DE2328037A1 - METHOD OF FLUORINATING THE SURFACE OF RUBBER PRODUCTS - Google Patents

Description

PATENT LAWYERS. D-8 MUNICH 90 HfAFiAHILFPLATZ 2 Sr S

dr. O. DITTMANN

K. L ·. SHIP P-S MUNCHEK 95

DR. A. V. FünfBR 2328037 POSTBOX 950160

DIPL.ISG.P.STRBHL TELEPHONE (0811) 4583

dr. XJ. SCHÜBBIrHOPF TELEGB. auromarcpat Munich

D ₁ PI. IKQ. D. BBBINGHAUS TELEX 5-23565 AURO D

DA-9470. ■ '"' June 1, 1973

1. Sinowij Naumowitsch Nudelraan, chemist, USSR, Moscow,

2. Ivan Petrovich Prokudin, chemist, USSR, Moscow

PROCESS FOR FLUORINATION OF THE OBERIXAX FROM RUBBER. ' PRODUCTS ■

The invention relates to methods of plating the surface of rubber products with anti-ion pentafluoride.

Rubber with a fluorinated surface is low Coefficient of friction, with products made of such rubber, e.g. reinforced Sealing sleeves, for hermetically sealing friction assemblies be used.

• It is a method of plating the surface of Rubber products by immersing them in a bath with a fluorinating agent, the liquid antimony pentafluoride, and then Washing of the Guinmie products. with water, one.

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5 to 20% aqueous solution of alkali metal carbonate, and .. again known with 'water (see © UdSSK author'schßin no'; 23017 ?, " Bulletin for Inventions and Discoveries of the USSR, No. 8, \

1972). . ■ -... · ■

• A disadvantage of this method is a very large ; use of antimony pentafluoride as a result of its entrainment through the surface of rubber products. Particularly large amounts of antimony pentafluoride are produced by figurines carried away. If you look at such products after the out-. take from the bath above this bath for the most complete possible drainage of the liquid, this takes a lot of time to complete, resulting in uneven fluorination of the Surface of the product and even leads to its destruction. '■

On average per 1 m of the surface of rubber products (e.g. adored sealing sleeves. made of rubber with an outer diameter of about 100 mm) consumes 2 to 4 kg of antimony pentafluoride. As a result of such a high '·. · A large-scale industrial application of the known process for fluorinating the surface of rubber is unprofitable.

Another disadvantage of the known method is that when a product is immersed, the configuration becomes more complicated in the bath with the antimony pentafluoride air bags can form on the surface of the named product in individual places, which prevent access to the flaorie

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prevent medium to these points. This makes the Uneven fluorination of the surface of the product. '

'Another part of the known process is also included associated with the entrainment of the antimonpent afluoride through the product, especially in those places where longer adhesion the liquid is possible. When transferring the product; · Ses from the bath with the antimony pentafluoride into the water When washing, the antimonpent afluorid reacts violently with water, developing hydrogen fluoride and a significant, Amount of heat. These two factors have an intense effect on the öummi and lead to partial damage to it.

Also, there are some disadvantages of fluorination with the liquid ant imonpent afluor id associated with the need to work with larger masses of the aggressive liquid (Expenditure for the transport of the liquid, for its heating, etc.). -

. '. "" ■■ The purpose of the present invention is to provide the above

Avoid disadvantages. ■

The invention was based on the task in which

"'Process for the fluorination of the surface of rubber certificates, which in the treatment of these products with a

, Fluorinating agent, the antimony pentafluoride, at a temperature of 20 to 14O ⁰ C and then washing it with a 3 to 20% aqueous solution of alkali metal, carbonate and water, the conditions for treating the products with the antimony pentafluoride so too

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change so that the unproductive entrainment of the same by the products is practically completely ruled out, admission of the fluorinating agent anywhere on the surface the au-fluorinating gumming certificate is made possible, local damage "to the fluorinated rubber as a result of a Overheating and exposure to hydrogen fluoride when washing s of the rubber product are excluded and the need is avoided with larger masses of the liquid ■ Antimony pentafluoride to work. · ".

This object is achieved according to the invention in that m _a n die. Treatment of rubber products with dom Antiiaonpenta- "fluoride by holding them in a stream of the reagent gas - which is a mixture of the antimony pentafluoride vapors with a carrier gas inert under the conditions of the treatment process.""

Se rubber product-such a gas phase treatment of the 'makes it possible to reduce the unproductive consumption of Antimonpentafluprid due dss entrainment thereof by the surface of the products referred to virtually entirely of _T ■ ■ shut, and the consumption of the Fluorierungsmit'tels' is from 2 up to 4 kg / m rubber, as is the case in the known liquid phase process, to 100 to 200 g / m ² . Lower rubber,

. Another advantage of the proposed method 'is' it that the intimony pentafluoride in the gas phase is the same Access to the entire surface of the Guamia product depends on its configuration, whereby a

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uniform coating of this surface is brought about, When carrying out the plurizing process under the conditions of the proposed method, the possibility "speed of damage to the fluorinated rubber in the process Washing completely excluded because on the surface of the Güminierzeugnis after your removal of the same from the Fluorination reactor only traces of anti-pentafluoride remain, the presence of which does not lead to a violent reaction with water. The proposed method possesses compared to the known still, some advantages that. with the Exclusion from the work of larger masses of liquid antimony pentafluoride are connected (economic efficiency of the transport of the liquid "antimony pentafluoride, low energy consumption, for heating it, etc.). "·

The treatment of rubber products is expediently carried out in the flow of the reagent gas at a concentration of the antimony pentafluoride in the reagent gas of 150 to $ 10 mg / l Reagent gas ".

The multiplicity of the reagent gas exchange is kept in the Pluorierungsreaktor in a range of 10 to 20 volumes / h.

The treatment of the G-ummierzeugnisse in the stream of Reagen.55gases one leads advantageously at a temperature of 40 to 100 ⁰ G through.

The flow of the reagent gas, directed to the treatment of the

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Gluniaieraeugigungen, can through. Bubbling through the carrier gas 'through liquid antimony pentafluoride, which has a temperature of 20 to 80 ⁰ G, or by continuous' evaporation of a jet of the liquid anti-inone pentafluoride generated in the stream of the carrier gas at a temperature of 150 to 1? 0 ⁰ C is initiated.

Any gas can be used as the carrier gas, which-s among the Conditions of treatment of rubber products with PLuo-rinse agent inert, e.g. helium, argon, nitrogen can be used. The latter is due to its accessibility preferred. When fluorinating the surface of against oxidation Resistant rubber, e.g. rubber based on fluororubbers, can also use air as a carrier gas · who »= the. .

The proposed method for fluorinating the upper *. area · of rubber products is carried out as follows.

The liquid antimony pentafluoride brings m _& n into an evaporator. A container made of a material resistant to the action of antimony pentafluoride, for example aluminum, serves as the evaporator. The inside of the holder can be lined with polytetrafluorethylene. Said container is provided with a pressure mixer for introducing the carrier gas and a pipe for leading out the reagent gas. Said container also has a heating jacket, preferably with electrical heating, for holding the liquid antimony pentafluoride in the evaporator at the required temperature (in one area

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from 20 to 80 ^° C. depending on the type of rubber to be fluorinated). -

The vaporizer described with the liquid iintiiaonpentafluorid the carrier gas is fed in at a constant speed and the heagent gas is passed out of the evaporator out, which is a mixture of antimony penta-fluoride vapors with represents the carrier gas. The concentration of antimony pentafluoride in the reagent gas, depending on the type of the rubber to be fluorinated by the speed of the The carrier gas bubbling through the liquid antimony pentafluoride as well as by the temperature of the antimony pentafluoride in the evaporator, preferably by the latter method, can be regulated by the speed of the Dü ^ -chsprudelns of the carrier gas is kept constant and optimal for the particular volume of the fluorination reactor. ' The preferred concentration of the antimony pent af luoride in the As indicated above, carrier gas is in the range of 150 to 510 mg / 1 reagent gas. .

That from the evaporator in the form of a continuous The reagent gas emerging from the stream is fed to the fluorination reactor for the treatment of rubber products.

With the method described, the flow of the reagent gas, which is fed to the fluorination reactor, such as follows. Through a vaporizer, the one out one resistant to the action of the intimonp ent afluoride Material executed heated container of small dimensions

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represents, one leads at one above the Siodpunkt of the Antimony pentafluoride lying temperature, from 150 to 1? O ° C in. With constant velocity the flow of the reagent gas by. The stream mentioned is passed continuously in the form of a jet of liquid antimony pentafluoride, which at entry, evaporated monentan into the heated evaporator, carried away by the stream of reagent gas and out. is led out of the evaporator.

The rubber products to be fluorinated should be pure Have a surface that is free from mechanical impurities, from the oil migrating from the rubber (plasticizer) etc. is. Therefore, if necessary, the rubber products are washed with an aqueous solution before fluorination Solution of soap or some other surfactant Substance, for example the polyoxyethylated alkylphenol, or with an organic solvent, for example Aze- " clay, and then dries.

The fluorination of the surface of rubber products is carried out in a reactor, which is a container, the one against the action of antimony pentafluoride Made of resistant material, with a hermetically sealable lid, pipes for introducing the reagent gas and for leading out the exhaust gas as well as with a. Heating jacket ·, preferably provided with electrical heating is. Before they are introduced into the reactor, the rubber products are placed in a container, the aluminum disk

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which are drawn together in the center with a steel or aluminum rod. The products are arranged in the reactor in such a way that free access of the reagent gas to all surfaces to be fluorinated is guaranteed. The products were then clamped between the aforementioned panes and the container was introduced into the fluorination reactor together with the rubber jars. The reactor is closed and the temperature necessary for carrying out the fluorination process is generated in it. As pointed out above, the 'fluorination ^{temperature is in a range from 20 to 140 0} C, preferably from 40 to 100 ⁰ C, and is selected depending on the type of rubber to be fluorinated The reagent gas emerging from the vaporizer passes through at a rate which corresponds to the specified degree of exchange of the reagent gas in the reactor, which is preferably 10 to 20 volume / hour can be increased or decreased. However, lowering the degree of exchange to less than 10%

e lutnen / St to worsen the uniformity of the fluorination lead, while increasing the degree of exchange

to more than 20 volumes / pc to an unproductive one Breakthrough of larger amounts of the unreacted antimony pentafluoride '-. through the fluorination reactor and a large load- ' the device that collects the antimony pentafluoride.

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- ίο - ■ ■.

The fluorination. is made under the above-mentioned conditions performed for a period of time determined by the Type of rubber to be fluorinated is determined and is preferably in a range of 10 to 60 minutes. After completion of the fluorination, the reactor is filled with pure Carrier gas to blow off the converted antimony pentafluoride and other volatile fluorine compounds from the surface the rubber products and the inner walls of the reactor rinsed; Bas blow-off is expedient until a concentration of the Antiiaonpentafluorids in the atmosphere of the Reactor of less than 0.003 mg / l.

The from the reactor during the fluorination, and the Blowing off emerging gases "is passed through devices, ■■ the unreacted antimony pentafluoride and for the Abfüh ^ -oü in undesirable impurities in the atmosphere (hydrogen fluoride, etc.) .catch and return the antimony pentafluoride in the evaporator. The pure carrier gas, separated from the unused Antimonp ent af luorid and the other volatile fluorine compounds, can be discharged into the atmosphere or fed back into the technological cycle (the evaporator for the. Positioning of the reagent gas and the fluorination reactor for blowing off supplied).

After the blow-off has ended, the reactor is opened, the container with the Guiamier products is carried out and placed in an ash bath, which contains a 5 to 20% aqueous solution of alkali metal carbonate, for example I \ ^r at-

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rium carbonate. The. The purpose of the wash bath is to remove the fluorine and antimony compounds from the surface of the Guimnier products that remain there after being blown off. Dqd. The container is kept in the bath mentioned for .5 to 10 minutes, then brought into the water -B in, where the gumming - "-." Certificates have been washed for 5 to 10 minutes. Then you take the container out of the water _f "carries the .GummierZeugnisse out of this and dries them, for example in the air or in a drying drum (with warm air).

The fluorination according to the proposed method can be gums that are resistant to the action of strong heterolytic reagents (the antimony pentafluoride is such a reagent), ¹ ZB. Rubber on the basis of hydrocarbon or Halogenkohlenw ater off st polymer (ζ.B _1, of ITaturkautsaLa ^, stereoregular butadiene and isoprene, Buna S, chloroprene rubber, ethylene-propylene rubber, fluorine-containing monomers and other Kopolymerisaten) and Buna ^ - etc. subject to ground. . . '

In the proposed method, the consumption of the anti-pentafluoride depends on the type of rubber to be fluorinated. For example, when fluorinating rubber on the basis of natural, Buna N and Buna S, the consumption of antimony pentafiluoride is around 50 to 100 g / nr of the fluorinated surface and when fluorinating rubber on the basis of chloroprene rubber 200 g / m ^{2 of} the fluorinated surface. . For a better understanding of the present invention, ground

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the following examples of the implementation of the proposed method for fluorinating the surface of rubber products cited.

Example 1. To produce reagent gas, an evaporator was used, which is an aluminum container 30 cm in diameter and 40 cm in height, equipped with a jacket with electrical heating and Ronr lines for introducing the carrier gas (the dry nitrogen) and leading out the

• · r -

Reagent gas is provided. A pressure mixer was connected to the pipeline for introducing nitrogen, which almost reached to the bottom of the evaporator.

10 kg of liquid antimony pentafluoride were placed in the evaporator and the electric heater was switched on. After achieving a temperature of the liquid antimony pentafluoride in the evaporator 40 ⁰ G were blown through by this nitrogen. The resulting reagent gas, which is a mixture of the vapors of antimony pentafluoride with the carrier gas, emerged from the evaporator and entered the fluorination reactor as a continuous stream for treatment of the rubber products. '. .

DeT fluorination would subject the surface of rubber products made from Buna N-based rubber containing 40% acrylonitrile members. The rubber products provided metal-reinforced sealing collars with an outer diameter of 100 mm and plates with the

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Measurements 140 χ 140 χ 2 mm. The above-mentioned sealing sleeves in a number of 500 pieces and the plates in a number of 3 pieces were placed in a container that represents aluminum washers, which are in the center with a steel or Aluminum rod are contracted. These products were arranged in the container in such a way that free access of the reagent gas to all pools to be fluorinated is guaranteed. Then the rubber products became; clamped between the above-mentioned aluminum disks and the container introduced together with the products in the "'fluoro ie tion s • reactor. Dex · reactor was sealed and up to? setting an internal temperature. 50 C heated" was then passed through the reactor at the said "temperature" a stream of the reagent gas emerging from the evaporator for 40 minutes. Of the. Degree of exchange

aes reagent gas in'dem fluorination reactor was 20 "Volume / St, the concentration of antimony pentafluoride in the reagent 25 mg / 1 reagent. ■

After completion of the fluorination, the reactor was ^{flushed with pure nitrogen at a temperature of ^ Q 0} C for 40 minutes. Then the nitrogen supply was interrupted, the reactor opened and the container with the rubber products in a vessel with 10 ^ iger aqueous Introduced solution of sodium carbonate, where this was kept for 5 to 10 minutes while stirring the solution. "Then you put the container in a vessel with water, where the" Gucsiier-

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Test pieces were washed for 5 to 10 minutes, after which. man took the container out of the water, from this the • Carrying out rubber products and putting them in the air or in '·. "a drying drum (with warm air) dried. · ...

The Guinmie products with a fluorinated surface were subjected to a test to determine the coefficient of sliding friction, the temperature in the. Contact ζ one "GuiaiaiAietall" _r (in, the friction zone) and the tensile strength of the rubber 2 kp / cm measured.

The following results were obtained (the same characteristic values for non-fluorinated rubber are given in brackets): slip index · 0.5 (1 »4); Temperature in the friction zone 88 ⁰ G (210 ⁰ C); Tensile strength of the rubber 140 kg / cm ² · (150 kg / cm ² ). The rubber fluorinated with liquid antimony pentafluoride had a tensile strength of 110 kgf / cm with the same coefficient of sliding friction. . ■

The service life of the rubber sealing sleeves' with fluorinated Surface in an automobile assembly up to the occurrence of a Leks associated with the bursting and keratinization of the working edge of the cuff, amounted to 160,000 km and for the like Cuffs with non-fluorinated surface 80000 kai.

Example 2. Rubber products "made of rubber on the basis of Buna 1Ϊ, which contains 40% acrylonitrile members, with a"

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high plasticizer content (50% dibutyl sebazinate were produced, before fluorination they were washed · with acetone ζ to remove the plasticizer that had leaked to the surface of the rubber and kept in the air for 15 hours to remove ■ acetone. '.'_; - ·

The preparation of the reagent gas and the fluorination the surface of the rubber products, followed by .. Rinsing the fluorination reactor and washing the Guiruaierz'eug- * Hisse was carried out as described in Example! '. ".

• When examining gourami products with fluorinated ' . Surface under the "conditions" described in Example 1, the following results were obtained (the same characteristic values for non-fluorinated rubber are given in brackets): Sliding coefficient 0.3 (1> 5) temperature in the friction zone 86 ⁰ C (220 ⁰ C); tensile strength of the rubber 150 kp / cm ² (1 ^ 0 Ιφ / cm ² ).

EXAMPLE 5 Rubber products made from rubber on the basis of Buna N, which contains 40% acrylonitrile members and had a heavily contaminated surface, were washed with an aqueous solution of a surface-active substance (sodium stearate ·, Or of polyoxyethylene octylphenol) and then 'with water and air-dried. ■ "". '■ "'. · '

. The preparation of the Re age η zg as es as well as the. Fluorination of Surface of the Guiamier products with subsequent rinsing, of the fluorination reactor and washing of the gunuier products was carried out as described in Example 1.

• ·

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When testing rubber products with fluorinated upper. area under the conditions described in Example 1 The following results were obtained (the same characteristic values for non-fluorinated rubber are given in brackets): Gleitreibuhgs- ·.

number 0.5 (13), * temperature in the friction zone 81 ° C (210 ⁰ C); '

* 2 "2

Tensile strength of the rubber 150 kp / cm (1 ^ 0 kp / cm).

Example 4. The surface of rubber products, which were made of rubber based on ethylene-propylene rubber and were plates with the dimensions 140 × 140 × 2 mm, was subjected to fluorination. . .

The preparation of the reagent gas and the fluorination of the surface of the greenery products with subsequent rinsing. of the fluorination reactor and washing of rubber products carried out analogously to Example 1.

"The temperature of the liquid antimony pentafluoride in the evaporator was 3O ⁰ G _1, the temperature in the fluorine

tion reactor 70 ⁰ C, the degree of exchange of the reagent gas in the fluorination reactor 10 volume / h, the concentration of antimony pentafluoride in the reagent gas 200 mg / 1 reagent gas, the duration of the fluorination process ID Minuteii, the duration of the flushing of the fluorination reactor at a temperature of 70 ⁰ C 30 minutes. . · ··.

. The rubber products with fluorinated surface were subjected

one exam by taking the coefficient of static

i '

Rebung on a tribometer and "the tensile strength of the rubber" determined. The following results were obtained (In K

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The same parameters are given for non-fluorinated Gu'ami)! Static friction coefficient 0.15 '. ·. (l »0);"

P 2

Tensile strength of the rubber 120 kp / cm (120'kp / cm).

Example 5. The surface of the rubber products made from rubber based on chloroprene caachuk was subjected to fluorination. ·. '

The 'preparation of the reagent gas as well as the fluorination / the Surface of the rubber products with subsequent rinsing the fluorination reactor and washing the. GummierZeugnisse was carried out ', analogously to Example 1, the conditions under' the preparation of the reagent gas, the fluorination of the surface, the rubber products and the flushing of the fluorination reactor are listed in Table 1. - ■■■ '·. ··

• 1 tempera • 20th tempera Multiple Tabel 1 • 30th conditions Mr. 2. ture of 25th ture in Ness- Conc Last 45 the flush of 3 liquid 30th Fluorine of the stepped ion of 60 of fluorine Ver gene anti .r- exchange of the Jüa— ■: Fluo- rungsreaictors see below monpenta- reactor, des.Re t imott- rie. Tempe- duration " ches fluorids ⁰ C agent - penta- guessing rature of in the gases im fluo- proaes- O ₀ . ■ rinsing Steam boat- Fluorine rids in ses, 'lung, ⁰ C rungsre- Reageriz- ~ min mm akfcor,. · gas,. - VoI urn n / 3ü mg / 1. . ■ ■, "- 40 - 20th 40 30 45 20th 150 45 30 55 10 180 55 -30 - ■ 200

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Subjected the rubber products with fluorinated surface mgn a test among those described in Examples I and 4 Conditions. The exam results are in the Table 2 listed. For comparison, the table shows the results an .analog test of the rubber he certificates with non-fluorinated Surface '. . '·

Table 2 '

Designation, the characteristic values

Rubber products with surface, fluorinated under the conditions with different conditions. not-r

Experiments · fluorinated

Attempt 1. Attempt 2 Attempt .3 ' ^Surface

Coefficient of st-ati- "."

see friction 0.12 0.12

Equal with a friction coefficient of 0.5 0.3

Partial capacity in the contact. ·.

zone "Guinmi / raetall ¹¹ -, ^ 95 oil

Tensile strength of the rubber,
kp / cm ² . · · 170. 170

0.12 0.2>

-75

1.2

170

EXAMPLE 6. The surface of the guillotine products made from. Rubber based on! Taturkautschuk.

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The preparation of the reagent gas and the fluorination of the surface of the rubber products with subsequent flushing of the fluorination reactor and washing of the rubber products were carried out analogously to Example 1. The temperature of the liquid antimony pentafluoride was in the evaporator '5O ⁰ C, the temperature in the fluorination reactor 45 ° C, the degree of exchange of Keagenzgases ■ "f in the fluorine ~

■ rungsreaktor 20 volume / h, the duration of the Fluorierungsproze'sses 60 minutes, 'the duration of the flushing of the Fluorierungsreal -: - tor at a temperature of 4-5 ⁰ C 60 minutes.

The rubber products with fluorinated surfaces were subjected to a test by determining the coefficient of static uplift on a tribometer, as well as the tensile strength of the rubber and the elongation at break. The following results were obtained (the same parameters are given in brackets for non-fluorinated rubber): coefficient of static friction 0.15 × (1.0); Tensile strength of the rubber 210 kg / cm ² (220 kg / cm ² ); Elongation at break ^ 0% (460%).

Example 7 » i ^ ü ^ the production of Seagen ^z gas vervven-. One found an evaporator which is a 300 mm long aluminum tube with an inner diameter of 50 mm and a wall thickness of 20 mm. At the "end faces" the evaporator had a connection with a tube for introducing the carrier gas on one side and a connection for discharging the reagent gas on the other side Resistance thermometer · built in. In

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Distance of 50 mm from the end face with the socket for an ^ introduction of the carrier gas existed in the wall of the evaporator eine.Öffnung into which a Polytetrafluoräthylenkapil-Ia ^ e O ₅ I mm in diameter was used ^1; associated with · a container j containing liquid ühtimonpentaf.luorid ,, 'connected ·

was «, ·: '

The ¥ he steam he was up to reaching a temperature

-. heated by 160 ⁰ C »Then one passed through the Yer-. damper the carrier gas (air) and passed through the capillary liquid antimony pentafluoride in the form of a thin jet at a speed of 2 g / min = the in-the-Ver. · "■ • damper reagent gas formed is led in the form of a kontixaiie-NATURAL stream the Fluox-ierungsreaktor to ₉ by capacity of this ■ beforehand by an intermediate container of ^ O liters by directed ₅ where the reagent auf'eine temperature was heated, the the temperature in the fluorination reactor is the same

The gum products made from rubber on the basis of fluorine rubber (copolymer of vinylidene fluoride with trifluorochloroethylene) were introduced into the reactor and the surface of the rubber products was fluorinated. with subsequent rinsing of the reactor and washing the Gummierzeugnisse'.analog to Example 1 "In this case, the temperature in the fluorination reactor 100 ⁰ C, the degree of exchange - the reagent gas in said reactor 20 volume / St j ion, the concentrate it .d antimony pentafluoride in to the "

310 _m g / l reagent gas, the duration of the fluorination »40985 1/0554

processes 15 minutes, the duration of the flushing of the fluorinating actuator at a temperature of 10O ⁰ C JO minutes., '■

The rubber products with fluorinated surface were subjected to a test under the conditions described in Examples 1 and 4 * The following results were obtained (the same parameters for non-fluorinated rubber are given in brackets) s Coefficient of static friction O ₈ 11 · (I ₅₁ O) $ · Coefficient of sliding friction Ο ₈ 28. (1 _δ 5) ϊ Temperature in the contact zone ⁸ 'Rubber / Hetal "? 5 ° C (190 °) | Tensile strength of the rubber 220 kp / on ² (250 kp / cm ² ) o. · :, ■ ·

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Claims (1)

PATENT CLAIM «- ^ ^ ^! "Process for the fluorination of the surface of rubber products by treating such products with a dam Fluoriarungsraiütelg antimony pentafluoride, wherein einar temperature of 20 to 14O ⁰ C and washing it with a 5 to. 20% aqueous solution, of alkali metal carbonate and with ..V / ater, characterized ge characterizing zeiehn © t ₉ that the treatment of the Guimnierzeugnisse called performs ₈ indene. If this in a stream of a test tube holding _s which is a mixture of antimony pentafluoride vapors with a carrier gas "which is inert under the conditions of the treatment process. 2 «Method according to claim I _5, characterized in that the treatment of the guaai products is carried out at a concentration of the minon pentafluoride in the reagent gas of between 1 and 3IO mg / l reagent gas 3 · Method according to claim 1 and 2 _p . characterized gek.zeichj that the treatment of the rubber products with ein.m degree of exchange of the reagent gas. ν in the Pluorierungsreaktor -from 10 to 20 volume / h is carried out. 4. Method _% according to claim. 1-3 »characterized in that the treatment of the Guinea egg products is carried out at a temperature of 40 to'ICO ⁰ C«, 409851/0554 · $ <, Method according to claim 1- = 4 _S da dar ch "g © ke η η ζ e i HOt ₈ that the current of the for the treatment of the gummed products is passed through s the bubbling of the carrier gas through the liquid / uatimon = pentafluoride ₈ which has a temperature of 20 to 80 ⁰ C _s generated ".". 6 ₀ The method of claim 1 = 4 ,, characterized g- -e- kennzeichnetj that the "for the treatment of rubberised products of the current conducted by ßeagenzgases kontinuierliehe evaporation of a introduced into the flow of carrier gas at a temperature of 150 to 17O ⁰ C the beam Antimorque pentafluorids produces wireL 7 ο Method according to Claim 1 = 6 ₉ characterized in that nitrogen is used as the carrier gas ο. . . '"' ■ '"" 8ο method according to claim l ~ 6 ₀ thereby .. g ek ö η η. "ζ β ic Ii ae tji that air was used as the carrier gas 409 ^ 851/0554.