NON-MELT-FABRICABLE GRANULAR MODIFIED TERAFLUOROETHYLENE POLYMER

Abstract: A non-melt-fabricable granular modified polytetraf­ luoroethylene in which the modifying comonomer is a fluorinated alkyl ethylene of the formula R f - CH = CH₂. The polymer is useful in ram extrusion and in making molded articles.

Description: TITLE MODIFIED GRANULAR POLYTETRAFLUOROETHYLENE FIELD OF THE INVENTION This invention relates to improved granular polytetrafluoroethylene compositions which contain a small amount of at least one selected fluoroalkyl ethylene copolymerized therewith, and to processes for preparing such compositions. BACKGROUND OF THE INVENTION Granular polytetrafluoroethylene molding resins are employed in molding and ram extrusion processes to produce billets and other plastic articles. Granular polytetrafluoroethylene is prepared by polymejrizing tetrafluoroethylene by a process in which little or no dispersing agent is employed and agitation is carried out vigorously in order to produce a precipitated resin. This resin is commonly. referred to as "granular" resin. The procedure is called "suspension polymerization". aZen the term "granular" is used herein, it is used to denote the resin formed by the suspension polymerization procedure. There is another polytetrafluoroethylene material that is referred to by those skilled in art as "fine powder polytetrafluoroethylene11. To make this so-called "fine powder", a process called "aqueous dispersion polymerization" is used. In this process 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 aqueous dispersion polymerization, precipitation (i.e., coagulation) of the resin particles is avoided during polymerization. The dispersion may be used as such, or the dispersed particles may be coagulated in a separate step and the resulting "fine powder" obtained. The two poiymerization procedures produce distinctly different products. The granular product can be molded in various forms, whereas the fine powder produced by the aqueous dispersion method cannot be molded but must be fabricated by dispersion coating or by adding a lubricant for paste extrusion. In contrast, granular resin is incapable of being paste extruded. Tetrafluoroethylene polymers produced by the aqueous dispersion polymerization method are generally not suited to ram extrusion processing, since they have a very soft sensitive grain, and, due to their molecular weight being lower compared with granular polymers, give extrudates with low mechanical strength. Suspension polymerization of tetrafluoroethylene to obtain granular product is generally carried out by filling the polymerization reactor, which is equipped with an agitating system, with an aqueous medium in which a catalyst forming free radicals, optionally a buffer, and optionally a small amount of a fluorinated emulsifier. The air is removed and tetrafluoroethylene is fed into the reactor. After polymerization has started, gaseous tetrafluoroethylene is fed at a rate corresponding to the polymer amount being formed, while keeping the polymerization pressure constant. It has previously been known that if a small amount of comonomer is present, the properties of the resulting modified granular polytetrafluoroethylene particles can be altered. For example, sinterability can be improved and crystallinity reduced. Two comonomers preferred by the art are hexafluoropropylene, CF3-CF=CF2, and perfluoro(propyl vinyl ether)1 CF3CF2CF2-O-CF=CF2. This is evident from British patentl,116,210 and U.S.P. 3,855,191. However, using perfluoro(propyl vinyl ether), the melt viscosity of the resulting granular copolymer is relatively low, and large billets molded therefrom have a tendency to deform (sag) under their own weight during sintering. It would be desirable to find a comonomer which can be used to make a granular copolymer having a higher melt viscosity. Use of hexafluoropropylene is not completely satisfactory either. Presence of this comonomer causes the resulting copolymer to be less thermally stable than tetrafluoroethylene homopolymer. Evidence of such instability is shown at column 1, lines 29-30 of U.S.P. 3,855,391. It would be desirable to find a comonomer which would not deleteriously affect the thermal stability of the copolymer significantly. SUMMARY OF THE INVENTION This invention is a granular modified polytetrafluoroethylene composition comprising tetrafluoroethylene polymer containing polymerized units of at least one copolymerizable monomer of the formula R - CH = CH2 present in an amount which does not cause the melt viscosity of the resulting polyner to be less than about 1 X 108 PaS at 380 C., wherein Rf is a fluorinated alkyl radical of 2-10 carbon atoms which is perfluorinated or which is perfluorinated except for the presence of one substituent attached to a carbon atom of the Rf. radical which substituent is selected from hydrogen or halogen other than fluorine. DESCRIPTION The polymers of this invention are of high molecular weight as indicated by their inability to be fabricated by melt flow procedures such as melt extrusion or injection molding. Thus they are "non-melt-fabricable", i.e. are not extrudable from a melt. They are made by the suspension tetrafluoroethylene polymerization process and thus are the so-called "granular" tetrafluoroethylene polymers. In view of their non-melt-fabricable nature, the copolymers generally have melt viscosities above 1 x 108 PaS measured at 380"C. These high melt viscosities are obtained by keeping the amount of comonomer low. For.example, the amount of polymerized comonomer units present complementally to the tetrafluoroethylene units will be preferably less than 2 percent by weight of total polymer weight and generally less than 0.5%, and most preferably less than 0.2%. As a minimum amount present, preferably at least 0.01% of the comonomer will be present in copolymerized form. The comonomers have the formula Rf - CH = CH2. Rf can be perfluorinated, (F(CF2+n, wherein n is an integer of 2-10 carbon atoms, or Rf can be perfluorinated except for one substituent which replaces a fluorine atom, which substituent is H or other halogen, (C1, Br or I), preferably C1 or Br. Examples of comonomers that can be used to make the polymers of this invention include CF3-CF2-CH=CH2; CF3(CF2) 9CH=CH2; CF2H-CF2-CH=CH2 CF2H(CF2)9CH=CH2; CF2Br-CF2-CH=CH2; CF2B CF2Br ( CF2 ) gCH=CH2 CF3-CFH-CF2-CH=CH2, and the like. Mixtures of comonomers may be used. Perfluorobutyl ethylene, CF3-(CF2)3CH=CH2 is preferred. The process used to prepare the polymers of this invention is the usual suspension polymerization process used to prepare granular polytetrafluoroethylene. Such polymerization is described in a number of patents such as U.S. Patent 3,245,972 and U.S.P. 3,855,191. In brief, tetrafluoroethylene is pressured into an autoclave containing water and conventional free-radical polymerization initiators along with optionally buffer and optionally a small amount (up to about 200 ppm based on H20) of an emulsifying agent. The reaction mixture is agitated and the polymerization is carried out at suitable temperatures and pressures. Upon completion of the polymerization, the polymer is isolated and dried. The comonomers may be added as a precharge, but since the comonomers react much faster than tetrafluoroethylene monomer, it is preferred to add comonomer throughout the course of the polymerization in order to obtain a polymer that contains comonomer units distributed relatively evenly throughout the polymer chain in the small amounts present. Thus, comonomer is preferably both precharged to the polymerization vessel and added subsequently during polymerization, either in increments or continuously. It is important not to add too much comonomer at any one time since it may react with itself if too much is present. The polymerization temperature will ordinarily be between 50-120"C and the initiator will be a peroxide or persulfate. Inorganic persulfates, such as ammonium persulfate, are preferred. A buffer to maintain pH at between 6-9 may be used if desired. In addition, a small amount of a dispersing agent (e.g. up to 100 or 200 ppm based on water present) may be employed in order to increase the surface area of the resulting polymer particles. Agitation-will be sufficient to ensure coagulation of the polymer particles as the polymerization proceeds. The polymers of this invention have high melt viscosities and are suitable for preparing billets. (Billets are useful to skive into tapes or sheets). The polymers also exhibit high dielectric strength which makes them useful for electrical grade skived tape; low deformation under load which makes them useful for gaskets; high flexural strength which makes them useful for bellows and membranes; and low gas permeability which makes them useful for chemical lining and diaphragms. A distinction must be made between the granular (suspension made) polymers of this invention and tetrafluoroethylene copolymers having a higher content of comonomer. The latter contains enough comonomer to permit them to be processed from a melt by extrusion methods customary for thermoplastics. The granular suspension-made polymers of this invention, like unmodified polytetrafluoroethylene itself, belong to the type of tetrafluoroethylene polymers that are not extrudable from the melt, and special molding methods must be used to fabricate them. Furthermore, being suspension-made, the polymers of this invention have a morphology which differs from that of dispersion-prepared fine powder polymers. These latter polymers are produced in the presence of such high amounts of emulsifier that, after polymerization has ended, they remain in colloidal distribution in the aqueous medium. These fine powder polymers are obtained from the colloidal dispersion by coagulation and on coagulation form agglomerates from colloidal primary particles that have an average particle diameter of about 0.1 to 0.5L(m. As is known to one skilled in the art, they can not be molded by ram extrusion or mold-sinter processing techniques, even if they contain comonomer modifiers. Properties of the polymers obtained in the Examples which follow are obtained according to the procedures set forth below: 1) Determination of comonomer content Comonomer content in the copolymers was determined by Fourier Transform (FT) IR spectroscopy. Ten mil cold pressed films were prepared and spectra were obtained on Nicolet 7000 FT -l IR spectrophotometer at a resolution of 4 cm The -CH2- bending vibration at 880 cm was used, calibrated using NMR analysis. The absorbance at 880 cm 1 was calculated by taking the difference -l between absorbances at 888 and 880 cm . For perfluorobutyl ethylene (PFBE) comonomer, the calculation used is as follows Wt. % PFBE A 880 cm 1 - tO.00064 x t) X 100 t x 0.97 where t = Thickness in mils and A = absorbance. 2) Standard Specific Gravity (SSG) Standard specific gravity (SSG) of the molding powder is measured by water displacement of a standard molded test specimen in accordance with ASTM D1457-69. The standard molded part is formed by preforming 12.0 g. of the moldingipowder in a 2.86 cm. diameter die at a pressure of 34.48 and 6.90 MPa (352 and 70.4 kg/cm2), followed by the sintering cycle of the preform of heating from 300 to 380"C. at 2eC./min., holding at 3809C. for 30 minutes, cooling to 2950C. at 10C./min. and holding at this temperature for 25 minutes, after which the specimen is cooled to room temperature and tested for specific gravity. 3) Specific Surface Area (SSA) SSA was measured by a "Quantasorb" surface area analyzer. The measurement was made on raw polymer obtained directly from the polykettle vessel after washing and drying. 4) Melt Viscosity Melt viscosity is calculated by measuring the tensile creep of a sintered -piece held at 3800C. Specifically, 12 g. of molding powder is placed in a 7.6 cm. diameter mold between 0.152 cm. rubber cauls and paper spacers. Pressure is then slowly applied 2 on the mold until a value of 40.5kg./cm. is obtained. This pressure is held for 5 minutes and then released slowly. After the sample disc is removed from the mold and separated from the cauls and paper spacers, it is sintered at 380"C. for 30 minutes. The oven is then cooled to290"C, at a rate of about 10C. a minute and the sample is removed. A crack-free rectangular sliver with the following dimensions is cut: 0.152 to 0.165 cm. wide, 0.152 to 0.165 cm. thick, and at least 6 cm. long. The dimensions are measured accurately and the cross-sectional area is calculated. The sample sliver is attached at each end to quartz rods by wrapping with silver-coated cooper wire. The distance between wrappings is 4.0 cm. This quartz rod-sample assembly is placed in a columnar oven where the 4 cm. test length is brought to a temperature of 380 2 C. A weight is then attached to the bottom quartz rod to give a total weight suspended from the sample sliver of about 17 g. The elongation measurements vs. time are obtained, and the best average value for the creep curve in the interval between 100 and 130 minutes is measured. The apparent melt viscosity is then calculated from the relationship ilapp = (tLtg)/3(dLt/dt)AT wherein ;;app = (apparent) melt viscosity in shear, poises W = tensile load on sample, g Lt = length of sample (at 3800C.) cms. (4.32 cm) g = gravitational constant, 980 cm./sec.2 (dLt /dt) = rate of elongation of sample under load = slope of elongation vs. time plot, cm./sec. AT = cross-sectional area of sample (at 380 C), T2 cm - area increases 37% at 380"C over that at room temperature 5) Dielectric Strength Dielectric strength was measured by preforming 140 g powder into a 5.6 cm diameter molding and sintering at 380 C for 3 1/2 hours, heating at 6 C/min from 2900 to 380"C and cooling at 1OC/min from 3800C to 2900C. The measurement was made on 5-ml tape using Beckman Model PA5 AC Dielectric Strength Test Set. 6) TGA TGA was obtained using a Du Pont 951 TGA Analyzer. The weight loss was determined at a constant temperature for 2 and 4 hr. (negative weight loss actually indicates wt. again.) 7) Tensile Strength and Elongation Tensile strength and elongation were measured in accordance with ASTM D-1457-69. EXAMPLES Example 1 A 38-liter polykettle vessel was charged with 21.8 kg of demineralized water, 0.30 g (13.8 ppm) ammonium perfluorooctanoate (APFC) dispersant, and 3.0 g ammonium persulfate (APS) initiator. The contents of the vessel were heated to 65"C and evacuated. The vessel was agitated with a 2-blade 45" pitch agitator at 600 RPM. One ml perfluorobutylethylene (PFBE) was injected into the vessel with a syringe. Tetrafluoroethylene (TFE) was then added to the vessel until the pressure was 1.72 x 106 Pa. After the polymerization began, as evidenced by a drop in pressure, TFE was added to maintain the pressure at 1.72 X 106 Pa and an additional 8 ml PFBE was continuously added with a microfeeder at the rate of 0.1 ml per min. After the desired amount of TFE had been added, the feed was stopped and the mixture was allowed to react down to 5.5 x 10 Pa pressure. Reaction time was 95 minutes. 8.2 kg TFE was polymerized. After venting and evacuation, the pressure in the vessel was brought back to atmospheric with nitrogen and the contents cooled to below 50"C. The polymer was discharged from the vessel and the adhesions were separated. The polymer was cut to less than 0.03 mm average particle size. The polymer properties are given in Table 1. Examples 2-5 Example 1 was repeated with the following ingredient amounts. The polymer properties are given in Table 1. Ex. 2 Ex. 3 Ex. 4 Ex. 5 APFC, g 0.30 0.30 0.30 0.10 APS, g 0.75 3.0 2.0 1.0 PFBE Precharge, ml 0 0.5 1.0 1.0 PFBE Microfed, ml 5.1 4.2 8.0 1.0 Microfeeder Rate, ml/min 0.1 0.06 0.1 0.02 TFE Reacted, kg. 6.0 8.2 6.2 8.2 Reaction Time, min 122 69 123 85 Table 1 PHYSICAL PROPERTIES OF POLYMERS Ex. 1 Ex. 2 Ex. 3 Esr. 4 Ex. 5 % PFBE by Wt. 0.12 0.10 0.01 0.24 0.01 SSG measured at 34.48 M Pa 2.174 2.165 2.175 2.163 2.162 SSG measured at 6.90 M Pa - 2.161 2.175 2.162 2.159 SSA, m2/g - 4.5 3.5 (Raw Polymer) Melting Point, CC 345 347 345 343 346 Viscosity, PaS* 0.6xl0 0.6x10 1.0x109 1.6x109 4.0x109 Dielectric 1755 1570 - 1789 1860 Strength (34.48) (34.48) - (13.8) (13.8) v/mil (Preform Press, M Pa) TGA (% Wt Loss at 377 C) -0.5/2 hr - - - 0/4 hr Tensile Strength - 32.9 - - (measured at 6.90 MPa , MPa preform pressure) Elongation, % - 449 - - - Ram Extrusion of 6 mm Rod at '6 m/hr: Tensile Strength, M Pa - 19.3 - Elongation, 9s - - 298 Comparison A -. Properties of the copolymer of Example 1 were compared with a copolymer made of tetrafluoroethylene and pefluoro(propyl vinyl ether) (PPVE). This comparison copolymer was prepared according to the procedure used to prepare the copolymer of Example 1. The ingredients and other relevant process data were as follows: APFC, g 0.3 APS, g 0.65 PPVE, Precharge, M1 0.5 PPVE Microfed, M1 10 Microfeeder Rate, ml/min 0.1 TFE reacted, kg 7.7 Reaction Time, min 140 Property data of this PPVE Modified tetrafluoroethylene copolymer is compared with that of the ExampLe 1 copolymer as follows: TABLE 2 Example 1 Comparative Example % Comonomer by Wt. 0.12 PFBE 0.08 PPVE SSG at preform pressure 34.48 M Pa 2.174 2.173 Melting Point, C 345 347 Melt Viscosity, 0.6 X 109 1.1 X 108 Pa.S. Dielectric Strength, vlmil (Preform Press, M Pa) 1755 (34.48) 1700 (34.48) TGA (% Wt loss at -0.5/2 hr (wt. gain) 0/2 hr 377"C) It is seen from this data that melt viscosity of the PPVE-modified polymer (comparative example) is lower than that for the PFBE-modified resin of Example 1, even though SSG is virtually the same. A high melt viscosity for the molding resins is desired for heavy billets to retain shape at sintering temperatures. Comparison B A copolymer was prepared by reacting tetrafluoroethylene and hexafluoropropylene (HFP) following the procedure of Example 1, except that APS used was 0.70 g, C-8 used was 0.30 g, HFP was precharged only (=13 g); temp = 60 Ç. The amount of copolymerized HFP in the copolymer was 0.07% by weight. The HFP modified copolymer was compared with the copolymer of Example 2 for thermal stability, with the following results: PFBE-Modified HFP-Modified Copolymer Copolymer Thermal Instability Index 4 25 (TII) - ASTM Method D-1457 % Ht. Loss in N2 at 370"C/3hr 0.0059 0.0084 Low TII means better stability. Thus, it is seen that the PFBE-modified copolymer of this invention is more thermally stable. COMPARISON C 160 g plaque moldings of 5.6 cm diameter of the polymers of Example 1 and a sample like Comparison A (PPVE), but different in that it was prepared on manufacturing scale with modified recipe, with PPVE precharged only (mv = 1.6X108 Pa S), were sintered at 380"C for 5 hours in air with a 4.8 kg weight that covered the plaque on top of each of the moldings. The sintered moldings had the following dimensions: Example 1 Sample like Comparison A Avg. Thickness, cm 3.1 2.7 Top Diameter, cm 5.5 5.8 Bottom Diameter, cm 5.6 5.7 The molding of Example 1 was normal in appearance, while the molding of the comparison was significantly distorted. The thickness of the comparison (2.7 cm) is smaller than that before sintering (2.85 cm) in spite of the growth normally experienced during sintering. The diameter (5.7-5.8 cm) is generally larger than that before sintering (5.7 cm) in spite of the shrinkage normally experienced during sintering.

Claims: CLAIMS: 1. A non-melt-fabricable granular modified polytetrafluoroethylene composition comprising tetrafluoroethylene polymer containing polymerized units of at least one copolymerizable monomer of the formula R - CH = CH2 2 present in an amount which does not cause the melt viscosity to be less than about 1 X 10 PaS at 380eC., wherein Rf is a fluorinated alkyl radical of 2-10 carbon atoms which is either perfluorinated or which is perfluorinated except for the presence of one substituent attached to a carbon atom of the R radical which substituent is selected from hydrogen or halogen other than fluorine. 2. The composition of Claim 1 wherein the copolymerizable monomer of the formula Rf - CH = CH2 is one in which Rf is perfluorinated. 3. The composition of Claim 1 wherein the copolymerizable monomer of the formula R - CH = CH2 is perfluorobutyl ethylene. 4. The composition of Claim 1, 2 or 3 wherein the copolymerizable monomer is present in an amount of less than 2% by weight, preferably less than 0.5% by Weight, based on weight of polymer. 5. The composition of Claim 1, 2 or 3 in the form of a molding resin or in the form of a molded article. 6. In the process for polymerizing tetrafluoroethylene and it least one comonomer to make a non-melt-fabricab:e granular modified polytetrafluoroethylene composition by carrying out the suspension polymerization of tetrafluoroethylene and at least one said comonomer, the improvement comprising (1) employing as the comonomer a monomer of the formula R - CH = CH2 wherein Rf is a fluorinated alkyl radical of 2-10 carbon atoms which is either perfluorinated or which is perfluorinated except for the presence of one substituent attached to a carbon atom of the Rf radical which substituent is selected from hydrogen or halogen other than fluorine, and (2) adding said comonomer throughout the course of the polymerization. 7. Process for shaping a molding resin in which the resin is made of a composition defined in Claim 1, which comprises ram extruding said resin.

Inventors: MALHOTRA, SATISH CHANDRA
Applicants: E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1983
Main classification: C08F214
IPC codes: C08F14, C08F214, C08F2