PROCESS FOR THE SUSPENSION POLYMERIZATION OF TETRAFLUOROETHYLENE

Abstract: The use of a small amount of a sulfonate of the formula F(CF₂ -CF₂ ) n CH₂-CH₂SO₃M, wherein n is a number from 2 to 6 and M is a monovalent cation, during suspension polymerization of tetrafluoroethylene has been found to reduce the amount of adhesions formed during the polymerization.

Description: DESCRIPTION TITLE: "PROCESS FOR THE SUSPENSION POLYMERIZATION OF TETRAFLUOROETHYLENE" Homopolymerization of tetrafluoroethylene in aqueous medium can be carried out by two distinctly different procedures. In one procedure, called suspension polymerization, very little dispersing agent is employed and agitation is carried out vigorously in order to produce a precipitated resin, commonly referred to as "granular" resin. In the other procedure, sufficient dispersing agent is employed and agitation is mild in order to produce small colloidal size particles dispersed in the aqueous reaction medium. In this second procedure, called aqueous dispersion polymerization, precipitation (i.e. coagulation) of resin particles is avoided. The two procedures produce distinctly different products. Granular resin can be molded in various forms, whereas resin produced by the aqueous dispersion method cannot be molded but is fabricated by dispersion coating or by converting to powder for paste extrusion with a lubricating medium. Granular resin is incapable of being paste extruded or dispersion coated. A disadvantage which sometimes occurs during aqueous suspension polymerization is formation of adhesions, i.e. unwieldy large clumps of resin particles, which form in the polymerization equipment, especially along walls of the reactor, and may clog the equipment as well as reduce yield of recoverable polymer. This formation of adhesions is particularly evident when ionic polymerization initiators are employed. Methods developed in the art to reduce the amount of adhesions formed have heretofore been directed to making the walls of the reaction vessel slick or smooth to make it difficult for the adhesions to build up. SU?4t4ARY OF THE INVENTION In this invention, formation of adhesions during aqueous suspension polymerization of tetrafluoroethylene in an aqueous medium to obtain a granular tetrafluoroethylene resin is reduced by carrying out the polymerization in the presence of a sulfonate of the formula F+CF2-CF2tnCH2-CH2SO3M) wherein n is a cardinal number of between 2 and 6 and M is a cation having a valence of 1, wherein said sulfonate is present in a concentration of between about 5 to 150 ppm based on amount of water used in the polymerization. DESCRIPTION OF THE INVENTION The polymerization of tetrafluoroethylene in aqueous medium to produce granular tetrafluoroethylene polymer is well known in the art. Tetrafluoroethylene (TFE) monomer is typically admixed or contacted with an aqueous medium (i.e. water) containing a polymerization initiator. Ordinarily, TFE monomer is introduced into the medium under pressure. Typical conditions include polymerization temperatures of 40-1200C; preferably 60-900C; and pressures of 10-50x 105 Pa. The polymerization is ordinarily carried out in a vigorously stirred autoclave. Initiators that can be employed are usually ionic initiators. Examples of ionic polymerization initiators include inorganic persulfates such as ammonium per sulfate or alkali metal per sulfates such as potassium persulfate and the like. The initiator is added prior to initiation of polymerization. The amount of initiator employed depends on the temperature of polymerization, the nature of the initiator, the molecular weight of the polymer desired, and the rate of reaction desired. Thus, the amount will vary depending on the results desired by one skilled in the art. Ordinarily, the amount will be between 1 and 200 ppm based on water present. A small amount of dispersing agent is often present in the suspension polymerization mixture. Ordinarily it is an anionic substantially nontelogenic dispersing agent. The amount employed aids in promoting particle nuclei formation but it is not an amount sufficient to cause particles to remain in the dispersion. Commonly employed dispersing agents are fluorinated carboxylates containing 7-20 carbon atoms, such as ammonium polyfluorocarboxylates. The amount of dispersing agent present is ordinarily between about 5 ppm and 150 ppm based on weight of water employed in the aqueous disperion, which is insufficient to cause formation of colloidal polymer particles. The dispersing agent is added prior to initiation of polymerization. The invention herein lies in replacing these polyfluorocarboxylates with the sulfonates described herein. Sometimes, if desired, a small amount of a nonionic dispersing agent can be added, such as "Triton" X-100, to the sulfonate. Polymerization is ordinarily carried out until the solids level (i.e., polymer content) of the aqueous mixture is between about 15 and 40 percent by weight of the mixture. The sulfonate F*CF2-CFzEnCH2-CH2SO3M employed in the reaction is most readily available as a mixture of compounds in which n is a cardinal number of 2-6. Preferably the average value of n will be about 4. The cation M is preferably hydrogen, ammonium or an alkali metal, and most preferably is H+, NH4, Na +, Li+ or K+. The resin produced herein is of the same quality and is useful in the same manner as granular tetrafluoroethylene polymers known heretofore. For example, the polymers are useful in making molded articles. The Examples hereinbelow describe the invention in greater detail, while the comparisons compare a known commonly used surfactant. EXAMPLES AND COMPARISONS A clean 38-liter polykettle was charged with the specified amount of dimineralized water, a specified solution (0.226 grams/liter concentration) of an octyl phenyl polyethylene oxide surfactant ("Triton" X-100, Rohm and Haas Company) and the indicated sulfonate surfactant (or known commonly used surfactant). The contents of the polykettle were heated to 650C and evacuated and purged three times with nitrogen. The polykettle was agitated with a two-blade, 450 pitch agitator at 600 rpm. Tetrafluorethylene was then added to the evacuated polykettle until the pressure was 1.72 x 106 Pa. A solution of ammonium per sulfate (1.0 grams/liter) was then pumped into the polykettle at the rate of 50 ml/min until the desired amount was added. After the polymerization began, as evidenced by a drop in pressure, tetrafluoroethylene was added to maintain the pressure at 1.72 x 106 Pa. After the desired amount of tetrafluoroethylene had been added, the feed was stopped and the polykettle was allowed to react down. A vacuum was applied if necessary. The pressure on the polykettle was brought back to atmospheric and the contents cooled to 50 C. The polymer was discharged from the polykettle and separated from the water. The adhesions were removed from the granular polymer and scraped from the interior of the polykettle if necessary. The adhesions were combined and weighed. The tables following records the pertinent data of the Examples and Comparisons run. TABLE I - EXAMPLES Example Surfactant ml Type Amount TFE Water Ammonium Triton Adhesions Grams PPM Kg Kg Persulfate X-100 kg (Based Grams PPM Solu on Water) on Water) CO.226 g/l) 1A Ammonium 1.0 52 11.45 19.1 0.20 10 13 0 Salt of perfluoro alkyl (avg. C-8) ethane sulfonic acid 1B Same as 1A 1.5 78 11.45 19.1 0.20 10 13 2.05 2A Same as 1A 1.2 63 10.6 19.1 0.20 10 13 0.9 2B Same as 1A 1.2 63 10.6 19.1 0.20 10 13 0.3 3A perfluoro 1.05 50 10.6 21.0 0.20 9.5 16 0.2 alkyl (avg. C-8) ethane sulfonic acid 3B Same as 3A 1.32 69 10.6 19.1 0.20 10 13 0.7 4 Same as 1A 1.0 52 10.6 19.1 0.15 7.9 13 0.2 5 Same as 1A 0.8 42 10.6 19.1 0.10 5.2 13 3.2 TABLE I - COMPARISONS Comparison Surfactant ml Type Amount TFE Water Ammonium Triton Adhesions Grams PPM Kg Kg Persulfate X-100 kg (Based Grams PPM Solu on Water) on Water) CO.226 g/l) C-1 Ammonium Perfluoro Caprylate 1.3 71 11.45 18.2 0.20 11 13 5.45 C-2 Same as C-1 1.2 63 10.6 19.1 0.20 10 13 4.6 C-3 Same as C-1 1.0 52 10.6 19.1 0.15 7.9 13 set-up C-4 Same as C-1 0.8 42 10.6 19.1 0.10 5.2 13 5.7 As is seen from Tables I and II, in general, adhesions are much less using an perfluoroalkyl ethane sulfonate or acid than using ammonium perfluorocaprylate, a known commonly used surfactant.

Claims: CLAIMS 1. A process for the suspension polymerization of tetrafluoroethylene in the presence of an ionic initiator in an aqueous medium at a temperature of 400 C to 1200C to obtain precipitated polymeric tetrafluoroethylene, characterised by employing in the aqueous medium a sulfonate of the formula FtCF2-CF2tnCH2-CH2SO3M wherein n is a cardinal number of from 2 to 6 and M is a cation having a valence of 1, wherein said sulfonate is present in a concentration of between 5 and 150 ppm based on amount of water used in the polymerization. 2. A process according to claim 1 wherein n has an average value of about 4. 3. A process according to claim 1 or 2 wherein M is hydrogen, ammonium, sodium, lithium or potassium. 4. Use of a granular tetrafluoroethylene resin produced by a process as claimed in claim 1, 2 or 3 in the production of molded articles.

Inventors: CAVANAUGH, ROBERT JOHN
Applicants: E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1983
Main classification: C08F14
IPC codes: C08F14, C08F2