Nucleating agents for thermoplastic resins

Abstract: This invention relates to the use of a special class of sulfonic and phosphonic acids, and salts of the acids, to give improved nucleation for foam extrusion of thermoplastics using either dissolved gas or chemical blowing agents to produce foam.

Description: FIELD OF THE INVENTION This invention relates to the use of a special class of sulfonic and phosphonic acids, and salts of the acids, to give improved nucleation for foam extrusion of thermoplastics using either dissolved gas or chemical blowing agents to produce foam. BACKGROUND OF THE INVENTION Conductive wire is often used to transmit electronic signals. The wire must be protected, or insulated, and thermoplastic coatings are ordinarily used for this. The thermoplastic is extruded from a molten state onto and around the wire. The thermoplastic materials are selected on the basis of having a low dielectric constant and a low dissipation factor. It has previously been found that if the thermoplastic material is foamed as it is applied to the wire, the dielectric constant is desirably lowered, due to the formation of numerous small non-interconnected cells in the foam. In U.S. 3,072,583 is disclosed a nucleated foaming process for extruding perfluorinated polymer foam around transmission wire with a dissolved gas blowing agent. Foamed insulation using other thermoplastic materials, especially polyolefins, is also widely used. A nucleating agent is needed in the foaming process to achieve uniform, small-diameter cell structure. A preferred art-recognized nucleating agent for fluoropolymer resins is boron nitride, an inert white ceramic powder. A 0.5-2.0 weight % loading of boron nitride, based on polymer, normally provides adequate foam cell nucleation. The lower the specific gravity of the molten resin, the more nucleant is needed, on a weight basis. Thus, an ethylene(E)/tetrafluoroethylene(TFE) copolymer(ETFE copolymer) with a melt specific gravity of about 1.3 requires more nucleant than a tetrafluoroethylene(TFE)/hexafluoropropylene(HFP) copolymer(TFE/HFP copolymer) at a melt specific gravity of 1.6. U.S. 4,764,538 discloses synergistic combinations of boron nitride and certain inorganic salts which give greatly enhanced foam nucleation in fluoropolymers. This combination not only allows a significant reduction in the amount of boron nitride needed but also gives improved foam in terms of smaller cells. Improved capacitance and diameter uniformity are also attained. The present invention provides a special class of sulfonic and phosphonic acids, and salts of the acids, which give very efficient nucleation of a wide variety of thermoplastic materials at low concentrations without the use of boron nitride or any other traditional type of nucleating agent. U.S. 3,554,932 discloses an extrusion mixture of thermoplastic polymer in the melt state which further comprises a liquid volatilizable blowing agent and suspended therein a foam nucleating agent of which at least the surface consists of fluorocarbon. As used herein the term "thermoplastic" means and is intended to include any organic material that is rendered soft and moldable by application of heat (Hackh's Chemical Dictionary, Julius Grant, 4th edition, McGraw-Hill Book Company, New York, New York). Other terms used synonymously herein with "thermoplastic" and "thermoplastic material" are "thermoplastic resin" and "polymer," it being understood that the resin or polymer must be capable of being rendered soft and moldable by application of heat, that is, it is melt processible. The term "composition" as it is used herein is intended to include the thermoplastic material and other ingredients or additives which, individually, may or may not be melt processible, as will be discussed in greater detail in the Detailed Description of the Invention. The compositions of this invention are useful in producing foams for other applications as well as for wire coating. Such examples include, but are not intended to be limited to, foamed sheet for electrical insulation, heat insulation and cushioning; foamed pipe and tubing; and injection molded pieces. SUMMARY OF THE INVENTION This invention resides in a foamable thermoplastic resin extrusion composition, wherein the resin is melt processible fluoropolymer, homogeneously containing as a nucleating agent a nucleating-effective amount of at least one thermally stable compound which is selected from the group consisting of sulfonic and phosphonic acids and salts thereof which compositions significantly enhance foam nucleation, as evidenced by smaller foam cells, higher foam void contents, and/or greater uniformity of cell size. These compositions contain 50 to 8000 ppm, preferably 250 to 3000 ppm, by weight, for most compositions, of one or more of the acids and/or salts which are of the formula [Z(CF 2 ) x (CF 2 CFX) p (R') y (CH 2 ) z RO 3 ] n M wherein: the bivalent groups, except for RO 3 , may be present in any sequence; Z is CCl 3 , CCl 2 H, H, F, Cl or Br; each X, independently, is selected from H, F, Cl and CF 3 ; R is sulfur or phosphorus; M is H or a metallic, ammonium, substituted ammonium or quaternary ammonium cation; x is an integer and is 0 to 20; p is an integer and is 0 to 6; y is 0 or 1; z is an integer and is 0 to 20; x + y + z + p is a positive integer or, if x + y + z + p is 0, Z is CCl 3 or CCl 2 H; n is the valence of M; and R' is selected from a C 5-6 perfluorinated alicyclic ring diradical; a C 1-16 perfluorinated aliphatic polyether diradical with repeat units selected from [CF 2 O], [CF 2 CF 2 O], and [CF 2 CF(CF 3 )O]; and a substituted or unsubstituted aromatic diradical, in which case, Z is H. Preferably, M is a metallic cation. When M is H, the resultant sulfonic or phosphonic acid may not be effective in all thermoplastic resin compositions. When M is selected so as to be other than a metallic cation or H, it preferably should be such that the resulting nucleating agent is stable at the foam processing temperature. Failure to provide such consideration in the selection of M may lead to in situ decomposition of the cationic moiety, with resultant conversion of M to H. The significance of this aspect of the invention will be readily understood in view of the significance of M on the foaming process, as described hereinafter in the Detailed Description of the Invention. The stability of the nucleating agent at the foam processing temperature must be considered not only in connection with the selection of M but also in connection with the selection of the other symbols in the above formula. More specifically, it is to be understood that the nucleating agent should be stable at the foam processing temperature which can vary substantially depending on the thermoplastic being foamed. Thus, in the above formula, when each of x, p and y is 0, z is 1 to 10 and Z is CCl 3 or CCl 2 H, the resultant nucleating agent, for example, trichloroethane sulfonic acid or its M salt will be stable at normal polyethylene foam-processing temperatures, such as below about 315°C, but it will not be stable at the temperature needed to foam high-melting thermoplastics. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 provides graphical data which may be used in the selection of M in the formula for the nucleating agent (a TBSA salt, defined hereinafter) in the foaming of TFE/HFP copolymer. Figure 2 provides graphical data which may be used in the selection of M in the formula for the nucleating agent (a TBSA salt) in the foaming of polyethylene. DETAILED DESCRIPTION OF THE INVENTION The thermoplastic resins useful in the present invention include all such fluoropolymers which can be foamed by a gas injection process and/or by use of a chemical blowing agent. In particular, suitable thermoplastics are those with a dielectric constant of less than 18, preferably less than 12, for example, 10.2. Especially suitable for making foamed electrical insulation by this invention are those fluoropolymers with a dielectric constant of less than 3. Suitable thermoplastics include melt processible fluoropolymers; and blends of polymers with non-polymeric materials, for example, pigments, fire retardants, minerals and carbon, that is, any material commonly present in foamed compositions. In other words, the invention is useful with any virgin or blended resin that is capable of being foamed by a gas injection process or by means of a chemical blowing agent. Foamed fluoropolymer wire insulation, is generally produced in the art by a continuous, gas injection process using chlorodifluoromethane(F-22), nitrogen, carbon dioxide, or other gas or gas mixture which is soluble in the molten resin, using an extruder screw designed for foam operations, and using boron nitride as a nucleating agent. In such processes the gas dissolves in the molten resin inside the extruder. Absorption follows Henry's Gas Law which states that the equilibrium value of the mole fracticn of gas dissolved in a liquid is directly proportional to the partial pressure of the gas above the liquid surface. By adjusting the gas pressure in the extruder, the amount of gas dissolved in the melt can be controlled. Generally, the greater the amount of gas dissolved in the melt, the greater the void volume in the resulting foam. Chlorodifluoromethane(F-22) is especially suited for foaming because it easily dissolves in molten fluoropolymer resins, and its thermal stability is adequate to survive the holdup time in the extruder when mixed with molten resin at temperatures up to 380°C. As an alternative process, a chemical blowing agent (a chemical which is unstable at the polymer processing temperature and liberates a gas, such as nitrogen, carbon dioxide or hydrogen) can be incorporated into the thermoplastic to provide the dissolved gas which causes bubble formation. Preferred examples of the process for producing a foam: The process wherein the nucleating agent is selected from (a) free acids and salts of partially or totally fluorinated aliphatic sulfonic and phosphonic acids, which optionally may contain cycloalkyl groups and/or ether oxygen; and (b) free acids and salts of aromatic sulfonic and phosphonic acids, in which the aromatic ring, optionally, is substituted with alkyl, fluorine-containing alkyl, and/or hydroxyl groups. The process wherein the nucleating agent contains only two of the diradical units selected from (CF 2 ) x , (CF 2 CFX) p , (R') y , and (CH 2 ) z . The process wherein the nucleating agent has a total of no more than 20 carbon atoms and M is selected from H, K, Na, Ba, Zr, Cr, Ce, Al, Sr, Ca, Zn, Li, Fe, and triethyl ammonium. The process wherein the nucleating agent comprises at least one salt of the acid of the formula F(CF 2 ) x (CH 2 ) z SO 3 H, in which x is 6 to 12 and z is 0, 1, or 2. The process wherein the nucleating agent is the potassium salt of perfluorooctane sulfonic acid, and the concentration of nucleating agent, based on the composition, is 500-3000 ppm. The process wherein the thermoplastic resin is a tetrafluoroethylene/hexafluoropropylene copolymer, the average cell size is less than 100 micrometers, and the void content is greater than 60%. The process wherein the thermoplastic resin is an ethylene/tetrafluoroethylene copolymer, the average cell size is less than 100 micrometers, and the void content is greater than 50%. The process wherein the thermoplastic resin is an ethylene/tetrafluoroethylene/perfluorobutyl ethylene copolymer. Foam cell formation actually starts shortly after the molten resin containing the blowing agent passes out of the extrusion die. The gas dissolved in the molten resin comes out of solution because of the sudden drop in melt pressure as the extrudate exits the extrusion die. As shown in U. S. 4,764,538, extrusion speed and drawdown influence foaming. The polymer is solidified when the extrudate enters water in a cooling trough, stopping foam cell growth. A nucleating agent is needed to achieve uniform, small-diameter cell structure. The preferred commonly used nucleating agent for fluoropolymer resins has been boron nitride, an inert white ceramic powder. The present invention covers a special family of sulfonic and phosphonic acids, and salts of the acids, which give very efficient nucleation at low concentrations. The optimum nucleating agent and concentration depend on the specific polymer and conditions employed in the foaming process. The nucleating agent of this invention can be blended with virgin or blended polymers, as powder or pellets, and extruded to give a homogeneous composition containing the desired amount of the nucleating agent, generally 50-8000 ppm, preferably 250-3000 ppm. Alternatively, the agent can be added to the virgin or blended polymer as a concentrate which may contain 5-20 times the desired amount of nucleating agent, and then the concentrate is mixed with 20-5 parts of virgin or blended polymer before the foaming step. With chemically blown compositions the blowing agent and nucleating agent can be blended with virgin or blended polymer powder and either compacted into pellets at room temperature to avoid premature decomposition of the blowing agent, or extrusion-compounded at a temperature at which the blowing agent is not decomposed to a substantial extent. Figure 1 and Examples 2 and 3 show how routine experimentation can help select the best cation for foaming a particular resin (TFE/HFP copolymer) with a room temperature dielectric constant of 2.05 with CHF 2 Cl using a salt of Telomer B sulfonic acid(TBSA). Telomer B sulfonic acid is of the formula F(CF 2 ) n CH 2 CH 2 SO 3 H wherein n is a mixture of 6, 8, 10 and possibly 12, predominantly 8. The results for different cations are plotted on the Figure 1 graph using the atomic radius of the cation as abscissa and cation valence as ordinate; above the point for each cation is shown the minimum average diameter of the foam cells in micrometers for the optimum concentration tested. It is desirable to have very small cells and high foam void content. It can be seen in Figure 1 that the cations giving cell diameters equal to or less than about 200 micrometers fall between the two outer lines (the preferred range). The cations giving still smaller cell diameters, equal to or less than about 75 micrometers, fall between the two inner lines (optimum range). As is apparent, for TFE/HFP copolymer the best cations are Zr ++++ , Fe +++ , and Ba ++ . The preferred nucleating agent concentration for these cations with this copolymer is 500-2000 ppm. Thus, Figure 1 provides a means for predicting how other salts of TBSA will perform in TFE/HFP copolymers with CHF 2 Cl as blowing agent. Similar performance is observed when the thermoplastic resin is a copolymer of tetrafluoroethylene and a perfluoro(alkyl vinyl ether), such as perfluoro(propyl vinyl ether). Table 1 which follows shows the great difference in nucleating efficiency of various bivalent salts of TBSA in the experiments depicted in Figure 1. It also shows that efficient nucleation results in both high void content in the foam and small diameters of the foam cells. In Table 1 and in all the remaining tables herein, the following abbreviations are used: SPC: Specific Void Content AFCD: Average Foam Cell Diameter (at mid-wall) M: Micrometers %V: % Voids in Foam as Calculated from the Measured Dielectric Constant cc/cm 3 : Cell Count/cm 3 at the Specific Void Content Conc.: Concentration Ex St: Extrusion Stability DC: Dielectric Constant FCC: Foam Core Capacitance (lowest value) pF/m: Picofarads/meter C: Capacitance TBSA Salt cc/cm 3 %V AFCD (M) Barium 2,300,000 55 75 Strontium 763,000 59 100 Calcium 72,200 41 220 Zinc 24,800 20 508 Figure 2 and Example 11 show a similar plot for a polyethylene which has a room temperature dielectric constant of 2.3. Salts of the same TBSA (as in Figure 1 and Examples 2 and 3) were used, with nitrogen as the blowing agent. Figure 2 has the same general appearance as Figure 1, but a narrower optimum range has been chosen (cell diameters equal to or less than about 50 micrometers), and the polymer and blowing agent are different. Figure 2 shows that with this polyethylene the preferred TBSA salts are those of Cr +++ , Fe +++ , and Ca ++ . The preferred nucleating agent concentration for these cations with this polymer is 1000-3000 ppm. One might expect that fluorine-free salts, such as sodium lauryl sulfate, would be effective nucleating agents for polyethylene, just as the fluorine-containing salts of this invention are for fluoropolymers. Surprisingly, this is not always the case, as shown by Comparative Example B between Examples 11 and 12 herein. Comparative Examples A and B show, also, the inoperability of other compounds as nucleating agents. Also demonstrated in the examples herein are foamed compositions comprising ethylene/tetrafluoroethylene copolymers. Preferred nucleating agents for such resins include the calcium salt of Telomer B sulfonic acid and the potassium salt of a perfluorinated alkane sulfonic acid of 1-10 carbon atoms. A preferred concentration of such nucleating agents, based on the composition, is 1000 to 3000 ppm. The broad applicability of the invention is further demonstrated in the examples using polyolefins as the thermoplastic resin. Examples of polyolefins include, but are not limited to, polyethylenes, linear and branched, low density and high density. Blends of polyethylenes, and blends of polyethylene or polyethylenes with other thermoplastic resins are operable herein. Preferred nucleating agents with polyethylene-containing thermoplastic resins are the potassium salt of perfluorooctane sulfonic acid, and the calcium, iron or chromium salt of TBSA, at a preferred concentration of 1000 to 3000 ppm, based on the composition. In general, polymers having high dielectric constants respond best to TBSA salts with small cation radius and low valence. As the acid strength and/or chain length of the salt anion change in any given polymer, the optimum cation also tends to change. In the polyethylene of Example 11 the optimum cation for a TBSA salt is chromium, whereas with a perfluorooctanesulfonic acid the optimum cation is potassium; with trifluoromethanesulfonic acid, sodium is the best cation of those tested. Thus, as the strength of the sulfonic acid increases and/or chain length decreases, the optimum cation moves down or to the left in a plot, such as in Figure 2. The phosphonic acids, and their salts, of this invention give results similar to those described above for the sulfonic acids and their salts. It is to be understood that routine experimentation may be required to find the optimum cation and anion for each thermoplastic, with dependence also on variables such as the molecular weight distribution of the thermoplastic, the polarity of the gas used, and the extrusion temperature. However, as demonstrated herein, efficient nucleation is achievable with the nucleating agents of the invention in a wide variety of polymers. The present invention provides means for producing foamed thermoplastics having a combination of a uniformly small cell size, less than 400 micrometers, and a very high void content, greater than 50%. For example, using TFE/HFP copolymer thermoplastics, cell sizes of less than 100 micrometers (average) and void contents of greater than 60% can be achieved. Using polyethylene thermoplastics, cell sizes of less than 100 micrometers (average) and void contents of greater than 50% can be achieved. Foams of similar structure (as with polyethylenes) can also be produced using E/TFE copolymers as the thermoplastic. EXPERIMENTAL DETAILS In the examples herein the foaming process was carried out by either a continuous gas injection foaming process or by extruding a composition containing a chemical blowing agent in the same extruder, with no gas injection. The continuous gas injection foaming process was normally carried out using chlorodifluoromethane (F-22) or nitrogen as the blowing agent. Other known blowing agents could be used to give substantially the same results. The foam void level was controlled by the pressure of the blowing agent. The extruder screw design allowed for gas injection and had a mixing torpedo (as disclosed in U.S. 3,006,029) to provide a uniform melt. This mixing torpedo allowed each resin cube blend to become a uniform melt mixture while traversing the length of the screw. Nucleated compositions for the gas injection process can be prepared by cube blending of the resin (melt cut or strand cut) with a nucleating agent concentrate prepared by blending the sulfonic or phosphonic acid, or its salt, in the form of a powder, with resin powder and/or cubes, and extruding on a 28 mm Werner & Pfleiderer (W&P) twin screw extruder with a strand cutter to pelletize. The resulting cube blends were fed directly to the wire coating extruder hopper. ETFE copolymer compositions containing chemical blowing agents were prepared by blending the chemical blowing agent and nucleating agent with polymer powder and compacting into cylindrical pellets about 3 mm in diameter and 6 mm in length with a lab model California Pellet Mill. These pellets were fed directly to the wire coating extruder hopper. Foam cell size was determined at mid-wall of the foam by visual examination with a microscope or by taking a picture of a thin section of foamed wire insulation at 20-30X magnification and visually determining average cell size. In some examples the number of cells/cm 3 is also given. This value is calculated from the foam void level and the average cell diameter. Additional abbreviations used in the examples are shown in Table 2. In reciting specific polymer compositions in the table, there is no intent to limit the scope of the polymers operable herein to those specific compositions. Typical conditions used in the examples that follow are shown in Table 3. Regarding Table 3, in Column C a Maillefer extruder was used to produce the foam and an Entwistle extruder was used to produce the skin. In Column H the extruder was a Davis-Standard. In all other columns the extruder was an Entwistle. Further regarding Table 3, in Column A, a B&H 75 crosshead was used; in all other columns the crosshead was a Maillefer 4/6F. Finally, the Column C conditions were carried out to produce a foam-skin construction, using two extruders and a single crosshead. Foam cell size depends not only on the nucleating agent, but also on other variables, such as wire speed and, in the case of melt draw extrusion, cone length (the distance from the die exit to the point where the molten tubular polymer forms on the wire), as explained in U. S. 4,764,538. Cone length is related to the applied vacuum inside the cone. TFE/HFP copolymer a copolymer of 12.3 wt % HFP and the balance TFE with a melt flow rate of 6.6 at 372° C as measured by ASTM D-2116-83 PAVE perfluoro(alkyl vinyl ether) EVA Ethylene/Vinyl Acetate PVF 2 Poly(vinylidene fluoride) boron nitride SHP-325 grade from Carborundum Corp., having a BET surface area of 8.6 m 2 /g polyarylate aromatic polyester of Bisphenol A and isophthalic acid, with a melt viscosity at 330°C of 1600 Pa·s at 100 sec -1 and 2800 Pa·s at 10 sec -1 E/TFE copolymer copolymer of 19.6 wt % ethylene, 2.2 wt % perfluorobutyl ethylene, and the balance TFE, with a melt flow rate of 14 at 297°C by ASTM D-3159-83 Ficel ® Ficel ® AF-100 formulated zinc compound, a chemical blowing agent from Sherex Chemical Co. Expandex ® Expandex ® 175, barium salt of 5-phenyl tetrazole, a chemical blowing agent of Olin Chemicals, Stamford, Connecticut TFE/PPVE(1) copolymer copolymer of TFE and 3.9 wt. % perfluoro(propyl vinyl ether), with a melt viscosity of 2.2 x 10 4 poise at 372°C TFE/PPVE(2) copolymer copolymer of TFE and 3.9 wt. % perfluoro(propyl vinyl ether), with a melt viscosity of 4.25 x 10 4 poise at 372°C E/CTFE copolymer copolymer of ethylene and chlorotrifluoroethylene FEP copolymer copolymer of TFE and 12.3 wt. % hexafluoropropylene, with a melt flow rate of 6.6 at 372°C (ASTM D-2116-83) ZrS-10 zirconium (+4) salt of TBSA CrS-10 chromium (+3) salt of TBSA CeS-10 cerium (+4) salt of TBSA KS-10 potassium salt of TBSA HS-10 TBSA AS-10 aluminum salt of TBSA SrS-10 strontium salt of TBSA CaS-10 calcium salt of TBSA ZnS-10 zinc salt of TBSA BaS-10 barium salt of TBSA LS-10 lithium salt of TBSA FS-10 iron (+3) salt of TBSA TEAS-10 triethylamine salt of TBSA BS-6A barium p-(perfluoro[1,3-dimethylbutyl]) benzene sulfonate BS-9A barium p-(perfluoro[1,3,5-trimethylhexyl]) benzene sulfonate BaS-Al(H) barium p-toluene sulfonate BaP-A barium benzene phosphonate NaP-A sodium benzene phosphonate NaS-A(II) 4,5-dihydroxy-m-benzene disulfonic acid disodium salt BS-8 barium perfluorooctane sulfonate KS-8 potassium perfluorooctane sulfonate KS-8C potassium perfluorocyclohexylethane sulfonate NaS-1 sodium trifluoromethane sulfonate KS-1 potassium trifluoromethane sulfonate KS-1(H) potassium methane sulfonate BaS-3(H) barium propane sulfonate NaTCA sodium trichloroacetate BTBP barium salt of F(CF 2 ) n CH 2 CH 2 PO 3 H wherein n is a mixutre of 6, 8, 10 and possibly 12, predominantly 8 NTBP sodium salt of F(CF 2 ) n CH 2 CH 2 PO 3 H wherein n is a mixture of 6, 8, 10 and possibly 12, predominantly 8 LL1121B barium perfluoro(2,5-dimethyl)-3,6-dioxatridecanoate BC14(06) barium perfluoro 3,5,7,9,11,13-hexaoxatetradecanoate BS-12(H) barium lauryl sulfate NS-12(H) sodium lauryl sulfate CC-18(H) calcium stearate BaC-8 barium perfluorooctanoate BaC-9 barium perfluorononanoate AWG-26 Solid copper wire 404 micrometers in diameter AWG-24 Solid copper wire 510 micrometers in diameter AWG-22 Solid copper wire 635 micrometers in diameter Specific examples of the foamable composition are those in which the nucleating agent contains only two of the diradical units selected from (CF 2 ) x , (CF 2 CFX) p , (R') y , and (CH 2 ) z ; in which the nucleating agent has a total of no more than 20 carbon atoms and M is selected from H, K, Na, Ba, Zr, Cr, Ce, Al, Sr, Ca, Zn, Li, Fe, and triethyl ammonium; in which the nucleating agent comprises at least one salt of the acid of the formula F(CH 2 ) x (CH 2 ) z SO 3 H, in which x is 6 to 12 and z is 0, 1, or 2; in which the nucleating agent is the potassium salt of perfluorooctane sulfonic acid, and the concentration of nucleating agent, based on the composition, is 500-3000 ppm; in which R is sulfur; in which R is phosphorus; in which M is a metallic cation; in which Z is F, R is sulfur, M is selected from barium, iron and zirconium, x is a mixture of 6, 8, 10 and possibly 12, predominantly 8, y and p are 0, and z is 2; in which the concentration of nucleating agent, based on the composition, is 250 to 2000 ppm; in which the concentration of nucleating agent, based on the composition, is 500 to 2000 ppm; in which Z is F, R is sulfur, M is potassium, x is 1 to 10, and each of y, p and z is 0; in which the thermoplastic resin is a polyolefin; in which at least one additional nucleating agent is contained; in which the additional nucleating agent is boron nitride; in which the additional nucleating agents are boron nitride and calcium tetraborate; in which a chemical blowing agent is contained; in which the blowing agent is a formulated zinc compound or a high temperature azo compound, and the nucleating agent is the potassium salt of a perfluorinated alkane sulfonic acid; in which Z is F, R is sulfur, M is calcium, x is a mixture of 6, 8, 10 and possibly 12, predominantly 8, y and p are 0, and z is 2, and the blowing agent is a formulated zinc compound or a high temperature azo compound. Example 1 A. TFE/HFP copolymer was cube blended with a 5 weight percent boron nitride concentrate (compounded with TFE/HFP copolymer in a 28 mm W&P twin screw extruder as described earlier) in the ratio needed to give a product with 0.25% boron nitride. B. A second composition was prepared from TFE/HFP copolymer by blending a 5 weight % boron nitride concentrate plus a 0.3 weight % KS-10 concentrate to give 0.25% boron nitride and 330 ppm KS-10. C. A third composition was prepared from TFE/HFP copolymer by blending with a 5 weight percent boron nitride concentrate plus a concentrate containing 0.3% calcium tetraborate to give 0.25% boron nitride and 125 ppm calcium tetraborate. D. A fourth composition was prepared from TFE/HFP copolymer by blending with a 5 weight % boron nitride concentrate plus a concentrate containing 0.3% calcium tetraborate and a 0.3 weight % TBSA concentrate to give 0.25% boron nitride and 125 ppm calcium tetraborate plus 330 ppm of TBSA. These four compositions were extruded onto wire under the conditions of Table 3, Column A with the following results: Composition %V AFCD (M) cc/cm 3 A. 55 381 18,000 B. 60 152 312,000 C. 55 100 2,800,000 D. 58 76 12,000,000 As seen from these results, the KS-10 can be used with boron nitride, and it gives enhanced foam nucleation. Similarly, TBSA can be used in conjunction with boron nitride and calcium tetraborate, and it gives enhanced nucleation. Example 2 TFE/HFP copolymer was blended with a 5% boron nitride concentrate and with a 0.3% BaS-10 concentrate to give the compositions shown in Table 5. Each composition was foamed onto wire using the conditions of Table 3, Column A. Additive Conc. (ppm) AFCD (M) None - 635 Boron nitride 5000 125 BaS-10 125 760 BaS-10 500 100 BaS-10 1000 75 BaS-10 1500 255 As shown above, BaS-10 is a very effective nucleant at low concentrations compared with boron nitride, a traditional nucleating agent used with TFE/HFP copolymers. It should also be noted that there is an optimum concentration for the BaS-10 nucleating agent. Example 3 Samples of TFE/HFP copolymer containing several concentrations of various salts of TBSA were prepared by blending virgin resin with the appropriate ratio of concentrate containing 0.3% of the fluorosulfonic acid salt. These compositions were foamed onto wire as described in Table 3, Column A, with the results shown in Table 6. The last column shows the deviation from the average diameter (3300 micrometers) of the foam insulated wire. Additive Conc. (ppm) AFCD (M) %V Deviation (M) Boron nitride (control) 5500 127 58 ± 76 ZrS-10 75 685 61 ± 127 300 387 58 ± 127 500 76 67 ± 76 1000 76 65 ± 76 2000 203 65 ± 127 3000 203 56 ± 127 CrS-10 75 635 52 ± 50 300 431 59 ± 76 500 101 62 ± 50 1500 127 62 ± 50 2000 89 37 - 3000 - CeS-10 63 559 63 ± 127 250 635 65 ± 127 500 762 72 ± 127 1000 381 66 ± 76 2000 178 67 ± 76 3000 127 62 ± 50 KS-10 63 762 78 ± 127 250 304 65 ± 76 500 241 66 ± 76 1000 228 64 ± 76 2000 - HS-10 63 762 61 ± 76 250 203 65 ± 76 500 127 64 ± 76 1000 127 61 ± 76 AS-10 500 889 60 ± 100 1000 127 58 ± 50 2000 139 60 SrS-10 500 139 58 ± 100 2000 127 59 ± 75 3000 228 57 ± 127 CaS-10 500 203 41 ± 76 1000 228 41 ± 100 1500 406 41 ± 127 Zn-10 1000 508 20 ± 127 2000 381 20 ± 127 3000 381 20 ± 127 BaS-10 125 762 20 500 101 55 ± 50 1000 76 55 ± 50 1500 254 40 ± 150 LS-10 500 178 55 ± 75 1000 178 56 ± 75 FS-10 75 406 52 ± 250 150 101 55 ± 50 300 101 58 ± 50 500 76 55 ± 50 1000 76 55 ± 59 As seen above, all of these fluorosulfonic acid salts (and the HS-10 itself) function as nucleating agents. Some are much better than others and the performance of each one varies with concentration. In addition to cell size and void content variation, there are significant fluctuations in diameter and capacitance. Example 4 A series of samples containing various levels of salts of three other types of sulfonic acids and a phosphonic acid were also prepared, extended in TFE/HFP copolymer and foamed onto wire, as described in Example 3, with the results shown in Table 7. The last column shows the deviation from the average diameter (3300 micrometers) of the foam insulated wire. Additive Conc. (ppm) AFCD (M) %V Deviation (M) BS-9A 500 762 75 1000 762 62 2000 381 60 ± 75 3000 253 54 ± 75 BS-8 500 254 56 ± 100 1000 228 57 ± 75 2000 101 59 ± 50 KS-8C 1500 635 40 ± 200 3000 400 40 ± 200 BTBP 1500 64 80 ± 200 3000 25-67 ∼ 70 As seen from the above results, the three barium salts are effective as nucleating agents for TFE/HFP copolymers, whereas the potassium salt is not. Comparative Example A In contrast to Examples 3 and 4, samples containing various levels of other types of salts (not within the invention) in TFE/HFP copolymers were prepared in the same manner from concentrates containing 0.3% of the salt. These compositions were also foamed onto wire as described in Table 3, Column A with the results shown in Table 8. Additives Conc. (ppm) AFCD (M) %V LL1121B 500 1016 65 1000 558 46 2000 1016 45 3000 1016 63 BC14(06) 500 890 52 1000 762 55 2000 890 55 3000 1016 62 BS-12(H) 500 431 57 1000 711 52 2000 889 57 3000 889 57 CC-18(H) 500 685 60 1000 1270 62 2000 1524 63 BaC-8 500 635 46 1000 635 45 BaC-9 500 1016 42 1000 762 53 1500 889 53 Example 5 Compositions with tetrafluoroethylene(TFE)/perfluoro(propyl vinyl ether) (PPVE) copolymers (TFE/PPVE copolymers) were made up using a 0.3% concentrate of BaS-10 as described in Example 2. These compositions were foamed onto wire according to the conditions of Table 3, Column A. The results are shown in Table 9. The capacitance and diameter stability during extrusion are shown in the last column. Additive Conc. (ppm) AFCD (M) %V Remarks TFE/PPVE(1) Boron nitride (control) 5000 300 55 BaS-10 63 406 51 125 330 57 250 304 55 500 304 55 1000 102 55 2000 89 57 3000 127 54 TFE/PPVE(2) Boron nitride (control) 5000 255 55 BaS-10 500 286 57 1000 191 58 2500 51 60 3000 76 62 As seen from these results, BaS-10 is an effective nucleating agent for TFE/PPVE copolymer resins. Note that there is an optimum concentration range to achieve the smallest cell size. Example 6 ETFE copolymer containing 2 wt. % boron nitride or varying amounts of fluorosulfonic acid salts as indicated in Table 10 was foamed onto wire at about 40 meters/minute according to the conditions of Table 3, Column B. This produced a 0.7 mm thick foamed insulation on AWG-24 solid copper wire having capacitance values near 60 pF/m at a foam void level of about 60% (Table 10 except for KS-8 and KS-8C). For KS-8 and KS-8C this produced a 0.28 mm thick foamed insulation on AWG-24 wire having capacitance values near 136 pF/m (a foam void level of about 42%). Relative foaming performance, as indicated by insulation diameter and capacitance variability and by foam cell size, is shown in Table 10. The last column shows the deviation from the average core diameter of 1900 micrometers and the deviation from the average capacitance of 62-69 pF/m, except for KS-8 and KS-8C wherein the deviations are from an average core diameter of 1068 micrometers and an average capacitance of 138 pF/m. Additive Conc. (ppm) AFCD (M) Deviation (M; pF/m) None None 432 LS-10 750 - 1500 - 3000 - CaS-10 750 76 1500 51 ± 13; ± 0.3 3000 51 BaS-10 750 178 1500 178 ± 38; ± 1.5 3000 178 ZnS-10 750 432 1500 432 ± 40; - 15 3000 432 AS-10 750 500 1500 432 ± 50; - 15 3000 483 FS-10 750 635 1500 635 ± 10; ± 0.3 3000 500 KS-8 250 127 500 114 1000 76 ± 10; ± 0.3 2000 50 3000 89 KS-8C 250 178 500 152 ± 10; ± 0.3 2000 64 3000 38 - 76 Example 7 BaS-10 was evaluated as a nucleating agent for ETFE copolymer in a high speed extrusion (625 m/min.) of thin wall foam-skin insulation on AWG-24 solid copper wire. Conditions used are given in Table 3, Column C and the results are given in Table 11. A dielectric constant of 1.7 corresponds to a foam void level of 48%. Additive C (pF/m) Diameter (M) Foam DC AFCD (M) Ex St 2% BN (Control Resin) 121.4 ± 1.0 1092 ± 50 1.68 50 500 ppm BaS-10 132.2 ± 0.3 1049 ± 13 1.71 50 1000 ppm BaS-10 125.3 ± 0.3 1054 ± 13 1.63 38 2000 ppm BaS-10 131.2 ± 0.3 1049 ± 13 1.70 25 3000 ppm BaS-10 128.9 ± 1.6 1049 ± 25 1.68 50 As seen from the above results, BaS-10 not only gives small cell size but it also improves both diameter and capacitance control in this miniature foam. Example 8 An E/CTFE copolymer (Halar® 500 available from Ausimont Chemical Co.) was foamed with CHF 2 Cl gas injection using a start-stop extrusion procedure. This technique was necessary to avoid immediate plugging of the gas injection probe (improper screw design). The foaming process was carried out according to the conditions given in Table 3, Column D. Nucleated compositions were prepared using a 0.3% concentrate of the salt in the copolymer. The results are given in Table 12. Additive Conc. (ppm) FCC (pF/m) Foam DC %V AFCD (M) cc/cm 3 None 0 98.4 2.01 28 304 336,000 CaS-10 1500 96.8 2.20 20 203 800,000 CaS-10 3000 75.5 1.78 43 102 15,000,000 As seen from the results, CaS-10 is a very effective foam nucleant. Example 9 HAP-E/TFE, a chemical-blown ETFE copolymer foam resin commercially available from Chromatics, Inc. (Bethel, Connecticut) was foamed onto wire with and without added BaS-10 using the extrusion setup shown in Table 3, Column E. In each case, the HAP-E/TFE (210 grade) was blended into a 50/50 mix with ETFE copolymer (one virgin and one containing 0.3% BaS-10). The results are shown in Table 13. No Added Nucleant Added Nucleant 1500 ppm BS-10 Solid AWG-22 Dia (mm) 0.635 0.635 C (pF/m) 91.9 74.2 Stability of C (pF/m) ± 3.3 ± 0.7 Foam Diameter (mm) 2.39 2.54 D C 2.0 1.85 %V 30 35 AFCD (M) 230 38 cc/cm 3 at 33% voids 38,000 13,000,000 As seen from the results, this nucleating agent is very effective in this system. Example 10 Chemical-blown ETFE copolymer compositions were prepared by dry blending powdered ETFE copolymer with Ficel® and the sulfonic acid salt indicated in Table 14. The blends were pelletized in a lab scale California Pellet Mill before evaluation. The compositions were foamed onto wire according to conditions given in Table 3, Column E. The results are given in Table 14. In each case the amount of blowing agent was 0.38 wt. %. Additive Conc. BaS-10 1000 ppm CaS-10 1000 ppm KS-8 1000 ppm KS-8 3000 ppm C (pF/m) 170.6 175.5 198.4 183.7 Foam Diameter (mm) 1.17 1.15 1.10 1.08 DC 1.9 1.9 1.9 1.75 %V 36 36 36 45 AFCD (M) 76 51 51 38 cc/cm 3 1,500,000 6,500,000 6,500,000 18,000,000 As seen from the results, these compositions give good quality foam with small cell size. Although the above description and the claims which follow include preferred embodiments of the invention, it is to be understood that there is no intent to limit the invention to the precise constructions herein disclosed and claimed, and all right is reserved to all changes and modifications coming within the scope of the invention as defined herein. Specific examples of preferred embodiments of foamed structures are structures in which the thermoplastic resin is a tetrafluoroethylene/hexafluoropropylene copolymer, the average cell size is less than 100 micrometers, and the void content is greater than 60%; in which the thermoplastic resin is an ethylene/tetrafluoroethylene copolymer, the average cell size is less than 100 micrometers, and the void content is greater than 50%; in which the thermoplastic resin is an ethylene/tetrafluoroethylene/perfluorobutyl ethylene copolymer.

Claims: Foamable thermoplastic resin extrusion composition, wherein said resin is melt processible fluoropolymer, homogeneously containing as a nucleating agent a nucleating-effective amount of at least one thermally stable compound which is selected from the group consisting of sulfonic and phosphonic acids and salts thereof. The foamable composition of Claim 1 in which the nucleating agent is selected from (a) free acids and salts of partially or totally fluorinated aliphatic sulfonic and phosphonic acids, which optionally may contain cycloalkyl groups and/or ether oxygen; and (b) free acids and salts of aromatic sulfonic and phosphonic acids, in which the aromatic ring, optionally, is substituted with alkyl, fluorine-containing alkyl, and/or hydroxyl groups. The foamable composition of Claim 1 in which the nucleating agent is of the formula [Z(CF 2 ) x (CF 2 CFX) p (R') y (CH 2 ) z RO 3 ] n M wherein: the bivalent groups, except for RO 3 , may be present in any sequence; Z is selected from CCl 3 , CCl 2 H, H, F, C1, and Br; each X, independently, is selected from H, F, Cl and CF 3 ; R is selected from sulfur and phosphorus; M is selected from H and a metallic, ammonium, substituted ammonium and quaternary ammonium cation; each of x and z, independently, is an integer and is 0 to 20; p is an integer and is 0 to 6; y is 0 or 1; x + y + z + p is a positive integer or, if x + y + z + p is 0, then Z is CCl 3 or CCl 2 H; n is the valence of M; and R' is selected from a C 5-6 perfluorinated alicyclic ring diradical; a C 1-16 perfluorinated aliphatic polyether diradical with repeat units selected from [CF 2 O], [CF 2 CF 2 O], and [CF 2 CF(CF 3 )O]; and a substituted or unsubstituted aromatic diradical, in which case, Z is H. Composition of Claim 1 wherein the thermoplastic resin is a fluoropolymer selected from: (a) a homopolymer of chlorotrifluoroethylene or 2,2-difluoroethylene; (b) a copolymer of tetrafluoroethylene and chlorotrifluoroethylene or 2,2-difluoroethylene; or (c) a copolymer of at least one of the monomers of (a) and (b) and one or more of the monomers selected from ethylene, terminally unsaturated perfluoroalkene of 3-8 carbon atoms, perfluoro(alkyl vinyl ether) of 3-8 carbon atoms, oxy-containing perfluoro(alkyl vinyl ether) of 5-12 carbon atoms, and perfluoroalkyl ethylene of 3-8 carbon atoms. Composition of Claim 3 wherein the thermoplastic resin is an ethylene/tetrafluorethylene/perfluorobutyl ethylene copolymer and the concentration of nucleating agent, based on the composition, is 1000 to 3000 ppm, wherein Z is F; R is sulfur; M is calcium; x is a mixture of 6, 8, 10 and possibly 12, predominantly 8; y and p are O; and z is 2. A process for producing a foam of a homogeneous fluoropolymer thermoplastic resin composition starting from a thermoplastic resin extrusion composition, wherein said resin is melt processible fluoropolymer resin, characterized in that the process is carried out with a nucleating-effective amount of at least one thermally stable compound selected from the group consisting of sulfonic and phosphonic acids and salts thereof, so as to produce a foam having uniformity of cell size, small cell size, and high void content. Process of Claim 6 wherein the nucleating agent is of the formula [Z(CF 2 ) x (CF 2 CFX) p (R') y (CH 2 ) z RO 3 ] n M wherein: the bivalent groups, except for RO 3 , may be present in any sequence; Z is selected from CCl 3 , CCl 2 H, H, F, Cl, and Br; each X, independently, is selected from H, F, Cl and CF 3 ; R is selected from sulfur and phosphorus; M is selected from H and a metallic, ammonium, substituted ammonium and quaternary ammonium cation; each of x and z, independently, is an integer and is 0 to 20; p is an integer and is 0 to 6; y is 0 or 1; + y + z + p is a positive integer or, if x + y + z + p is 0, then Z is CCl 3 or CCl 2 H; n is the valence of M; and R' is selected from a C 5-6 perfluorinated alicyclic ring diradical; a C 1-16 perfluorinated aliphatic polyether diradical with repeat units selected from [CF 2 O], [CF 2 CF 2 O], and [CF 2 CF(CF 3 )O]; and a substituted or unsubstituted aromatic diradical, in which case, Z is H. Foamed thermoplastic resin extrusion composition, wherein said resin is melt processible fluoropolymer, produced by the process for producing a foam of a homogeneous fluoropolymer thermoplastic resin composition, characterized in that the foaming process is carried out on the homogeneous resin composition which contains a nucleating-effective amount of a nucleating agent of the formula [Z(CF 2 ) x (CF 2 CFX) p (R') y (CH 2 ) z RO 3 ] n M wherein: the bivalent groups, except for RO 3 , may be present in any sequence; Z is CCl 3 , CCl 2 H, H, F, Cl or Br; each X, independently, is selected from H, F, Cl and CF 3 ; R is sulfur or phosphorus; M is H or a metallic, ammonium, substituted ammonium or quaternary ammonium cation; x is an integer and is 0 to 20; p is an integer and is 0 to 6; y is 0 or 1; z is an integer and is 0 to 20; x + y + z + p is a positive integer or, if x + y + z + p is 0, Z is CCl 3 or CCl 2 H; n is the valence of M; and R' is selected from a C 5-6 perfluorinated alicyclic ring diradical; a C 1-16 perfluorinated aliphatic polyether diradical with repeat units selected from [CF 2 O], [CF 2 CF 2 O] and [CF 2 CF(CF 3 )O]; and a substituted or unsubstituted aromatic diradical, in which case, Z is H, so as to produce a foam having uniformity of cell size, small cell size, and high void content.

Inventors: BUCKMASTER MARLIN DWIGHT, RANDA STUART KARL, BUCKMASTER, MARLIN DWIGHT, RANDA, STUART KARL
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1990
Main classification: C08J9
IPC codes: C08K5, C08L101, C08J9