is molybdenum disulfide modified with diphenylphosphinic acid

Wear and tear Friction coefficient Wear and tear coefficient of friction at room temperature g at 1 g 3 hours 1 hours 3 hours during_on-time_ 0.0079 0.0004 0.073 0.0021 0.0003 0.062

Example 6 In this example, the plastic had the following composition by weight: 5 parts of a polyimide of the formula - J n where n = 100, 5 parts of a molybdenum disulphide having a particle size between 1-2 microns and modified with methylphenylphosphinic acid and containing 2 parts by weight -% phosphorus and 90 parts graphite.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

58935 18

Table IX

The friction reducing agent, if- The friction reducing agent in which sa is molybdenum disulphide is molybdenum disulphide modified with methylphenylphosphinic acid

Wear and tear Friction coefficient Wear and coefficient of friction at room temperature g at 1 g 3 hours 1 hours 3 hours

Example 7 In this example, the plastic had the following composition by weight: 15 parts of a polyimide of the formula "* n where n = 100, 40 parts of a molybdenum disulfide having a particle size between 1-2 microns and modified with metaphosphoric acid and containing 0.02 parts by weight -% phosphorus, 5 parts very fine carbon, 40 parts metallic silver powder and 1 part metallic nickel powder.

A

The plastic was pressed to a temperature of 350 ° C and a pressure of 1,000 kg / cm 2 and the resulting specimens were tested by repeating the methods of Example 1.

Table X

Friction reducing agent, if- Friction reducing agent containing sa molybdenum disulphide is molybdenum disulphide modified with metaphosphoric acid

Wear and tear Friction coefficient Wear and coefficient of friction at room temperature g at 1 g 3 hours 1 hours 3 hours

Example 8 In this example, the plastic had the following composition by weight: 5 parts of a polyimide of the formula 19 589 35 ζζΓ'-ίΟ ^ Ο- ° 0- - J n where n = 100 / and 95 parts of molybdenum disulphide / having a particle size of between 1 -2 microns and modified with di-n-butylphosphinic acid and containing 0.01% by weight of phosphorus.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table XI

The friction reducing agent, if- The friction reducing agent in which sa is molybdenum disulphide is molybdenum disulphide modified with di-n-butylphosphinic acid

Wear and tear Friction coefficient Wear and tear coefficient of friction at room temperature g_ at temperature g_ 1 hour 3 hours 1 hour 3 hours_ during_time_of_ 0.0036 0.0014 0.08 0.0022 0.0006 0.06

Example 9 In this example, the plastic had the following composition in parts by weight: 10 parts of a polyimide of the formula _J n where n = 100, 80 parts of a molybdenum disulphide having a particle size of 1-2 microns and modified with orthophosphoric acid and containing 0.05 parts by weight. % phosphorus, 5 parts very fine carbon, and 5 parts metallic molybdenum powder.

f * 20 58935

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table XII

Friction reducing agent, if- Friction reducing agent in which sa is molybdenum disulphide is molybdenum disulphide modified with orthophosphoric acid

Wear and tear of the room Friction coefficient of the room Friction coefficient of the room at temperature g at a temperature of 1 hour 3 hours 1 hour 3 hours over a period during time_ 0.0079 0.0005 0.072 0.0021 0.0004 0.062

Example 10 In this example, the plastic had the following composition by weight: 10 parts of a polyimide of the formula - h rcoXT ° T3:

Cv J "where n = 20, 30 parts of molybdenum disulphide with a particle size between 1-2 microns and treated with triphenyl phosphate and containing 0,05% by weight of phosphorus, 20 parts of molybdenum disulphide, 35 parts of graphite and 5 parts of metal molybdenum powder.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table XIII

Friction reducing agent, if- Friction reducing agent in which sa is molybdenum disulphide is triphenyl phosphate modified molybdenum disulphide

Wear and tear coefficient of wear and tear Friction coefficient of wear and tear at room temperature g at g 1 hour 3 hours 1 hour 3 hours_ during_time_of_ 0.0071 0.0005 0.057 0.0018 0.0004 0.055. ‘\’ 2i 58935

Example 11 In this example, the plastic had the following composition by weight: 20 parts of polyphenylquinoxaline having the formula n = 120, 43 parts of molybdenum disulfide having a particle size of 1-2 microns and modified hexa (1,1-dihydroperfluorobutoxy) cyclotriphosphazene and contains 0.1 part by weight of phosphorus, 3 parts of asbestos, 19 parts of graphite and 15 parts of metallic silver powder.

The plastic was compressed at a temperature of 400 ° C and a pressure of 1,000 kg / cm 2 into plain bearing retaining rings, which were then tested in a bench test at 300 and 350 ° C at a speed of 18,000 rpm and an axial load of 1 kg for a test time of 50 hours.

Table XIV

Friction Reducing Product __Test Results_____ Substance Type Test- Wear Test- Wear at heat- 50 h heat- at 50 h _status ° C g__Status ° C g_

Contains molybdenum ballan disulphide modified with pi-hexa (1,1-dihydrogen-roperfluorobutoxy ring 300 0,0090 350 0,0103 si) cyclotriphosphazene

Contains molybdenum disulphide 300 0.0220

Example 12 In this example, the plastic had the following composition by weight: 95 parts of polyphenylquinoxaline of formula 22 S 8935 where n = 160, 5 parts of molybdenum disulphide having a particle size between 1-2 microns and modified with dicyclohexylphosphinic acid and containing 0, 1% by weight of phosphorus.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table XV

The friction reducing agent, if- The friction reducing agent in which sa is molybdenum disulfide is dicyclohexylphosphine in the form of modified molybdenum sulfide

Wear at 300 ° C Coefficient of friction Wear at 300 ° C Coefficient of friction 1 h 2 h 3 h _; _ l_h_2 h 3 h_ 0.0675 0.0709 0.0679 0.16 0.0582 0.0603 0.0538 0 , 15

Example 13 In this example, the plastic had the following composition in parts by weight: 10 parts of polyphenylquinoxaline of the formula ~ / χτ-ο: χ-ο ° ο-Cr o —In where n = 180, 13 parts of molybdenum disulfide having a particle size of 1- 2 microns and modified with methylphosphonic acid and containing 0.05% by weight of phosphorus, 5 parts of graphite, 30 parts of very fine carbon, 1 part of asbestos, 40 parts of metallic copper powder, and 1 part of metallic silver powder.

. ,. ·. k1 »*" 58935 23

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table XVI

The friction reducing agent, if- The friction reducing agent in which sa is molybdenum disulphide is molybdenum disulphide modified with methylphosphonic acid

Wear at 300 ° C Coefficient of friction Wear at 300 ° C Coefficient of friction g g 1 h 2 h 3 h___l_h_2 h 3 h__ 0.1C28 0.1322 0.1542 0.12 0.0768 0.1025 0.0923 0.10

Example 14 In this example, the plastic had the following composition by weight: 20 parts of polyphenylquinoxaline of the formula 'Är-OCd · ^' jO U Jn where n = 200, 33 parts of molybdenum disulphide having a particle size of 1-2 microns and modified orthophosphoric acid and contains 0.02% by weight of phosphorus, 1 part of very fine carbon, 5 parts of asbestos, 40 parts of molybdenum metal powder and 1 part of copper metal powder.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table XVII

Friction reducing agent. Friction reducing agent with molybdenum disodium molybdenum disulphide modified with orthophosphoric acid

Wear at 300 ° C Coefficient of friction Wear at 300 ° C Coefficient of friction 9 9 1 h 2 h 3 h_l_h_2 h 3 h__ 0.0644 0.0542 0.0899 0.13 0.0585 0.0433 0.0584 0.12

Example 15 In this example, the plastic had the following composition by weight: 10 parts of polyphenylquinoxaline of the formula 24 5 8 9 3 5 10 ^ 9 ^ O Jb where n = 50, 49 parts of molybdenum disulfide having a particle size of 1-2 microns and having a particle size of modified with diphenylphosphinic acid and containing 0.07% by weight of phosphorus, 1 part of molybdenum metal powder, and 40 parts of nickel metal powder.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table XVIII

Friction Reducing Agent, Friction Reducing Agent Containing Molybdenum Disulfide with Diphenylphosphinic Acid Dia Modified Molybdenum Sulfide

Wear at 300 ° C Coefficient of friction Wear at 300 ° C Coefficient of friction g g 1 h 2 h 3 h_l_h__2 h _3_h____ 0.1058 0.1265 0.2045 0.15 0.0795 0.1137 0.1026 0.13

Example 16 In this example, the plastic had the following composition by weight: 5 parts of polyphenylquinoxaline of the formula 'iXr'

Lo b J.

wherein n = 20, 5 parts of molybdenum disulfide having a particle size between 1-2 microns and modified with diheptylphosphinic acid and containing 2% by weight of phosphorus, and 90 parts of graphite.

25 58935

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table XIX

Friction Reducing Agent with Friction Reducing Agent Containing Molybdenum Disulfide is Molybdenum Disulfide Modified with Diheptylphosphinic Acid

Wear at 300 ° C Coefficient of friction Consumption at 300 ° C Coefficient of friction g g 1 h 2 h 3 h_l_h_2 h 3 h_ 0.0155 0.0064 0.07 0.0072 0.0063 0.07

Example 17 In this example, the plastic had the following composition by weight: 15 parts of polyphenylquinoxaline of the formula. = OJ, where n = 120, 40 parts of molybdenum disulfide having a particle size of 1-2 microns and modified with methylphenylphosphinic acid and containing 0 .02% by weight of phosphorus, 4 parts of very fine carbon, 40 parts of metallic silver powder and 1 part of metallic nickel powder.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table XX

Friction reducing agent, if- Friction reducing agent containing sa is molybdenum disulfide molybdenum disulfide modified with methylphenylphosphinic acid

Wear at 300 ° C g Coefficient of friction Wear at 300 ° C g Coefficient of friction 1 h 2 h 3 h_l_h_2 h 3 h_ 0.2599 0.0987 0.1090 0.12 0.1011 0.0870 0.1005 0, 10

Example 18 In this example, the plastic had the following composition by weight: 5 parts of polyphenylquinoxaline of formula 26 58935 "* NN Π -f tCTTT T ~ w where n = 150, and 95 parts of molybdenum disulfide having a particle size of 1-2 microns and modified with triphenyl phosphate and containing 0.01% by weight of phosphorus.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table XXI

Friction reducing agent, if- Friction reducing agent in which sa is molybdenum disulphide is triphenyl phosphate modified molybdenum disulphide

Wear at 300 ° C Coefficient of friction Wear at 300 ° C Coefficient of friction 1 h 2 h 3 h_3 ^ _h_2 h 3 h_ 0.0350 0.0237 0.0174 0.10 0.0190 0.0147 0.0167 0 , 09

Example 19 In this example, the plastic had the following composition by weight: 95 parts of polyphenylquinoxaline of formula

O Q

wherein n = 160, 4 parts of molybdenum disulphide having a particle size of 1-2 microns and modified with diphenylphosphinic acid and containing 0.1% by weight of phosphorus and 1 part of molybdenum disulphide.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

t, \ 27 589 35

Table XXII

The friction reducing agent, if- The friction reducing agent in which sa is molybdenum disulphide is molybdenum disulphide modified with diphenyldosphinic acid

Wear at 300 ° C g Coefficient of friction Wear at 300 ° C g Coefficient of friction 1 h 2 h 3 h_l_h_2 h 3 h_ 0.0675 0.0709 0.0679 0.16 0.0593 0.0615 0.0558 0, 15

Example 20 In this example, the plastic had the following composition by weight: 5 parts of polyphenylquinoxaline of the formula -fry ύύκϊ-Q ~ with n = 200, 5 parts of mtblybenedisulfide having a particle size of 1-2 microns and modified with triphenyl phosphate and containing 0, 1% by weight of phosphorus, and 90 parts of molybdenum disulfide.

The plastic was compressed and the resulting specimens were tested by repeating the methods of Example 1.

Table XXIII

Friction reducing agent, if- Friction reducing agent in which sa is molybdenum disulphide is triphenyl phosphate modified molybdenum disulphide

Wear at 300 ° C g Friction coefficient Wear at 300 ° C g Friction coefficient n 1 h 2 h 3 h_l_h_2 h 3 h_ 0.0320 0.0210 0.0138 0.10 0.0220 0.0155 0.0158 0 , 09

Example 21 In this example, the plastic had the following composition by weight: 40 parts of polyphenylquinoxaline of formula 58935

O Q

N ^ »" τοςττ ^ · J n where n = 300, 5 parts of molybdenum disulfide having a particle size of 1-2 microns and modified with 1,1-dihydroperfluorobutyl diphenyl phosphate and containing 0.07% by weight of phosphorus and 55 parts of graphite.

The plastic was pressed to a temperature of 400 ° C and a pressure of 2 between 2,000-2,500 kg / cm 2 and the resulting specimens were tested by repeating the methods of Example 1.

Table XXIV

The friction reducing agent, if- The friction reducing agent in which sa is molybdenum disulfide is 1,1-dihydroperfluorobutyl phosphate modified molybdenum disulfide

Wear at 300 ° C g Coefficient of friction Wear at 300 ° C g Coefficient of friction 1 h 2 h 3 h_l_h_2 h 3 h_ 0.0012 0.0011 0.0019 0.06 0.0010 0.0009 0.0007 0, 05

Example 22 In this example, the plastic had the following composition in parts by weight: 40 parts of polyphenylquinoxaline of the formula -r1? 0γΌ) - where n = 200, 5 parts of molybdenum disulphide with a particle size of 1-2 microns, modified with hexaphenoxycyclotriphosphazene and containing 0.05% by weight of phosphorus, and 55 parts of graphite.

The plastic was pressed at a temperature of 400 ° C and a pressure of 1,500 kg / cm and the resulting specimens were tested by repeating the methods of Example 1.

29 5 8 9 3 5

Table XXV

Friction Reducing Agent with A Friction Reducing Agent Containing Molybdenum Disulfide is Hexophenoxycyclotriphosphazene Modified Molybdenum Disulfide

Wear at 300 ° C g Coefficient of friction Wear at 300 ° C g Coefficient of friction 1 h 2 h 3 h_l_h_2 h 3 h_ 0.0013 0.0012 0.0016 0.06 0.001 0.0009 0.0009 0.05

Claims (10)

1. Self-lubricating anti-friction material on the basis of a nitrogen-containing polymer and containing filler, characterized in that the nitrogen-containing polymer may consist of either a meltable polyimide or a polyphenylquinoxaline taken in a quantity of from about 5% to about 95% and that the filler may be either molybdenum disulfide modified with phosphorus-containing acids or phosphorus-containing esters, wherein the content of phosphorus in the modified molybdenum disulfide is between 0.01 and 2% by weight and the content of the modified molybdenum disulfide disulfide. is from 5 to 95% by weight, or a mixture of molybdenum disulfide and modified molybdenum disulfide, the molybdenum disulfide component being from 1 to 90% by weight of the self-lubricating anti-friction material. Self-lubricating anti-friction material according to claim 1, characterized in that the nitrogen-containing polymer is a fusible polyimide of the general formula co-H 2 N-CO CO Jn where f - © ~ CHT- © -> -Oy \ <y '-0 "/ CV- €> -; 0 - 0 o * CO n = from 20 to 400 or greater. 3. Self-lubricating anti-friction material according to claim 1, characterized in that the nitrogen-containing polymer is a polyphenylquinoxaline of the general formula (R) = -O-; -SC> 2-C0- ; or it is missing; 0 Ar 'O. -0-01 -O-0-O-: XX ^ O ~; n = from 50 to 300. 4. Self-lubricating anti-friction material according to claims 1-3, characterized in that the phosphorus-containing acids are ortho- and metaphosphoric acids; phosphonic acids of the general formula R "'- P ((OH) 2 or phosphinic acids of the general formula R111 O Rx \ P IV VRX (OH) wherein R111 and RIV may be alkyl, cycloalkyl or aryl, from to C ^ g , wherein R1 * 1 and RIV are the same or different. 5. Self-lubricating anti-friction material according to claims 1-3, characterized in that the phosphorus-containing esters may be phenyl (1,1-dihydroperfluoroalkyl) phosphates of the general formula