DE2311879A1 - ORGANIC SILICON COMPOUNDS CONTAINING FLUORINE - Google Patents

Description

PATENT LAWYERS

DR.-ING. H. FlNCKE DIPL. - ING. H. DOMR DIPL-ING. S. STAcGER 8 MUNICH 5

MÜLLERSTRASSE 31

Folder 23144 - Dr. K. Case Dw / MD 24833/25070

Imperial Chemical Industries Ltd. London, UK

Fluorine-containing organic silicon compounds

Priorities: 9-3-1972 and May 22, 1972 - Great Britain

The invention relates to fluorine-containing nosilicon compounds and particularly to silanes and siloxanes with one or more unsaturated fluorocarbons Substitution groups.

309843/1195

A number of silanes or siloxanes are known which contain fluorocarbon groups. However, in all of them the fluorocarbon group is a saturated group. Because of their nature, these materials have various disadvantages such as high cost.

The invention now relates to a new class of Silanes and siloxanes that contain at least one group of the general formula

CF ₀ JR CH ₀ SiE 'X 0,. _Λ η 2n-1 am 2m bc 5-bc

where R is a divalent group, S 'is a monovalent hydrocarbon group, X is a hydrolyzable group, η is 8, 10 or "2 , a is 0 or 1, m is 2, 3 or 4 , b is 0, 1 or 2, c is C, 1, 2 or 3 and b + c is not greater than 3.

The siloxanes according to the invention can in addition to the groups of one or more units specified above the general formulas

ZHSiQ and

where Z is a monovalent hydrocarbon group stands as it is generally known for siloxanyl units. Indeed, it is often preferred that Z represents a methyl group.

The group R can with oxygen, an alkylene group with not more than B carbon atoms, a polyoxyalkylene diol radical or a phenoxy or substituted phenoxy group.

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Monovalent substituents which εη-v? Esend in the Phenoxygrupper are alkyl and alkoxy groups and haloamines. Divalent substituents which a Heine or may also be present, are sulfonamido- and carboxyl groups which attach the phenoxy group to the group C E ~.

^rr πι 2i

The groups R ¹ can be alkyl, aryl, alkaryl, aralkyl or cycloalkyl groups, such as, for example, methyl, ethyl, propyl or phenyl groups. It is generally preferred that the R "groups be methyl groups.

The group X can be, for example, a halogen atom, an alkoxy group, a substituted alkoxy group or a polyoxyalkylene group. Suitable groups are, for example, fluorine, chlorine, bromine, methoxy, ilthoxy, propoxy, butoxy, methoxyethoxy, ethoxyethoxy, phenoxy and 2 ~ (N _i N-dimethylamino) ethoxy groups. It is normally preferred that the groups X be chloro-, methoxy-; or are ethoxy groups.

In a method for producing the invention Compounds in which R represents a phenoxy or substituted phenoxy group becomes an unsaturated one Tetrafluoroethylene oligomer of the general formula

where η is 8, 10 or 12, initially with an allyl phenol or substituted allylphenol implemented, whereupon then the compound obtained in this way with a silane or siloxane which has at least one hydrogen bonded to silicon atom has, is implemented. The reaction with the

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23ΊΊ879

Ally! Phenol or substituted allyl phenol can thereby be carried out that the reactants in the presence of a solvent such as dimethylformamide, and an acid acceptor, such as triethylamine, is stirred with one another. The product of this reaction is then treated with a Compound containing hydrogen bonded to silicon, reacted in the presence of a suitable catalyst. These products can also be made by first creating a compound of the oligomer and a sulfonylsubstituted phenol produces, for example as described in German patent application 16 98 523 · 2 is ·, and that thereupon a reaction with a suitable γ-aminoalkylsilane or -siloxane, for example / "- aminopropyltriathoxysilane, follows, or that alternatively the phenol / oligomer compound is reacted with an aminoolefin such as, for example, 3-amin.opropyl-i-ene and then the product with a silane or siloxane, which has at least one silicon-bonded hydrogen atom.

In another process for the preparation of the compounds according to the invention in which a is 0, a tetrafluoroethylene oligomer can be reacted with an alkenyl magnesium bromide and the product can then be reacted with a silane or siloxane which has at least one hydrogen atom bonded to silicon. The reaction can be carried out by adding the alkaliyl bromide and a tetrafluoroethylene oligomer simultaneously to a stirred suspension of magnesium in diethyl ether and then reacting the product obtained with the silicon compound. \

The reaction of the allyl fluorine compound with the silane | or Siloxane, which has at least one silicon-bonded hydrogen atom has, can in a known manner and in the presence

309843/1195

of a catalyst of the type known for such reactions "Suitable catalysts are for example chloroplatinic acid, cyclohexene / platinum (II) chloride and bis (diethyl sulfide) / platinum (II) -. chloride.

Suitable silanes for use in this reaction are for example trichlorosilane, methyldichlorosilane, Dimethylchlorosilane, trimethoxysilane, triethoxysilane, Methyl diethoxysilane and dimethyl methoxysilane.

The siloxanes according to the invention can either directly or by hydrolysis of a silane according to the invention alone or in the presence of one or more other hydrolyzable silanes.

They can also be produced by balancing. ^;

The products of the invention have a wide variety of uses. For example, they can be used for this to make the surface of glass hydrophobic and oleophobic. They are also useful for treatment or glazing of agricultural buildings, for example greenhouses, and in the treatment of Glass fibers used as filters for liquids and gases. They can also be used as an anti-foam agent, especially in non-aqueous systems, and as mold release agents be used.

Fluorocarbon derivatives, the silane or siloxane groups can be used for the treatment of fillers, such as glass fillers, in the manufacture of filled granular fluorocarbon polymers can be used. Preferably the filler is mixed with a solution of the derivative

309843/1195 \

in an organic solvent "treated to the filler to coat with the derivative and make it hydrophobic before it becomes a polymer with the fluorocarbon aqueous medium is agglomerated.

Plurcarbon derivatives containing a CF ~ _Λ group (in which

η 2η— ·

η = 8, 10 or 12), which are attached to a group of formula

^S1R '

is bound, for example compounds with at least one group of the formula

^C n ^P 2n-1 ^R ä ^G m ^H 2m ^SiRI b ^X c ° 5-bc

2 "

in which R, R ¹ , X, n, a, m, b and c have the meanings given above, can also be used. Particularly useful derivatives are compounds of the formula

and

The formation of agglomerates from a fluorocarbon polymer and a filler with a relatively small particle size is important in molding techniques hierbsi au * =; a poorly flowing polymer free fixed transmission

309843 / 1i9S

filled polymeric parts can be made. These particles are easier to handle than unagglomerated polymers and. I ¹ UIl materials, for example in an automatic molding machine.

The fact that the filler particles with "a surface-active Means are made hydrophobic, which occurs during agglomeration from an aqueous medium Withstand washing conditions as described below successful agglomeration of polymer and filler can be facilitated. In practice means this that a considerable proportion of the filler fed to the washing tank under suitable conditions; with the fluorocarbon polymer is agglomerated. Consequently waste of filler is reduced and the composition of the agglomerated product can be better can be predicted from the relative amounts of the polymer and filler used- It has been found Proved as a valuable invention that fluorocarbon derivatives as described above have been successful can be used in the treatment of fillers in this agglomeration process.

Fluorocarbon polymers in granular form are made by generally known methods obtained, for example by having monomer in an aqueous medium in In the absence of a stabilizing amount of emulsifier polymerizes. The obtained polymer is usually comminuted, for example by grinding, before a filler is incorporated. The fluorocarbon polymer can for example be a granular polytetrafluoroethylene (PTFE) or a copolymer of tetrafluoroethylene with up to 15% by weight of other monomers, such as ethylene, Vinyl chloride and hexafluoropropene.

309843/1195

The fillers that can be treated prior to incorporation into the fluorocarbon polymer are adjacent Glass metallic fillers such as aluminum, bronze, Copper, hiekel and iron, and mineral fillers, such as asbestos, mica, silicon dioxide and talc. When agglomeration consists of an aqueous kedium generally no need to handle fillers, which are already hydrophobic, such as graphite, to aid their agglomeration with the polymer.

When carrying out agglomeration from an aqueous medium, the granular polymer and the filler, both in fine particle form, the filler having been treated with the fluorocarbon derivative, can be introduced into a washing vessel in which they are agitated with water by suitable stirring means, until agglomerates of a suitable size containing both polymer and filler are formed. The agglomerates are then removed from the container and dried. A suitable Rührzeit.-is for example 2 to 4 st at 60 to 90 ⁰ C. Milled · _'Λ granular PTFE having an average particle size of 20 to 25 / · * - is a suitable polymer molding for use with, for example, finely divided glass fibers.

The invention is further illustrated by the following examples explains in more detail where all parts and percentages are expressed in weight.

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example 1

"5CC 2 parts tetrafluoroethylene pentamer, 1300 parts dimethy formamide, 482 parts of o-allylphenol and 380 parts of triethyl amine were stirred together at 25 ° C. for 28 hours. The lower one Layer was allowed to settle, separated, successively with 1500 parts of 5% sulfuric acid and 15C0 Washed portions of water and then azeotropically dried by refluxing with toluene under a Dean-3tark-? AHe. In addition to water, 262 parts of tetrafluoroethylene pentamer were removed via the Dean-Stark trap. The toluene was distilled off and the residue was fractionated in vacuo. There were 1168 parts of a Compound of formula

F ^ (A) obtained. Ep 83 ° C / 0.3 mm.

Analysis: Calculated for C ₁₉ H ₉ F ₁₉ O: C 37.1%; H 1.47%. found: C 37.0%, 36.7%; H 1.47%, 1.39% -

123 parts of compound A and 0.046 parts of bis-diäthylsulfid-platinum (II) chloride were heated to 120 C and ^9-then 60 parts Trichlorosilantropfenweise added. The reflux was maintained for 30 minutes. A vacuum distillation gave 140 parts of 01, Si (CH ₂ ), - o-CL-H ^ GC with a neutralization equivalent of 253 · redistillation gave an analytical sample. Kp 135 / 0.5 mm.

Analysis: found: C 30.3%, 29.9%; H 1.24%, 1.19%; F 47.9%,

48.7%.
for C ₁₉ H ₁₀ Cl ₃ F ₁₉ OSi: C 30.4%; H 1.3%; F 48.2%.

. (Neutralization equivalent 250).

309843/1195

BeisOJel 2

123 parts of compound A and 0.046 parts of bis (diäthylsulfid) -platin- (II) chloride were heated to 120 ⁰ C, and then 50 parts of methyldichlorosilane was added dropwise -during a period of 5 min added. The mixture was ^ 1 st 1/2 and heated to reflux then destillieret in vacuo.

In this way 92.5 parts of KeGl Si (CH ₂ ), - 0-C ₆ H ₄ CC ^ ₀ IL ₀

obtain. Kp 107 ° C / O.05 mm.

Analysis: Found: C 33.0%, 32.9%; H 1.85%, 1.85%; Cl 9.85%, 9.70%; for C ₂₀ H ₁₅ Cl ₂ F ₁₉ OSi: C 32.9%; H 1.8%; Cl 9.7%.

Example 3

A mixture of 281 parts of compound A, 300 parts of toluene and 0.125 parts of bis (diethyl sulfide) platinum (II) chloride was heated to reflux. Then 66.6 parts of trimethoxysilane was added dropwise to the refluxed solution. After the addition had ended, the solution was refluxed for a further 6 1/2 hours. Distillation in vacuo gave 232 parts of (MeO) ₅ Si (CH ₂ ), -O-C ₆ H ₄ OC ₁₀ F ^ ₉ . Bp 124 to 125 ° C / 0.15 mm.

Analysis: Found: C 36.2%, 26.3%; H 2.42% * 2.33%;

-OMe 12.1%, 12.4%.

Calculated for: C ₂₂ H ₁₉ F ₁₉ O ₄ Si: C 25.9%; H 2.6%;

-OMe 12.6%.

Example 4

222 parts 1,1,1,3,5,5,5-heptamethyitrisiloxane, 614 parts Compound A, 0.5 part of bis (diethyl sulfide) platinum (II) chloride

309843/1195

and 21C parts of toluene were heated to reflux for 30 minutes. Infrared analysis of the mixture showed no Si-H containing material was present. * Removal of volatile materials left 800 parts of the compound (Me _x SiO) ₂ Si (Me) CH ₂ CH ₂ CH ₂ -OC ₆ H ₄ OG _{10 as a residue} F ₁₉ back, which corresponds to 9c% of theory. An analytical sample was obtained by distillation in vacuo. Bp 14Γ: ° C / C, ^ nu

Analysis: Found: C 37.7%, 37.0%; H 3.69%, 3.68%; for C ₂₆ E ₃₁ F ₁ QO ₅ Si ₃ : C 37.3%; H 3.74%.

Seis-game 5

720 parts of the product from Example 2 were dissolved in 2500 parts of acetone and then 500 parts of v / water were added. After the exothermic reaction had subsided, the mixture was heated to reflux for 30 minutes, whereupon all volatiles were removed to a final pressure of. C, 5 THTL Eg were distilled off at ".00 ⁰ C. The product was at 100 ⁰ C a clear viscous liquid. It was highly viscous at 20 ⁰ C. It consisted of a polysiloxane having the repeating unit.

Analysis: Found: C 35.7%, 35.3%; H 1.50%, 1.80%; Si ^ -, 18%, calculated for _c . gf _a OSi: C 35.6%; H 1.9%; Si 4.2%.

309843 / 119S

-eisriele 6 to 10

5 substituted polysiloxanes of the formula

Ke
ί

Si-O-t-SiKe.

\ ^ \ Τ, ν

v: orin η stood for 8, 25, 50, 98 and 200, respectively, became as follows manufactured.

Bas Polysiloxan ^ iC (SiKeHO) _n SiMe ₃ , 1.7 parts of bis (diethyl sulfide) platinum (II) chloride, 500 parts of compound A and COO parts of toluene were heated to reflux. A few minutes after the start A lower layer separated from the reflux. The mixtures were refluxed for 4 hours and then the solvent was removed on a rotary evaporator. Theoretical yields were obtained. The parts of the starting polysiloxane are given in Table I.

Table I.

"n"

Share Poiysilcxsn

3 25

46.5 45.2

3 0: - ■ .: ■ :, 3 7 1 1 9 p

A foaming solution was prepared which was composed of a 2% strength solution of a mixture of 3 parts of butyl titanate, 3 parts of a methylpolysiloxane mixed polymer with Xe _x SiC., _/? - And SiG ^ units in a ratio of 1.2: 1, 3 parts of dimethylpolysiloxane with a viscosity of 300 c3 at 25 ^c 3 and 1 part of a dimethylpolysiloxane with a viscosity of 30.CCO cS at 25 ° C in ferchloroethylene. Eie siloxanes of Examples 6 to 10 and a cyclic siloxane F

were tested for their defoaming activity against this solution. A certain amount of Schäuaiungslösung was with 50 ppm of the siloxane as a 1% solution in CTCi ^ treated. The solution was shaken for 30 seconds and the Time to collapse of the foam was recorded and is reported in Table 11.

Table II

Sr-Ioxar:

Defoaming time ^^

c 10

17.1

3 0 y 8 4 3/1195

In the absence of a defoamer, the foam was stable for more than 5 min.

Example 11

^C 10 ^F 1Q ° YV SO ₉ NHCH ₀ CH ₅ CHJSi (OC-H-). Manufacture of ^υ '* \ = y ² " ² - ^2. ^ ² ^.

The following reagents would be used:

SO ₂ Cl,

(r-aminopropyltriethoxy ^ 82.8 g (0.4 mol) si lan) -

Sodium carbonate 43 g (0.4 mol)

"Arcton" 113 ** 1,2 1

Explanations:

* Manufactured according to the German patent application

P 16 98 523.2
* * 1,1,2-trifluoro ~ 1,2,2-trichloroethane

The aminosilane in 200 ml of "Arcton" 113 was added dropwise to a stirred solution of the sulfonyl chloride in 1 liter of "Arcton" containing the suspended sodium carbonate. After completion stirred Zugabe'wurde the mixture for another 30 min at 25 ⁰ C, filtered and evaporated to dryness to give 337 g of a colorless viscous liquid was obtained. The fluorosilane thus obtained was then distilled under vacuum to prepare an analytical sample.

309843/1 195

The spectroscopic measurements were in full agreement with the structure

CF CF ₂ CF ₃

\ I

\ I

- C - C CF /

CF ₃ - C - C = C - 0 < ⁷ ViO ₅ KKCH ₀ CH-Cr 'Si (OC_K_), 3 . \ / 2 2 2 ^ 2 j;

CF CI ^

match.

Spectroscopic measurements masses: no parent ion observed when ions are generated

m / e - 814 corresponding to output - 0, H ₁ -, ¹¹ '= 842 " ^tf - CH ^ ¹¹ =

"= 174" Loss of C ₂ H ₅ OH from ion m / e ¹¹ = 163 "Si (OC ₂ H ₅ ) ₃

19th
NMR -! "Peaks at the following positions in ppm solvent

(55,3) ■ CF-C --C = C-O-

(78 _; 8)

(104j0)

308643/1

H ¹ point. ·]! at the following positions in ppm

Η · - · ■ H

-O-

-SO ₂ -N -C- CC Si- (O-CE ₂ -CH ₃ O ₃ i ■ HH H. - (3j7S) (V9)

(7.10) (3.00) (6.08) (2 _; 96) (1, W) (O ₇

(0.56)

by

The same compound was also given below Reaction sequence established:

- .CH = CK ₂

SO ₂ HHCH ₂ CH =

Bis (diethyl sulfide) platinum (II) ■ chloride

■ ■ (EtO) ₃ SiH

, '· -. CH, ■■ - Si (OSt) -

Example 12

The following reagents were used:

^C 10 ^F 19 °

Potassium hydroxide ..
Isopropanol

.5 g (0.05 mol)

0.2 g 200 ml

3098 4 3/1195

ORiGfNAi INSPECTED

a solution of the fluorosilane (prepared according to the pre-; Example 11) in isopropanol, which contained the finely ground potassium hydroxide, was 15 min at 25 ° C touched. The solvent was then removed in vacuo and the polysiloxane was dissolved in. 1 ', 1,2-trifluoro-1,2,2-trichloroethane dissolved. The resulting solution was washed with v / ater, dried and reduced to a 20% (w / w) Concentrated solution, which was suitable for coating glass' surfaces.

Example 13

-t

48 ml of a 0.3% solution of a compound according to Example 11 was prepared in 1,1,2-5? Rifluoro-1,2,2-trichloroethane were with 400 g Owens-Corning | "Fiberglass" -709 glass fibers mixed.

The mixture, which essentially consisted of the glass fibers moistened with the solution, was ^{dried for 16 hours in an oven at 120 °} C. with a suitable solvent extraction system. 325 g of dried coated glass fibers were (manufactured by Imperial Chemical Industries Ltd., "Fluon" G163) was mixed with 875 g of PTFE. The 1.2 kg ■ vast mixture was stirred together with 20 1 water having a temperature less than 25 ° C in a 30 1 container is bracht.- An agitator in the vessel was at 450 U / min while the temperature raised to 80 ⁰ C and was held at this value for 2 st. The temperature was allowed to drop to less than 3C ^C , the stirrer stopped, and the slurry was transferred from the container to a dewatering table with 400A openings. The product which zürückblieb on the table, was 2 st dried at 200 ⁰ C and 3 st baked at 280 ⁰ C. The cooled product was sieved through a sieve with 1000 / ^ openings. That through

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- 18 - ■ ..- ■■■■

the sieve passing product was in the form of smooth, \? "glass-filled PTFE agglomerates with a measured glass content of 24.9%. Thus, of the 27% of the glass originally present, only slightly more than 2% was not agglomerated with the PTFE. The procedure was therefore very useful.

Example 14

Example 13 was repeated except that the solution prepared with the 400 g of glass fibers was mixed, from 18 ml of a

1%

Solution of the compound prepared according to Example 3 existed, to which 31 ml of a 1% aqueous acetic acid solution had been added. The ₄ S product which passed through a sieve with 1000 / ^ openings was an agglomerated glass-filled PTPE with a measured glass content of 24.8%. The agglomerates had smoother surfaces. The procedure was therefore very useful. ■

309843/1195 ORfGfNAi INSPECTED

Claims (1)

Claims 1. Silanes and siloxanes, characterized in that daE they have at least one group of the general formula: V2n-1 ^R a ^C m ^H 2m ^Si * b ^X c ° 3-bc -I wherein H stands for a divalent group, R 'stands for a · * monovalent Hydrocarbon group; X for a hydrolyzable Group, η is 8, 10 or 12, a is 0 or 1, m is 2, 3 or 4, b is 0, 1 or 2 stands, c stands for 0, - 1, 2 or 3 and b + c is not greater than is. I. 2. · Silanes and siloxanes according to claim 1, characterized indicates that the group R is an oxygen group, an alkylene group with no more than 8 carbon atoms, a polyoxyalkylene diol radical, is a phenoxy group or a substituted phenoxy group. 3. silanes and siloxanes according to claim 2, characterized in that the group R is a phenoxy group which has a sulfonamide group or a carbonyl group as a substituent, through which it is bonded to the group C H « is. · £ ·. Silanes and siloxanes according to one of the preceding claims, characterized in that the group R ^{1 is} an alkyl, aryl, alkaryl or cycloalkyl group. 309843/1195 5 «silanes and siloxanes according to claim 4, characterized in that the group R ¹ 'is a methyl, ethyl, propyl or phenyl group. 6. · Silanes and siloxanes according to one of the preceding Claims, 'characterized in that the group X is a Halogen atoms, an alkoxy or substituted alkoxy group or a polyoxyalkylene group. , ■ 7. silanes and siloxanes according to claim 6, characterized in that the group X is a chlorine or a Is kethoxy or ethoxy group. 5. Siloxanes according to one of the preceding claims, ■ characterized in that they additionally contain units of one or more of the following general _{formulas: · Z 5} SiO ^ y ₂ , Z ₂ SiO, ZSiO ₅ , ₂ , SiO ₂ , ZHSiO and HZ ₂ SiO ^_1/2: • wherein Z is a monovalent hydrocarbon group a for-. 9 siloxanes according to claim 8, characterized in that that Z stands for a methyl group. _. ",. '. C. Process for the preparation of silanes and siloxanes according to one of Claims 2 to 9i in which R stands for a phenoxy group or a substituted phenoxy group, characterized in that a tetrafluoroethylene oligomer of the general formula CpHp in which η stands for 8, 10 or 12 is used , with an allylphenol or a substituted allylphenol and then the product obtained in this way with a silane or siloxane which contains / reacts at least one hydrogen atom bonded to silicon. ■ " ¹ ^. Process for the preparation of silanes and siloxanes according to one of Claims 2 to -9, characterized in that 30984.3 / 1195 a compound of the general formula C -F- ^ OCgH SO ^ Cl v.-crin η stands for 8, 10 or 12, with a suitable one ^ -Aminoalkylsilane or -siloxane converts. 2. Process according to claim 11, characterized in that the γ-aminoalkyl group is a Γ-aminopropyl group. 13. Process for the preparation of silanes and siloxanes. according to one of claims 2 to 9, characterized in that a compound of the general formula GF ~ OCVE ^ oG ₀ Cl is reacted with a y-aminoolefin and the product is then reacted with; a silane or siloxane containing at least one silicon-bonded hydrogen atom. 14-, method according to claim 13, characterized in, that the, ^ "- aminoolefin is a 3-aminopropyl-1-ene. 15 · Process for the production of silanes and siloxanes according to any one of claims 1 to 9, wherein a is 0, characterized in that a compound of the general Formula C F-. where η is 8, 10 or 12, with an alkenylmagnesium bromide and then the product thus obtained with a silane or siloxane, the at least contains a silicon-bonded hydrogen atom, implements. '5. Process for the preparation of a filled fluorocarbon polymer from a filler and a granular fluorocarbon polymer, both in powder form, characterized in that the filler is treated with a fluorocarbon derivative and the filler is agglomerated together with the polymer from an aqueous medium, the fluorocarbon derivative being a silane or siloxane which contains a CF ^ p- ^ group, in which η is 8, 10 or 12, this group being ^{bonded to a group of the formula SiH} '^ _c 0 ₅ _ _b _ _c , in which R is a ² 309843/1195 ■ - 22 - ■■■■ - ■ represents a monovalent hydrocarbon group, X represents a hydrolyzable group, b represents 0 or Λ , c represents 0, 1, 2 or 3 and b + c is not greater than 3. " 17 · The method according to claims 1-6, characterized in that that the silane or siloxane fluorocarbon derivatives is a compound of claim 1. 13. The method according to claim 17 »characterized in that the fluorocarbon derivative _{C 10} P, _{g 0C 6} H ^ (CH ₂ ) ₃ Si (0CH ₅ ) ₅ or G ₁₀ F ₁₉ GC ₆ E ₄ -SO ₂ -IiH (CH ₂ ) ₃ 3i 19 · method according to one of claims "" G to "S, characterized in that the filler with a solution of the silane or siloxane is treated to make it · hydrophobic to make before going with granular polytetrafluoroethylene is mixed and agitated in an aqueous medium. · 20. Antifoam agent, characterized in that "it a silane or siloxane according to any one of claims 1 to 9 ent stop. : 309843/1195