DE2235885B2 - Fluorocarbon waxes, aqueous fluorocarbon wax dispersions and processes for their preparation - Google Patents

Description

CH ₂ - CH2

CF ₂ = CFX PC = H, CF ₃ , Cl, Br, J)

CF ₂ - CX ₂ (X = H, CI, Br, J)

10

or with mixtures of these comonomers in the presence of 0.1 to 15 percent by weight on the monomers used, a telegenic compound of the empirical formula

CH _n X ₄ .. ,, (i! = 0 to 3, X = Cl, Br) or

C _n F _{2n +} , J (n = 1 to 3) or the formulas
CH ₃ J ₁ CF ₂ J-CF ₂ J or
CFJ ₂ - CF _; .

or a mixture of said telogenic compounds in the presence of free radical-forming initiators, characterized in that in the aqueous, weakly alkaline phase in the presence of free radical-forming initiators and emulsifiers which are customary for tetrafluoroethylene dispersion homopolymerization, at temperatures from 0 to 40 ⁰ C and at pressures of 0 to 25 atm using a specific stirring energy in the range of 2.4 x 10 ^"5 to 3.5 10" ⁵ kgf · m / sec / cm ¹ telomeriiiert is.

2. The method nacili claim 1, characterized in that that the telogenic connection with the aqueous liquor is established.

3. The method according to claim 1, characterized in that that the telogenic connection with the tetrafluoroethylene, optionally with the monomer mixture, premixed in a mixed gas battery and this «mixture of the aqueous liquor is fed.

4. The method according to claim 1 to 3, characterized in that one with the aqueous liquor Fluorocarbon wax seed dispersion, obtained by the process according to claim 1, is presented, The proportion of seeds in the aqueous Flotlc is 0.3 to 3 percent by weight, based on the total weight the starting fleet is discontinued.

5. The method according to claim 4 thereby gekennleichnet. that the seed dispersion presented consists of the same monomers and with the help the same telephony was obtained as used in the main telephony.

6. Aqueous fluorocarbon wax dispersion, characterized in that they have been prepared by the method according to claim I bus 5 and spherically shaped telomerizate particles with an average particle diameter of 0.01 to 0.5 μ and with a narrow size distribution, expressed by the Value hf \ / 2 / d " ₀ < 0.35, included.

7. Fluorocarbon wax powder with an average molecular weight in the range from 10,000 to 200,000, characterized in that they have been prepared by the process of claims I to 5 and have an average particle size of the primary grain of 0.5 to 6 μ , these primary grain particles to meltjr than 70% are associated with a loose cluster of grapes 10 to 20 microns in diameter, furthermore that they have a redistribution of the primary grain, expressed by the size I d 1/2 / ί / _βΡ . of <0.9, a specific surface area of the powder., measured by the BET method. from 10 to 26nr / g. a total pore volume of 80 to 120 ^cm3 / 100 g dry substance, a transition temperature crystalline amorphous from 270 to 325 and an apparent melt viscosity of OJ · 10 ² have to 1 x IO ⁸ poise at 380 ⁰ C and 200kp'cnr.

According to the state of the art, there are so far two principal ways of producing fluorocarbon wax known:

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

The pyrolytic decomposition of fluoropolymers at temperatures above 400 "C is for example described in U.S. Patent 2,496,978; British Patent 1,047,776S and German Patent 1,049,099. However, the process has several Disadvantage. The fluoropolymer used as the starting product is due to its manufacture a extremely expensive product, so that the production route by pyrolysis is only feasible. when such polymers are generated as waste that cannot be used elsewhere. One Production of fluoropolymers for the sole purpose of subsequent pyrolytic degradation is out of the question for economic reasons. In the case of the pyrolysis itself, a considerable loss of bulging must also be accepted as a result, that the reaction cannot be directed to waxy products alone, but always alongside them incurred liquid and gaseous by-products. Auc ', 1 can be an elimination of hydrogen fluoride With all of their disadvantages with regard to corrosion of the reaction apparatus, never avoid them entirely. Ultimately, the product of such pyrolysis always falls in the form of compact blocks. Tubers or Cake on. and must then be brought to the desired grain size by grinding.

To circumvent these difficulties, attempts have already been made to use fluorocarbon wax by telomerization of fluorine-containing monomers at elevated pressure and temperature in the presence by radical initiators. In these In some cases, the solvent also takes on the role of telogen. Describe such procedures U.S. Patents 2,411,158, 2,433,844, 2,569,628 and 2,562,547. According to example 2 of GB-PS I 069089 a polytetra-polyurethane wax is obtained in carbon tetrachloride with a molecular weight of 20,000. US Pat. No. 3,105,824 also discloses a process known, in which the telomerization of tetrafluoroethylene in the telogen, little active 1,1,2-tri-

cblortrifluartithan as solvent under low levels of addition of a highly active telogen, such as methanol or methylcyclohexane, is carried out at temperatures ranging from 75 to 200 ^Q 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 resulting suspensions of the fluorocarbon wax in 1,1,2-trichlorotrifluoroethane are first mixed with water-soluble emulsifiers. Half of the solvent is then distilled off and then the remaining solvent is removed with the gradual addition of water and with stirring. This process is difficult because of the large number of process steps and also because of the need to recover and dry the solvent. In principle, it is possible to use them to obtain aqueous dispersions of fluorocarbon waxes, but only in the lower molecular weight range up to approximately 2000.

The fluorocarbon waxes with a molecular weight range that are particularly interesting for industrial use from 30,000 to 200,000, however, the first falls in the course of the aforementioned procedure produced suspension during production or within a short time.

This is apparently due to the rapid growth of the primary particles initially formed during the telomerization and especially during the removal of the solvent as a result of what is known for such solvents. Granulation reflection. Stable fluorocarbon waxes cannot be obtained by adding them either water-soluble 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 by telomerization of tetrafluoroethylene, optionally in a mixture of 0.1 to 40 mol percent - based on tetrafluoroethylene - on comonomers of the formula

45 CH ₂ = CH ₂

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

50

or with mixtures of these comonomers, in the presence of 0.1 to 15 percent by weight, based on used monomers, a telogenic compound of the empirical formula

CH _n X ₄ - "(η = 0 to 3, X = Cl, Br) or
C _n F _{2n +} IJ {n = 1 to 3) or the formulas
CH ₃ J ₅ CF ₂ J-CF ₂ J or
CW ₂ -CF ₃

55

60 homopolymerization are common, at temperatures from 0 to 40 ^J C and at pressures from 0 to 25 atmospheres using a specific stirring energy in the range from 2.4 · 10 " ⁵ to 3.5 · 10" ⁵ kp · m / sec / cm ^{3 is} telomerized.

The method 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 before Start of the reaction by adding an appropriate one Amount of dilute, aqueous ammonia solution adjusted to be weakly alkaline (pH 7.1 to 9). Telomerization could, in principle, also take place at pH values <7, i.e. in the acidic range. However, this leads to an undesirable one Reduction in the stability of the resulting dispersion and rlamit too undesirable increase in the grain diameter of the coagulated powder.

The telomerization takes place in the presence of water-soluble initiators and in the presence of water-soluble emulsifiers produced by the tetrafluoroethylene dispersion homopolymerization The initiators with a temperature range suitable for the stated temperature range are known and in use The decay half-life is mainly the known redox starter systems, such as ammonium persulphate / sodium bisulphite, Ammonium persulfate hydrazine, ammonium persulfate / iron (II) salts and Iron (III) -sa! Ze / sodium bisulfite. As suitable emulsifiers Particular mention should be made of ammonium or alkali salts of perfluorocarboxylic acids or r »-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 ° C., preferably between 20 and 35 ° 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 increased by about 50%. It lies between 2.4 · 10 ^-5 to 3.5 × 10 ^-5 kg · m / sec / cm ³ (in the homopolymerization of tetrafluoroethylene between about 1.2 x 10 ^"5 to 2 x 10" ⁵ kgf · m / sec / cm ³ ).

It is of particular advantage that the inventive Process can be carried out in the same equipment as the large-scale Tetrafluoroethylene dispersion polymerisation. As a starting monomer in the invention Process preferably used tetrafluoroethylene alone. However, tetrafluoroethylene can also be used together with comonomers of the formula

CH ₂ = CH ₂

CF ₂ = CFX (X = H, CF ₃ , Cl, Br ₁ J)
or CF ₂ = CX ₂ (X = H, Ci, Br, J)

or a mixture of said telogenic compounds in the presence of free radical initiators, which is characterized in that in aqueous, weakly alkaline phase in the presence of free radical initiators and emulsifiers, telomerized for the tetrafluoroethylene disperstons or with mixtures of such monomers will. These comonomers or monomer mixtures are used in amounts of 0.1 to 40 mol percent, preferably 1 to 15 mol percent, based on tetrafluoroethylene, are used. Besides the ethylene are to be mentioned as comonomers in particular tri-

22 36

fluoroblorethylene, trifluorophylene, trifluorobromine * ethylene, triffuoriodethylene, hexafluoropropylene and l.l-difluoro-a.a-dichloro-ethylene. As telogens are used compounds of the empirical formula

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

C _n F _{2n + 1} J (n = 1 to 3) or the formulas

CH ₃ J ₅ CF ₂ J-CF ₂ J or

CFJ ₂ - CF ₃ ίο

Of these compounds, particular mention should be made of dibromochloromethane, dichloromonobromium chloride, Methylene chloride, dibromodichloromethane, carbon tetrachloride, bromoforra, methyl iodide, Pentafiuorätbyljodid, Perfluorisopropyljodid and 1,1- and 1,2-diiodotetrafluoroethane. Particularly preferred is chloroform. The compounds mentioned can be used individually or as a mixture will. The telomerization is carried out in the presence of 0.1 to 15 percent by weight, preferably 0.4 to 10 percent by weight, of telogen or telogen mixture, based on the amount of the starting iron ore of the starting monomer mixture. In general, the telogen or the telogen mixture is set before the start added to the reaction of the aqueous liquor. However, it can also be telogen insofar as it is gaseous Compounds acts, mixed in a mixed gas battery with the monomer or monomers and together with these at constant pressure in the linearization autoclave to get promoted. In another embodiment, the feeding of the halogen also take place separately from the monomers with the aid of a microdosing device, with gaseous or volatile telogens into the liquid state.

In general, a purely aqueous liquor is presented with the indicated auxiliaries. But when within the specified range of the particle size of the initially resulting fluorocarbon wax dispersion a shift in the direction of the upper limit is desired, one according to the invention Process obtained fluorocarbon wax dispersion are presented as seeds. the aqueous? The liquor is adjusted so that the solids content of this seed is 0.3 to 3.0, preferably 0.5 to 2.0 percent by weight, based on the total weight of the starting liquor. Preferably a seed dispenser is used, which consists of the same i Starting monomers using the same Telogeue as those made using the then come to reaction in the main telomerization. However, it is also possible to use a seed with a different composition with regard to the starting monomers and / or a seed dispersion prepared with other telogens, obtained according to the invention Process to be submitted without the resulting dispersions or fluorocarbon wax powders in their Properties leave the scope of the invention.

It was extremely surprising that the Space-time yields of the process according to the invention in the order of magnitude of 150 to 300 g / l / h lying, d. H. in the same order of magnitude as the space-time yields of large-scale polymerisation of tetrafluoroethylene. In itself it should have been expected that the presence would be chain-transmitting Telogen compounds, as known in the art, delay the response and leads to a reduction in space-time yields.

The initially resulting fluorocarbon wax dispersions are surprisingly of an extraordinary stability. During telomerization and after the end of the same, no coagulate is formed in spite of the stricter stirring conditions observed. Therefore, the addition of pines overcoating agent, as is the case with tetrafluoroethylene polymerization is often used in the form of waxy hydrocarbons and the like, proven to be superfluous. The primary emerging Fluorocarbon wax dispersions boiled so stably that there was no difficulty in boiling up to a solids content of 40 percent by weight, based on the total weight of the dispersion, can be telomerized. Of course, you can also achieve very low solids contents, but you will usually at least up to 5 percent by weight, preferably up to 20 percent by weight, with solids content.

Higher solids contents of 40 percent by weight can be obtained by aftertreatment according to the usual methods the distillative concentration or the electrode canting achievable.

The invention thus also relates to aqueous fluorocarbon wax dispersions which are characterized in that they have been prepared by the process according to the invention and spherically shaped telomerizate particles with an average particle diameter of 0.01 to 0.5 μm and with a narrow size distribution, expressed by contain the value \ dl / 2 / d _m < 0.35.

This value \ d l./2/d _m is derived from the particle diameter distribution curve. This curve is obtained by counting the particle diameters which can be measured in the electron microscope image of the dispersion. Here, dtr corresponds to the abscissa value belonging to the curve maximum of the variable d _av . By di ^«1 center of the corresponding ordinate value, a straight line is drawn parallel to the abscissa axis and between the points of intersection of this straight line with the two AEST ^ n of the distribution curve lying with distance! d 1/2.

The mean particle diameter of the spherically shaped dispersion particles is preferably 0.03 to 0.2 μ; the value \ d \ / 2 / d _at , for the size distribution is preferably between> 0.20 and <0.35.

The fluorocarbon wax dispersions initially obtained are then optionally coagulated and dried to powder. The coagulation can in principle take place by customary methods, with Because of the high stability of these dispersions with regard to the agents to be used - chemical precipitants or mechanical energy - more severe conditions must be applied. Coagulation can be done by adding acids to the dispersion with simultaneous stirring, the dispersion being adjusted to a pH of 6 to 2. In concentrated hydrochloric acid is primarily used, but organic acids, such as acetic acid can be used. Precipitation electrolytes can also be used in place of acids are used in the form of concentrated salt solutions, such as solutions of sodium chloride, Ammonium chloride, ammonium carbonate and potassium carbonate.

The use of acid for coagulation, however, has the advantage that the subsequent neutralization of the precipitated dispersion with carbonates, especially ammonium carbonate, results in better and faster separation of the precipitated fine powdery wax from the mother liquor under the action of the CO _{1 released} . The wax floats on the surface after a short while and can thus be easily separated and washed by repeatedly adding water.

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

If the dispersion is coagulated by means other than acids, it is optional to neutralize beforehand

The drying of the precipitated coagulate to form the fluorocarbon wax powder is best done in circulating air or Vacuum drying ovens at temperatures from 80 to 200 "C, preferably 100 to 170 ° C.

In the known coagulation of polytetrafluoroethylene dispersions pulverulent Disperstonspolymerisate are obtained, which from agglomerates of Primary particles exist, the mean particle diameter of such agglomerates between 200 and 1000 μ lies. It was therefore extremely surprising and unforeseeable that the coagulation the fluorocarbon wax dispersions obtained by the process described too extraordinary finely divided powders with an average particle size of the primary grain of 0.5 to 6 μ, preferably of 1 to 3 μ. and leads to novel product properties.

The invention therefore also relates to fluorocarbon wax powders with an average molecular weight in the range from 10,000 to 200,000, preferably from 30,000 to 150,000, which are characterized. that they have been produced by the method according to the invention and the aforementioned particle size of the primary grain and a grain distribution of the primary grain, expressed by the size \ d I 2; d "< 0.9 (measured according to the method described above), these primary grain particles being more than 70 ⁰ O are associated to a loose, grape-shaped composite of 8 to 20 μ in diameter, and also a specific surface area of 10 to 26 m ² g (measured by the BET method). have a total pore volume of 80 to 120 cm ^J / 100 g dry substance, a transformation temperature crystalline / amorphous of 270 to 325 "C and an apparent melt viscosity of 0.7 t O ² to 1 · 10 * poise at 38O ° C and 20OkPZcBi ² .

The size distribution of the primary grain id 1/2 / d " is preferably ϊθ, 7 and <0.9. The preferred values for the conversion temperature crystalline / amorphous are 290 to 325 ° C for the apparent melt viscosity 1 · ΙΟ ³ to 1.5 · JO ⁷ poise (at 38O ° C and 20OkPZCm ² ).

The association of the primary source of the received Fluorocarbon wax powder into larger, grape-shaped Formed from 8 to 20 µ, preferably 10 to 15 µ, mean grain diameter and to an extent of> 70%, preferably 75 to 1 (10% of Total number of primary grain particles is when taking pictures enter determinable with the electron microscope. On the basis of this structure have the according to the invention Fluorocarbon wax powder has a fairly low tendency to form dust, which would otherwise occur during processing similar fine-sided materials appear unpleasant. Therefore read this Powder without any difficulties in non-dry

S cupboards to dry. The measurements of the total pore volume with the Hg-Pörosimetei (model 65, company Eirben, Milano) are based on the following principle: For mercury penetration it: a porous material is independent of the mean

ίο pore diameter, a certain pressure required. When the pressure is increased gradually, rush pore sizes filled with mercury. In addition to a so-called pore spectrum, the total pore volume through these measurements

integration is determined by the amount of mercury absorbed. The measurements showed the erfindungsgemälkn fluorocarbon wax-Pul vir in the pressure range from I to lOOOatü under detection of the Porenspektrinms 12.5 to 0.015 μ a C <esamtporenvolumen in the range of 80 to 120. preferably 90 to UO ^cm3 / 100 g dry matter. ^{In comparison, values of 50 to 60 cm 3} / -100 g dry substance were obtained for fluorocarbon waxes obtained by pyrolytic degradation under the same measurement conditions. Coagulates from dispersion polystyrene products of tetrafluoroethylene also provide values for the total pore / otumen which are in the range of the values for pyrolytic degradation waxes.

The specific surface area of the fluorocarbon wax powder according to the invention is determined according to the BET method (S. B r u η a u e r, P. H. E m met. G. J. Teller, J. Am. Chem. Soc. 60. 1938, P. 309), it yielded unexpectedly high values from 10 to

26m ² g, preferably from 12 to 20m ^{2 /} g. For comparison, the waxes obtained by pyrolytic degradation had an average grain diameter of about 6 μm, even after prior fine grinding. Values for the specific surface area from 3 to

6m ² / g. The dispersion polymers of polytetrafluoroethylene, which are suitable for paste extrusion because of their pore-rich structure, can only be achieved

7.6 to 9 m ^J g.

It was also found that the fluorocarbon wax powders according to the invention were unexpected using high stirring forces (for example using a high-speed stirrer \ om type Ultra-Turrax) at around 10,000 (J me too stable in organic solvents such as perchlorethylene, toluene and benzene Dispersions are redispersible. In this way stable dispersions could be obtained which, in the case of one mean particle diameter of about 0.1 μ bi: contain 2Gi weight percent solids. Pyrolyti

SS see degradation waxes show this property Redispersibility does not arise.

The fluorocarbon wax disperser according to the invention Sions can be used for various technical purposes. They can be used when opening lamination of foils made of polytetrafluoroethylene Tetrafluoroethylene copolymers and poly tetrafluoroethylene-nCompousds «on metal surface As an additive to polytetrafluoroethylene coating materials in the form of dispersions improve si

⁶ S the absence of pores and the adhesion to the substrate of such coatings. They can also serve for the impregnation of glass fibers and asbesi erzeiignissen, whereby they better in the material

409 58474

ίο

penetrate as polytetrafluoroethylene dispersions and in addition, the lower sintering temperature and the lower melt viscosity are advantageous. Stable Fluofcarbo wax dispersions can also be used with other aqueous plastic dispersions, such as. B. s Polyvinyl chloride, polytetrafluoroethylene and polystyrene oil are mixed in a dispersed state. If titanium precipitates such dispersions, in this way the uniform mixing with the fluorocarbon wax particles in the coagula is preserved and gives improved processability, e.g. B. as a release agent. Finally, the invention Fluorocarbon wax dispersions with exchange of the water in an organic solvent phase and then serve as dry lubricant sprays or in combination with others organic synthetic resin solutions as bonded coatings.

The fluorocarbon wax powder according to the invention are valuable additives for lubricants and polishes.

They can also be used as sprays because of their dispersed form in dispersion also as lubricants, but also for manufacture can be used for water- and oil-repellent coatings or coatings that protect against corrosion. In heartfelt Mixtures with other plastics, such as polypropylene. Polyamides. Phenolic or Epoxy resins, they can be used for the production of self-lubricating bearing parts in frictional loads Serving apparatus. Fluorocarbon waxes in very finely divided powder form have proven particularly useful for demoulding. Release agents and lubricants in plastics processing and in deep drawing of sheet metal proven. In all of these applications, the high degree of fineness of the fluorocarbon wax powders according to the invention is essential of considerable importance. This also applies in particular to additives to lubricants, as well as in the production of coatings, where the fine division is an essential brings about improved homogeneity.

The following examples are intended to explain the invention without limiting their scope.

40

h) work-up

The resulting fluorocarbon wax dispersion was reduced to a solids content of 10 to 20 percent by weight diluted by adding water, mixed with about 3 percent by weight of concentrated hydrochloric acid and stirred in the polymerization kettle at 130 to 140 rpm. The subsequent neutralization of the Hydrochloric acid with ammonium carbonate caused the coagulated product to float. The one in the lower Aqueous phase that had settled out of the kettle was drained through a bottom valve. By adding three times the product was washed by deionized water with stirring (20 rpm) and that quickly Settling wash water is drained after each washing process. The moist powder remaining in the kettle was then dried on metal sheets in a circulating air drying cabinet at 150 to 200.degree.

Tables I and II summarize the test batches with the addition of the starting monomer or monomers and telogens and the reaction conditions. In the experiments shown in Table I, the specific stirring energy was 3.0 ^{· 10 ~ s} kp · m / sec / cm ^{3. In} the experiments shown in Table II, 3.5 · 10 ~ ⁵ kp · m / sec / cm ³ . Unless already described above, the measured values given in Table III were obtained as follows: The mean particle size of the primary grain of the wax powder was determined by counting and measuring the particles visible in the electron microscopic powder image. The crystalline / amorphous transition point resulted from the differential thermal analysis of put samples.

To determine the melt viscosity, the procedure was as follows: The amount of the extruded Melt and the unit of time determined at a given temperature under a given pressure from a nozzle with given dimensions (Duahmesser and length) exits. The apparent melt viscosity is calculated from this

Examples

General work regulations
a) Telomerization

The telecommunication approaches were, if not otherwise noted, m equipped with propeller stirrers enamelled 40-1 stirred autoclave. 17 g of perfluorooctanoic acid were placed in the float made up of deionized water and placed in the stirred autoclave dissolved and the pH adjusted to 8 bad 9 by adding aqueous ammonia solution. The respective telogens were presented either with the aqueous liquor or together with the Monomers premixed in a mixed gas battery or added separately during the telomerization. After repeated flushing with nitrogen, the monomer or the monomer mix was in the Kettle pressed and the batch after reaching the reaction temperature and switching on the stirrer by adding 23 g of ammonium persulfate and 1, 6 g sodium bisulfite, partly dissolved in water, started.

P ■ .7 r ⁴ 8 / </

wherein

P = extrusion pressure [dyn / cm ² ],

™ r - nozzle radius [cm'j,

/ = Nozzle length [cm],

q = amount of extrudate escaped [cm ³ / see]

The melt extrusion "was carried out with a high pressure capillary viscosity meter from Gottfen under the following measuring conditions (unless otherwise stated): 38QPC, 200 kgf / cm ² extrusion" pressure. Nozzle dimensions 1 mtn diameter, 40 min

Length.

The extrudate advises given in cnrVmin. The BET measurements were carried out in part Absorption of argon at -195 ° C. The dispersion stability of the obtained fluorocarbon wax-Di

«5 spersions were measured with a rotary viscometer from Haake on dispersions with a solids content of 20%; indicated is the failure time in minutes. *

11

Table I Telomerization with mixing of the telogen with the or deo monomers in the mixed gas battery

Output monomial crcfs) Telogen pressure Temp. Submitted Solids Mean
Particle * Conversion Seed fraction,
related to
Atisgangsftotte echo the
received
Dispersion size of the
Primary grain lung Ver
search
No. (Wax temperature
crystalline
amorphous (Weight percent) (Weight percent) (atü) Γ C) (Weight (Weight powder) (Wax 99,5CF ₂ = CF ₂ 0.5CF ₃ -CF ₂ J. 19th 32 percent) percent) (μ) powder) 98,8CF ₂ = CF ₂ 1.2CF ₃ -CF ₂ J 14th 25th 0.8 ² ) 22nd 6th CQ 1 97,7CF ₂ = CF ₂ 2,3CF ₃ -CF ₂ J 17th 34 - 23 1.5 324 2 96,3CF ₂ = CF ₂ 3.7CF ₃ -CF ₂ J. 19th 32 - 27 2.0 320 3 94,6CF ₂ = CF ₂ 5.4CF ₃ -CF ₂ J ¹ ) 19th 32 - 30th 1.8 319 4th 90,2CF ₂ = CF ₂ 9.8 CF ₃ -CFJ-CF ₃ 19th 32 - 35 1.7 318 5 88, OCF ₂ = CF ₂ 12.0 CF ₃ -CFJ-CF ₃ 19th 32 - 28 1.5 317 6th 85.0CF ₂ = CF ₂ 15.0 CF ₃ -CFJ-CF ₃ 19th 32 1.5 ³ ) 21 2.5 310 7th 87,3CF ₂ = CF ₂ / 1.2CF ₃ -CF ₂ J 17th 32 - 28 2.0 311 8th 11.5 CF ₂ = CFCl - 20th 1.2 310 9 84,5CF ₂ = CF ₂ / 7.5 CF ₃ -CF ₂ J. 17th 36 299 8.0CF ₂ = CFCl - 25th 1.0 10 88,0CF ₂ = CF ₂ / 7.5 CF ₃ -CF ₂ J. 17th 32 292 4.5 CF ₂ = CH ₂ - 25th 1.1 11 80,5CF ₂ = CF ₂ / 7.5 CF ₃ -CF ₂ J. 17th 32 271 12.0 CF ₃ -CF = CF ₂ - 20th 1.5 12th 86.7CF ₂ = CF ₂ / 8.8 CF ₃ -CF ₂ -J 17th 32 318 4.5 CF ₃ -CF = CF ₂ - 20th 1.5 13th 92,0CF ₂ = CF ₂ / 2.0CF ₃ -CFjJ 17th 32 315 6.0 CF ₂ = CFBr - 17th 2.0 14th 91.0CF ₂ = CF ₂ , / 4.0 CF ₃ -CF ₂ J. 14th 15th 319 5.OCF ₂ = CFJ - 15th 1.7 15th 93.0CF ₂ = CF ₂ / 4.0CF ₂ J-CF ₂ J 20th 32 317 3.0CH ₂ = CH ₂ 2, O ⁴ ) 12th 2.6 16 316

') Metered in during the telomerization. ') Same composition of the seeds (as experiment 1). ³ ) Same composition of the seeds (as experiment 7). *) Composition of the seeds as in the experiment

Table II

Telomerization with presentation of the telogen in the aqueous starting liquor

Attempt no.

Second Monomers *

(Weight percent) ¹ )

pressure Temp. Submitted Solid Mean ' Around- SaaUrateiU content of Particle conversion related to
Starting CfQSltCOCfl
OlSpCISlÜH size of the tempcratui Tdogett (atü) ro fleet Primary
koms crystal in-
iuttorpti 17th 32 (Weight (Weight (Wax- {Wax J weight 14th 25th percent) percent) puiver) powder) percentj 14th 32 24 W. CQ CF ₃ -CF ₂ J (0.8) 17th 32 28 2.5 321 CF ₃ -CF ₂ J (2.4) 14th 32 - 34 4.5 317 CF ₃ -CF ₂ J (4.4) 17th 30th - 17th 1.2 307 C ₂ F ₄ Br ₂ (3.9) 17th 28 - 20th 3.0 327 CCl ₄ (I ₁ O) 17th 32 - 27 1.5 318 CHBr ₃ (1.0) 17th 32 - 19th 1.4 320 CHdBr ₂ (1.0) 17th 32 - 20th 1.7 324 CF ₃ J (O ^) - 20th XS 321 CHBiCl ₂ (1.0) - 20th 1.9 323 CHa ₃ (KO) 1.7 321

5 CF ₂ = CFQ (S) 6 7 8 9 10

M remainder against 100 to the sum of weight percent of second monomer + weight percent telogen lew. Not percent telogen aiii

= Percent by weight of tetraflaoroethylene used. *) The composition of the seeds as in the experiment on p.

Second
Monomer 22 35 885 L3 continuation Telogen pressure Temp. Submitted \ MiI (I. Around· Seed percentage. * 14 Particle conversion (Weight (Weight related to
Starting size of temperature percent) ¹ ) percent) (atü) (-C) fleet Primary
grain crystalline
amorphous CF ₂ = CH ₂ (5) CHCl ₃ (1.0) 14th 28 (Weight Solid (WachB- (Wax- - CHCl ₃ (3.7) 14th 28 percent) content of powder) pnlver) attempt
No. - CHCl ₃ (4.5) 14th 28 - received
Dispersion (μ) (Cl - CHCI ₃ (8.0) 14th 25th - 1.8 318 - CH ₂ CI ₂ (3.7) 14th 20th - (Weight 2.2 319 CF ₂ = CCI ₂ (5) CHCI ₃ (KO) 14th 32 - percent) t, 8 318 Π - CHCl ₃ (0.2) 14th 32 1.5 ^J ) 18th 1.3 315 12th ') Remainder against 100 from total - 20th 1.2 320 13th - 18th 2.5 318 14th 20th 2.5 322 15th 17th Weight percent second monomer f weight percent telogen or weight percent Telogen: i! Lc 16 20th 17th 20th

= Percent by weight of tetrafluoroethylene used. ^J) 2 isammensetzung sowing as Versjch fourteenth

Table III

Properties of the fluorocarbon wax powders and dispersions

attempt No. Tab. Rotovisko stability
the dispersion (Sec) Total-
pore
volume Extrudate Apparent
Melt viscosity Specific
surface
according to BET Primary grain
distribution
of the powder 1 I. (Min.) 50 (cnvVlOOg) (cm ^J Min.) (Poisc) <m ² / g) l «fl'2 / if" 2 I. Λ 20th 112 1.4 7200 15th 0.8 3 5 40 114 1.4 5140 17th 4th 5 30th 117 2.5 2995 22nd 5 4th 112 3.0 2406 22nd 6th 6th 20th 110 4.0 1800 16 0.75 7th 10 20th 116 45.0 160 18th 8th 8th 30th 115 60.0 120 14th 9 20th 10 113 75.0 96 19th 0.85 10 15th 25th 117 3.0 2406 20th 11 16 8th 115 44 165 23 12th 9 10 108 35 206 25th 13th 9 106 55 131 18th 14th 7th 20th 104 50 145 23 15th I. 4th 10 103 3.0 2406 17th 16 I. 3 30th 101 2.5 2995 14th 1 I. 5 45 105 3.0 2406 22nd 2 I. 6th 30th 107 1.0 7200 18th 0.78 3 I. 7th 10 107 10.0 720 22nd 4th I. 4th 15th 104 100.0 72 23 5 I. 2 10 102 0.3 2400 18th 6th I. 8th 25th 110 10.0 720 16 0.89 7th II 3 40 104 8.04 · 10 ³ *) 3.05 x 10 ^s 22nd 8th II 2 50 105 8.76 · 10 ^J *) 28 · 10 ^s 21 9 II 1 35 101 1.4 5140 19th 10 H 2 45 103 1.9 x 10 " ³ *) 134 ■ 10 ^s 17th 11 II 2 40 104 Z32 *) 1.1 · 10 * 15th 12th Il 8th 40 110 0.51 *) 50 · ΙΟ ³ 22nd 13th II 4th 10 107 Z88 *) 9000 24 14th II 25th 4th 105 5.8 *) 4400 20th 0.78 15th π 20th 50 118 213 *) 1200 16 16 II 6th 50 106 2.75 *) 9300 19th Π II 2 30th 10 « 0.51 *) 50 ΙΟ ³ 21 II 7th 108 2.17- HT ³ *) 113.4 10 ^s 16 0.88 II : Nozzle: 2.08 mm; Length: S mm II II II II *) 380 ⁰ C 73 kp cm ^J

Claims (1)

Claims; I. Process for the preparation of fluorocarbon waxes by telomerization of tetrafluoroethylene, optionally in a mixture with 0.1 to 40 mol percent - based on tetrafluoroethylene - of comonomers of the formula