DE2235885A1 - FLUORCARBON WAXES AND PROCESS FOR THE PREPARATION - Google Patents

Description

The invention relates to a method for manufacturing of fluorocarbon waxes by telomerization of tetrafluoroethylene or monomers mixed with Tetrafiuoräthylenra "; other olefinic monomers. The invention also relates to the more stable produced by this process: Fluorocarbon wax dispersions and fluorocarbon wax powder with an average molecular weight of 10,000 to 200 OGC.

According to the state of the art, there are two principal ones Production methods for fluorocarbon waxes known:

Manufactured by pyrolysis of fluoropolymers or telomerization of fluorine-containing monomers in organic solvents.

The pyrolytic decomposition of fluoropolymers at temperatures above 400 ° C is described, for example, in c_er U.S. Patent 2,496,978, British Patent 1,047,768 and German Patent 1,049,099. However, the process has several disadvantages. That as the starting product Fluoropolymers used is an extremely expensive product due to its production, so that the production route by pyrolysis is only feasible if such polymers are incurred as waste that cannot be otherwise can be used. A manufacture of fluoropolymers.

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solely with the aim of subsequent pyrolytic vision For economic reasons, dismantling is not an option. During the pyrolysis itself, there must also be a considerable loss of yield be accepted by the fact that the reaction cannot be directed to waxy products alone, but also liquid and gaseous by-products are always produced. Hydrogen fluoride can also be split off with all their disadvantages with regard to corrosion of the reaction apparatus, never completely avoid them. In the end the product of such pyrolysis always occurs in the form of compact blocks, tubers or cakes, and must then be brought to the desired grain size by grinding.

To circumvent these difficulties, attempts have already been made to produce fluorocarbon waxes by telomerization of fluorine-containing monomers at elevated pressure and elevated temperature in the presence of free radical initiators. In those cases in which the solvent simultaneously takes on the role of telogen, only low molecular weight waxes with less than 30 tetrafluoroethylene units are obtained. Such processes are described in US Pat. No. 2,411,158, 2,433,844, 2,569,628 and 2,562,547. US Pat. 1,2-trichlorotrifluoroethane as the solvent under low levels of addition of a highly active telogen, such as methanol or methylcyclohexane, is carried out at temperatures in the range of 75 ° to 20O ⁰ C. This procedure has the advantage over the previously mentioned one that the fluorocarbon wax can be converted from the originally purely organic solvent phase into the aqueous phase. For this purpose, the suspensions of the fluorocarbon wax obtained in 1,1,2-trichlorotrifluoroethane are first mixed with water-soluble emulsifiers

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offset. Then use half of the solvent distilled off and then the remaining solvent removed with the gradual addition of water and with stirring. This process is cumbersome because of the small number of process steps and also because of the necessary recovery and drying the solvent. It's basically possible to make aqueous dispersions of plaor carbon waxes obtainable, but only in the lower molecular weight range Ms approximately in the range of 2000.

In the case of the "particularly interesting" for technical applications However, fluorocarbon waxes having a molecular weight range of 30,000 to 200,000 falls under the above Procedure initially produced suspension already during production or within a short time.

This is evidently due to the rapid growth of the primary particles initially formed during telomerization and especially during the removal of the solvent due to the granulating effect known for such solvents. The production of stable dispersions of Pluor.-carbon waxes also does not succeed by adding water-soluble ones Emulsifiers still in the solvent phase and subsequent replacement of the organic solvent against water. . "" "" "

The present invention relates to a process for the production of fluorocarbon waxes, characterized in that that monomeric tetrafluoroethylene, optionally in a mixture with 0.1 to 40 mol% of comonomers of the formula

CHp - CHo

CF ₂ = CFX (X = H, CF ₃ , Cl ,: Br, J) ■ or CF ₂ = CX ₂ (X = H, Cl, Br, J)

or mixtures of these said comonomers in the presence of 0.1 to 15% by weight , based on the monomers used, of one

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telogenic compound of the formula

^CH n ^X 4_n (n = 0 to 3, X = Cl, Br)

CtUJ,

^C n ^F 2n ₊ 1 ^J (n-1MB3),

_{2 2} J or CFJ ₂ . CF ₃

or a mixture of said telogenic compounds in aqueous, weakly alkaline phase in the presence of initiators and emulsifiers used for tetrafluoroethylene dispersion homopolymerization are common at temperatures from 0 to 40 ° .C and at pressures of 0 to 25 atmospheres using a specific stirring energy in the range of 2.4. 10 to 3.5. 10 kp; m / sec / cm telomerized to form a stable fluorocarbon wax dispersion and this dispersion, if appropriate, subsequently is coagulated and dried.

The process according to the invention is carried out in a purely aqueous phase, in addition to the telogenic compound does not contain any organic solvents. The aqueous telomerization liquor is through before the start of the reaction Addition of a corresponding amount of dilute, aqueous ammonia solution adjusted to a weakly alkaline level (pH 7.1 to 9) The telomerization can in principle also be carried out at pH values ^ 7, i.e. in the acidic range. this however, leads to an undesirable reduction in the stability of the resulting dispersion and thus leads to a likewise undesirable increase in the grain diameter of the coagulated powder.

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The telomerization takes place in the presence of water-soluble initiators and in the fermentation of water-soluble emulsifiers, which are known and customary from the tetrafluoroethylene dispersion homopolymerization. The initiators with " one for that. The above-mentioned temperature range suitable decay half-life are mainly the known redox starter systems, such as ammonium persulphate / sodium bisulphite, Ammonium persulfate / hydrazine, ammonium persulfate / iron (II) salts and iron (III) salts / sodium bisulfite. As suitable emulsifiers Particular mention should be made of ammonium or alkali salts of perfluorocarboxylic acids or 4r-hydrofluorocarboxylic acids.

The telomerization is carried out at a pressure in the range from normal pressure to 25 atmospheres, preferably in the range from 6 to 18 atmospheres. The temperatures used are between 0 and 40 ⁰ O, preferably between 20 and 35 ⁰ C. To achieve a sufficient and constant telomerization rate, the specific stirring energy must be on average compared to the homopolymerization of tetrafluoroethylene in dispersion under comparable pressure, temperature and apparatus conditions can be raised by about $ 50. It is between 2.4 x 10 to 3.5 x 10 kp 7. M / sec / cm (in the case of the homopolymerization of tetrafluoroethylene approximately between 1.2 10 ^ to 2 χ 10 ^ kp? M / sec / cm).

It is of particular advantage that the process according to the invention can be carried out in the same apparatus like the large-scale tetrafluoroethylene dispersion polymerization. The starting monomer used in the process according to the invention preferably tetrafluoroethylene used alone. Tetra, fluoroethylene can, however, also together with comonomers of

Formula - ■ ^j

CH _2. = CH ₂ ,; ·

CF ₂ = CFX (X = H, CF ₃ , C £, Br, J), or CF ₂ = CX ₂ (X = H, Cl, Br, J)

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or telomerized with mixtures of such monomers. These comonomers or monomer mixtures are used in Amounts from 0.1 to 40 mol-? 6, preferably 1 to 15 mol- I ^, based on tetrafluoroethylene, used. In addition to the ethylene are available as comonomers. to mention in particular trifluorochloroethylene, Trifluoroethylene, trifluorobromethylene, trifluoroiodoethylene, Hexafluoropropylene and 1. i-Difluor ^^ - dichloroethylene. Compounds of the formula are used as telogens

^CH n ^X 4-n (n = 0 to 3, X >> Cl, Br), CH ₃ J, ⁰ An ₊ V ^{J (n = 1 to 3)} 'CP ₂ J. CP ₂ J, or CPJ ₂ . CP,.

Of these compounds, particular mention should be made of dibromochloromethane, dichloromonobromomethane, methylene chloride, dibromodichloromethane, carbon tetrachloride, bromoform, methyl iodide, pentafluoroethyl iodide, perfluoroisopropyl iodide and 1,1- and 1,2-diiodotetrafluoroethane. Chloroform is particularly preferred. The compounds mentioned can be used individually or as a mixture. The telomerization takes place in the presence of 9 % to 15% by weight, preferably 0.4 to 10% by weight, of telogen or a telogen mixture, based on the amount of starting monomer or starting monomer, narrowly. In general, the telogen or the telogen mixture is added to the aqueous plot before the start of the reaction. However, if it is a question of gaseous telogenic compounds, it can also be mixed with the monomer or monomers in a mixed gas battery and conveyed together with them at constant pressure into the telomerization autoclave. ! "■■ In another embodiment, the Telo can also be fed in separately from the monomer with the aid of a micro-

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dosing device take place, with gaseous or volatile Telogens are converted into the liquid state by a cooling device attached to the dosing system.

In general, a purely aqueous liquor is presented with the indicated auxiliaries. However, if within the specified Area of the particle size of the initially resulting fluorocarbon wax dispersion a shift in the direction of the upper limit is desired, a fluorocarbon wax dispersion obtained by the process according to the invention be presented as seeds. The aqueous liquor is adjusted so that the solids content of this seed is 0.3 to 3.0, preferably 0.5 to 2.0% by weight, based on the total weight of the starting liquor, amounts to. A seed dispersion is preferably used which is made from the same starting monomers mit.Hilfe the same telogens have been produced as those which then arrive at the "reaction" in the main telomerization. Es however, it is also possible to use one with regard to the starting monomers differently composed seeds and / or a seed dispersion produced with other telegenes, obtained according to the invention Process to be submitted without affecting the properties of the resulting dispersions or fluorocarbon wax powder leave the scope of the invention. ■ "'

It was extremely surprising that the tree-time yields of the process according to the invention are in the order of 150 to 300 g / l / h, ie in the same order of magnitude as the space-time yields of the large-scale polymerization of tetrafluoroethylene. In itself it should have been expected that the presence of chain-transferring. Telogen compounds, as known from the prior art, delay the reaction and reduce the space-time yields
leads. . '·

The initially resulting fluorocarbon wax dispersions
are surprisingly "extraordinarily stable. During the telomerization and after the end of the telomerization, despite the stricter stirring conditions, absolutely nothing occurs
Coagulate formation observed. Hence the addition of a

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Overlaying agent, as it is often used in tetrafluoroethylene polymerization in the form of waxy hydrocarbons and the like, has proven to be superfluous. The fluorocarbon wax dispersions that are primarily formed are so stable that they can be telomerized without difficulty up to a solids content of 40% by weight, based on the total weight of the dispersion. It is of course also possible to achieve very low solids contents, but usually at least up to 5% by weight, preferably up to 20 % by weight, solids content will be telomerized. Higher solids contents than 40 wt -.% Can be achieved by post-treatment according to the conventional methods of distillation, concentration or the electrodecantation.

The invention thus also relates to stable fluorocarbon wax dispersions, such as are obtainable by the process according to the invention, consisting of spherically shaped particles with an average particle diameter of 0.01 to 0.5 / U and with a narrow size distribution, expressed by the value Δ d 1/2 / d _av <0.35.

This value ^ j d 1/2 / d is taken from the particle diameter distribution curve derived. This curve is obtained by counting the numbers in the electron microscope image the particle diameter measurable in the dispersion. The abscissa value associated with the curve maximum corresponds to the variable d. A straight line is drawn through the middle of the corresponding ordinate value parallel to the abscissa axis and the line between The distance between the points of intersection of this straight line and the two branches of the distribution curve is denoted by / d d 1/2.

The mean particle diameter of the spherically shaped dispersion particles is preferably 0.03 to 0.2 / u; the value A. d 1/2 / d for the size distribution is preferably between> 80 and <0.35.

The fluorocarbon wax dispersions initially obtained are then optionally coagulated and dried to give a powder. The coagulation can in principle be carried out by customary methods, because of the high stability of these dispersions

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with regard to the means to be used - chemical precipitants or mechanical energy - more stringent conditions are applied Need to become. The coagulation can take place by adding acids to the dispersion with simultaneous stirring, whereby the dispersion is to be adjusted to a pH of 6 to 2. First and foremost, concentrated hydrochloric acid is used for this Question, however, organic acids such as acetic acid can also be used. Instead of acids you can Precipitation electrolytes in the form of concentrated salt solutions are also used, such as solutions of sodium chloride, Ammonium chloride, ammonium carbonate and potassium carbonate.

However, the use of acid for coagulation has the advantage that in the subsequent neutralization of the ι precipitated dispersion with carbonates, in particular ammonium carbonate, a better and faster separation of the precipitated finely powdered wax is achieved by the mother liquor under the action of the COp released. The wax after a short time it floats on the surface and can be easily separated and repeated by adding Water to be washed.

The dispersion can also be coagulated by mechanical stirring, with increased stirring energies of " 0.35 PS / 1 to 0.40 PS / l are to be used.

If the dispersion is coagulated in a way other than with the help of acids, it may have to be closed beforehand neutralize.

The drying of the precipitated coagulum to fluorocarbon wax powder is best carried out in convection or vacuum drying ovens at temperatures of 80 to 200 ° C, preferably from 100 ⁰ C to 170 ° C.

In the known coagulation of polytetrafluoroethylene dispersions powdery dispersion polymers are obtained which consist of agglomerates of primary particles, where is the mean particle diameter of such agglomerates

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is between 200 / rev and 1000 / rev. It was therefore extraordinary It is surprising and unforeseeable that the coagulation of the fluorocarbon wax dispersions obtained by the process described to extremely fine powders with an average particle size of the primary grain of 0.5 to 6 / U, preferably from 1 to 3 / u, and too novel Product properties leads to · .. "

The invention therefore also relates to fluorocarbon wax powders with an average molecular weight in the range from 10 to 200,000, preferably from 30,000 to 150,000, such as are obtainable by the process according to the invention. These fluorocarbon wax powders are characterized by their aforementioned particle size of the primary grain and by a grain distribution of the primary grain, expressed by the size ^ jd 1/2 / d <0.9 (measured according to the method described above), these primary grain particles being more than 70 % are associated with a loose, grape-shaped composite of 8 to 20 / U diameter, further by a specific surface area of 10 to 26 m / g (measured according to the BET method), by a total pore volume of 80 to 120 cm / 100 g of dry matter , by a transformation temperature crystalline / amorphous of 270 to 325 ⁰ C and by a

2 pp

apparent melt viscosity of 0.7 x 10 6 to 1. 10 poise

at 380 ⁰ C and 200 kp / cm ² .

The size distribution of the primary grain Δ d 1/2 / d is preferably> 0.7 and <0.9. The preferred values for the crystalline / amorphous transition temperature are 290 to 325 ° C., and 1 for the apparent melt viscosity. 10 ⁵ to 1.5 · 10 ⁷ poise (at 380 ° C

J.QQJ 2 \ and Arkp / cm).

The association of the primary grain of the fluorocarbon wax powder obtained to form larger, grape-shaped structures of 8 to 20, preferably 10 to 15 / u, mean grain diameter and to an extent of> 70 %, preferably 75 to 100 % of the total number of primary grain particles is Recordings can be determined under the electron microscope. Because of this structure, the fluorocarbon wax powders according to the invention have a fairly low tendency to form dust, which is otherwise unpleasant when processing similar finely divided materials. ■ This is why these powders can also be dried without difficulty in a circulating air drying cabinet. The measurements of the total

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pore volume: the Hg porosimeter (model 65, company Erben, Milano) is based on the following principle: A certain pressure is required for mercury to penetrate into a porous material, regardless of the mean pore diameter. When the pressure is increased gradually, all pore sizes are filled with mercury one after the other. In addition to a so-called pore spectrum, the total pore volume is determined from these measurements by integrating the amount of mercury absorbed. For the fluorocarbon wax powders according to the invention, the measurements resulted in the pressure range from 1 to 1000 atmospheres with detection of the pore spectrum from 12.5 to. 0.015 V- a total pore volume in the range from 80 to 120, preferably 90 to 110 cnr / 100 g dry matter. In comparison, values of 50 to 60 cm / 100 g dry matter were obtained for fluorocarbon waehse obtained by pyrolytic degradation under the same measuring conditions Range of values of pyrolytic degradation waxes.

The determination of the specific surface area of the invention Fluorocarbon wax powder is made according to the BET method (S.Brunauer, P.H. Emmet, G.J. Teller, J..Am.Chem. Soc. 60, 1938, p. 309). It gave unexpectedly high values of 10 to 26 m / g, preferably

wise from 12 to 20 m / g. For comparison, the waxes obtained by way of pyrolytic degradation showed themselves after previous fine grinding to approx. 6 u mean grain diameter, Values for the specific surface of 3 to 6 m / g. Because of their pore-rich structure for the Paste extrusion suitable dispersion polymers of the poly

tetrafiuoräthylens only reach 7.6 to 9 m / g.

It was also found that the fluorocarbon wax powders according to the invention were unexpectedly used high stirring forces (for example using a

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high-speed stirrer of the Ultra-Turrax type) at approx. 10,000 rpm in organic solvents such as perchlorethylene, Toluene and benzene, are redispersible to form stable dispersions. Stable dispersions could be obtained, those with an average particle diameter of about 0.1 / U contain up to 20 wt .-% solids. Pyrolytic degradation waxes do not have this property of redispersibility.

The fluorocarbon wax dispersers according to the invention are for various types Purposes technically applicable. They can be used when laminating foils made of polytetrafluoroethylene, PTFE copolymers and PTFE "compounds" on metal surfaces. As an additive to PTFE coating materials in the form of dispersions they improve the freedom from pores and the adhesion to the substrate of such coatings. You can also serve for the impregnation of glass fibers and asbestos products, whereby they penetrate the material better than polytetrafluoroethylene dispersions and also the lower sintering temperature and the lower melt viscosity are advantageous. Stable fluorocarbon wax dispersions can also be used with other aqueous plastic dispersions such as PVC, PTFE and polystyrene dispersions are mixed in a dispersed state. If such dispersions are precipitated, uniform mixing remains with the fluorocarbon wax particles in the coagulate and results in improved processability, e.g. as a release agent. Finally, the fluorocarbon wax dispersions according to the invention are converted into an organic solvent phase with exchange of the ytesser and then serve as drying, lubricating sprays or in combination with other organic synthetic resin solutions as bonded coatings. ,

The fluorocarbon wax powders according to the invention are valuable additives for lubricants and polishes. You can also Because of their finely divided form in dispersion they are used as sprays, which are also used as lubricants, but also for Manufacture of water and oil repellent or anti-corrosion protective coatings are applied. In intimate mixtures with other plastics, such as polypropylene,

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Polyamides, phenolic or epoxy resins, they can be used for production self-lubricating bearing parts in friction-loaded Serving apparatus. Fluorocarbon waxes in very finely divided powder form have proven particularly useful as demoulding, Release agents and lubricants have been tried and tested in plastics processing and in deep drawing of sheet metal. at In all of these applications, the high degree of fineness of the fluorocarbon wax powders according to the invention is of considerable importance Meaning. This is particularly true for additives to lubricants, as well as for the production of coatings and coatings, where the fineness results in a significantly improved homogeneity.

The following examples are intended to illustrate the invention without limiting its scope:

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Examples: General working regulations:

a) Telomerization

Unless otherwise noted, the telomere approaches were carried out in enamelled 40 1 stirred autoclaves equipped with propeller stirrers. In the stirred autoclave submitted liquor of 20 1 deionized water, 17 g of perfluorooctanoic acid were dissolved and the The pH is adjusted to 8 to 9 by adding aqueous ammonia solution. The respective telogens were either presented with the aqueous liquor or premixed together with the monomers in a mixed gas battery or metered in separately during the telomerization. After repeated purging with nitrogen, the monomer became or the monomer mixture pressed into the kettle and the batch after reaching the reaction temperature and switching on the stirrer by adding 2.8 g of ammonium persulfate and 1.76 g of sodium bisulfite, in part dissolved in water, started.

b) work-up

The resulting fluoro carbon wax dispersion was reduced to a solids content of 10 to 20% by weight by adding diluted by water, with approx. 3 wt. 56 more concentrated Hydrochloric acid is added and the mixture is stirred in the polymerization kettle at 130 to HO rpm. The subsequent neutralization the hydrochloric acid with ammonium carbonate made the coagulated product float. The one in the lower Aqueous phase which had settled in part of the kettle was drained off via a bottom valve. Duret three times the addition of Deionized water, the product was washed with stirring (20 rpm) and the rapidly settling The washing water is drained off after each washing process. That

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Moist powder remaining in the kettle was then

on sheets

dried.

on trays in a convection oven at 150 to 200 ⁰ C.

In Table-1 / Lind .2 the test batches with the addition of the or the set starting monomers and telogens and the Reaction conditions compiled. The measured values given in table 3 were, unless already described above, was obtained as follows: The mean particle size of the primary grain of the powder was determined by counting and measuring the in particles visible in the electron microscope image certainly. The transition point was crystalline / amorphous aus.der differential thermal analysis of powder samples.

The following procedure was used to determine the melt viscosity: The amount of the "extruded melt and the unit of time" were determined, which at a given temperature was below given pressure exits from a nozzle with given dimensions (diameter and length). The is calculated from this apparent melt viscosity .......

P .. fri. r ⁴

- '■ -8:. 1:. \ Q
where ■. '

τ- O -t

P = extrusion pressure Ldyn / cm J r = 4 nozzle radius Ecm

1 = nozzle length EcmJ

q = amount of extrudate escaping £ cm / secj

Melt extrusion was carried out with a high pressure capillary viscometer of the Göttfert company under the following

Measurement Conditions (unless otherwise stated): 380 ⁰ C

2
200 kp / cm extrusion pressure, nozzle dimensions 1 mm diameter, 40 mm length, the extrudate is given in cm / min. The BET measurements were carried out "under absorption of argon at -195 ⁰ C. The dispersion stability of the resulting fluorocarbon wax dispersions · was measured with a rotation

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viscometer of the FIr »θ Haaice ®n dispersions with 20 ^ solid content; indicated t &% the downtime in minutes.

3098Ö6 / 0S7O

Tabel

Telomerization with mixing of the telogen causes the monomer or monomers

in the mixed gas battery

Attempt starting monomers (s) telogen pressure temp No. wt .- ^ wt .- ^ atu. C proportion of seeds

> moved to Aus

Float by weight -io pesticide- average part content of the particle size obtained from the primary dispersion grain (wax- - $ powder) u

Transformation temperature crystalline amorphous (wax powder)

¹ Vn

1
2
3

4th
5
6th

yy, p 22

yo, ο ου ₂ = ojj 2
97.7 CF ₂ = CF ₂
96.3 CF ₂ = CP ₂
94.6 CP ₂ = CF ₂
90.2 CP ₂ = CP ₂

Cr) 7th 88.0 CP ₂ = CF ₂ ^^
O
in 8th 85.0 CP ₂ = CP ₂ 9 87.3 CF ₉ = CF ₉ / 11.5 \ jJ2 / - * · "■ v / J? O J- I.
r- 10 84.5
8.0 CF ₉ = CF ₉ /
CPo = CPCl INSP 11 88.0
4.5 CP ₂ = CF ₂ / (L c. 12th 80.5 CP ₉ = CF ₉ / m
O 12.0 CF | -CF = CF

0.5 CP ₃ -CP ₂ J 19

1.2 CP ₃ -CF ₂ J 1.4

2.3 CF ₃ -CP ₂ J 17 3.7 "CF ₃ -CF ₂ J 19

5.4 CF ₃ -CF ₂ J ¹ ) 19 9.8 CF, -CFJ-

12.0 CF., - CF J-
^ CF ₃

15.0 CF ^ -CPJ-

19 19 19

1.2 CP ₃ -CP ₂ J

7.5 CP ₃ -CP ₂ Y 17 7.5 CF ₃ -CF ₂ Y 17 7.5 CF ₃ -CP ₂ Y 17

32 25 34 32 32

32 32 32

32 36 32 32

0.8

2)

1.5

3)

1.5 2.0 1.8 1.7

1.5 2.5 2.0

1.2

1.0

1.1 1.5

324 320 3i9 318

317

311 310

299 292 271 318

TO U)

} metered in during the telomerization

2) Same composition of the seeds (like experiment

3) Same composition of the seeds (as experiment 7)

00

OO

Table 1 (continued)

Experiment starting monomers (s) Telogen Pressure Temp. Wt .- $ wt. - $> atü C seed content content of the particle size temperature

moved to Aus ^ obtained the primary crystal input liquor Granular dispersion (wax-amorphous

Wt. - <fo wt .- ^ powder / U (wax powder

13 86.7 CFp = CFp /

4.5 CF ₃ -CF = CF ₂ 8.8 CF ₃ -CF ₂ -J 17 32

14 92.0 CFp = CFp /

6.0 CF ₂ = CFBt 2.0 CF ₃ -CF ₂ J 17 32

• 15 91.0 CF ₉ = CF ₉ /

5.0 CF ^ = CF? 4.0 CF ₅ -CF ₂ JH

to 16 93.0 CFp = CFp / a \

^ 3.0 CH ₂ = CHI 4.0 CF ₂ J-CF ₂ J 20 32 2.0 ^;

CO
00
CD

20th 1.5 315 17th 2.0 319 15th 1.7 317 12th 2.6 3I6

4) Composition of the seeds as in the experiment

fabeile 2
Telomerization with presentation of cLes Telogeais in the aqueous

"Try ffr.

second monomers

Delogen

a do

Gate-laid solids avg. for sale - conversion of seeds - content - the size of the temperature

■ moved on from - obtained the test surface - crystalline - gaaigsflotte ^ dispersion koicns (wax-amorphous

'-fo, powder) Ai {W

' ~ G

1 2 3 4 5 .. € -. 7 8

10 11 12 13 1.4 15 16 17

<1.i

8} J (2.4)

4)). IT

14 H, Q) ... 1-7.

<1, O)

Ci ₁ O) IT ;.

, 0) 'jO)'

, 7)

, 5)

, Q)

3.7) 14

■, 0) "

GHGMO, 2)

32 25 32

32. 32

28 32

32 32

28:28 28th

25,

32 32

11, p. ⁴¹ .28

34.

17th

20th

19th

20th

20th

18th
20th
18th
20th
17th
20th
20th

2.5
4.5
1.2

3.0
1.5
1.4-1.7

2.5

1.7

1.8

2.2

1.8

■ 1.3

.1,2

321 317 307 327 318

324 321 323 321

318

319 318

315-

320

322

1) Remainder against 100 from total & ev? ..-- $ a further Honomeres + Sew ..- Tetrafluoroethylene used by weight

2) Composition of seeds as in the experiment

3) Composition of the seeds as in experiment 14.. .

Telogen

, - $ lied alone

Table 3 Properties of the fluorocarbon wax powder or dispersions

attempt No., tab.

Rotovisko stability d. Dispersion min. Sec.

Antipore extrudate το1useη

cb3 / 100 g cm3 / min.

Apparent Schnsel zvi B - viscosity poise

Specific BET surface area » ² / g

Primary grain distribution of the powder

av

1 4 ' 1 5 ¹ 1 VJl 1 4 ' 1 6 * 1 10 ' 1 8th· 1 20 ' 1 15 ' 1 16 » 1 9 ¹ 1 9 ' 1 V 1 4 ' 1 3 ¹ 1 5 ¹ 2 6 · 2 7 ¹ 2 4 · 2 ■ 2 · 2 8th' 2 3 ^f 2 2 · 2 ϊ · 2 2 ¹ 2 2 · 2 8th;· 2 4 * 2 25 · 2 2Λ ¹ 2 2 2 7 '

50 "20" 40 "30"

20 "20" 30 "10" 25 "8" 10 "

20 "10" 30 »· 45" 3.0 "10»

15 "1: 0" 25 «

40 "50" 35 * 45 " 4 $ * 40 "10 * * · 50 * 50 "30"

ΪΟ5 118 106 101 108

0.51 2.17 χ 10-3

113.4 χ 10-

15 17 22 22 16 18 14

19 20

23 25 18 23 17 14 22 18 22

23 18 16 22 21 19

17 15 22 24 20 16 19 21 16

0.8

0.75 0.85

0.78

0.89

0.88

-fe) 380 ⁰ C, 7.3 kp / cQ ^; Nozzle ι 2.08 ηα; Length 8 approx

Claims (7)

Claims Process for the production of fluorocarbon waxes by telomerization of tetrafluoroethylene or monomer mixtures of tetrafluoroethylene with other olefinic monomers, characterized in that monomeric tetrafluoroethylene, optionally in a mixture with 0.1 to 40 mol % of comonomers of the formula p p CF ₂ = CFX (X ==, H, CF ₃ , Cl, Br. J) or CF ₂ = CX ₂ (X = H, Cl, Br, J) or with mixtures of these said comonomers, in the presence of 0.1 to 15% by weight, based on the used Monomers, a telogenic compound of the formula ^CH n ^X 4-n (n = ( ) until 3, X = CH-J I!
I ■ ^C n ^F 2n ₊ 1 ^J (n = ' I Ms 3) ^: PT? T PT? T
LJ? pd. or pd or CFJ ₂ . CF ₃ or a mixture of said telogenic compounds in aqueous ,, weakly alkaline phase in the presence of Initiators and emulsifiers used for tetrafluoroethylene dispersion homopolymerization are common at temperatures from 0 to 40 ° C and at pressures from 0 to 25 atm using a specific stirring energy in the range of 2.4. 10 to 3.5-10 kp. m / sec / cnr telomerized to a stable fluorocarbon wax dispersion and this dispersion is then optionally coagulated and dried. 2.) The method according to claim 1, characterized in that the telogenic compound · ** presented with the aqueous liquor will. ] · ... ' ]: -22-, 309886 / 0S70 j 3.) The method according to claim 1, characterized in that the telogenic compound with the monomeric tetrafluoroethylene, optionally with the monomer mixture, in a mixed gas battery premixed and this mixture is fed to the aqueous liquor. 4.) Process according to claim 1 to 3, characterized in that a fluorocarbon wax seed dispersion with the aqueous liquor, obtained by the method according to claim 1, is presented, the proportion of seeds in the aqueous liquor being 0.3 to 3% by weight, based on the total weight of the starting liquor. 5.) The method according to claim 4, characterized in that the The seed dispersion presented consists of the same monomers and was obtained with the aid of the same telogens as they were be used in the main telomerization. 6.) Stable fluorocarbon wax dispersions, obtainable by the process according to claim 1 to -5 »consisting of spherically shaped particles with an average particle diameter of 0 _f 01 to 0.5 / u and with a narrow size distribution, expressed by the value ^ id 1/2 / d <0.35. 7) fluorocarbon wax powder with an average molecular weight in the range from 10,000 to 200,000, obtainable by the process of claims 1 to 5, characterized in that they have an average particle size of the primary grain of 0.5 to 6 / U, these Primärkornteilchen more loose than 70% to a, grape-like composite 10 to 20 / associated u diameter, further that it has a particle size distribution of the primary grain is expressed by the size ^ d ^1/2 / ^d _av "of <0.9, a specific surface area of the powder, measured by the BET method, of 10 to 26 m / g, a total pore volume of 80 to 120 cm / 100 g dry matter, a crystalline / amorphous transition temperature of 270 to 325 and an apparent melt viscosity of 0.7 x 10 ² own. 0.7 x 10 ² to 1 χ 10 ⁸ poise at 380 ° C and 200 kp / pm ² 309886/0570