Patent Publication Number: US-5530078-A

Title: Preparation of a modified polytetrafluoroethylene and use thereof

Description:
DESCRIPTION 
     The invention relates to a process for preparing a polytetrafluoroethylene (PTFE) modified with perfluoro(alkyl vinyl ether) (PAVE) units and the use thereof for the preform free-sintering technique. &#34;Modified&#34; PTFE means that the tetrafluoroethylene (TFE) polymer contains relatively small proportions of ether units, namely usually below 0.1 mol %, and that the copolymer, like the homopolymeric PTFE, is not processible from the melt. On the other hand, the content of ether units in the polymer must be sufficiently high for the tendency to crystallization from the melt to be inhibited and for the amorphous content to be increased within certain limits. In this way, the good mechanical properties such as tensile strength and elongation at break of the unmodified PTFE are achieved even at significantly lower molecular weights. 
     The lower molecular weights of the modified products are evident in a melt viscosity by the Ajroldi method (U.S. Pat. No. 3 855 191, column 8) of from about 1 to 100 GPas, while the melt viscosity of the unmodified polymers for comparably good mechanical properties is more than 300 GPas. 
     This drastic lowering of the melt viscosity improves the properties of the shaped parts produced from these modified molding powders. Since the particles of the molding powder melt together more easily, the shaped parts contain fewer pores and consequently have an improved electrical breakdown resistance; in addition, the creep resistance is almost doubled. In particular, however, the weldability of the shaped parts is considerably improved. 
     As already mentioned above, the invention also provides for the use of the modified PTFE for the preform free-sintering technique. For this purpose, good millability of the raw polymer is imperative. In contrast thereto, ram extrusion requires a hard, i.e. poorly millable, grain and good flowability. 
     The invention provides a process for preparing polymers of TFE containing from 0.02 to 0.25% by weight of PAVE units having from 1 to 4 carbon atoms in the perfluoroalkyl chain, which comprises polymerizing the monomers by the suspension process in aqueous medium using an initiator containing manganese in a higher oxidation state at a temperature below 60° C. For use according to the invention, the raw polymer thus obtained is milled to an average particle size of from 10 to 50 μm. 
     The preferred PAVE is perfluoro(n-propyl vinyl ether), hereinafter referred to as PPVE. 
     The polymerization temperature is preferably in a range from 10° to 50° C., the polymerization pressure is in the range from 4 to 25 bar, in particular from 5 to 15 bar. 
     Suitable initiators are salts of permanganic, manganic and manganous acid. Preference is given to the permanganates, in particular the alkali metal permanganates. They are advantageously used in combination with a soluble oxalate such as ammonium oxalate or an alkali metal oxalate. 
     Further preferred embodiments of the invention are illustrated below in more detail. 
     The preparation of copolymers comprising TFE and PAVE units using permanganate and similar initiators is already known. Thus, U.S. Pat. No. 4,262,101 discloses the preparation of a terpolymer by copolymerization of TFE with from 1 to 6 mol % of PAVE and from 5 to 25 mol % of hexafluoropropene in the presence of a chain transfer agent. The polymerization temperature can be from 10 to 150° C., preferably from 10 to 50° C. The terpolymer thus obtained is processible from the melt. 
     U.S. Pat. No. 4,078,134 discloses the polymerization of TFE with only very small amounts of PAVE, namely from 0.0004 to 0.0029 mol %. The preferred polymerization temperature is from 10° to 35° C., in the examples using potassium permanganate as initiator it is 15° or 25° C. The products thus obtained are distinguished both from unmodified PTFE and from the products having higher proportions of modifier, namely above 0.0029 mol% (column 4, lines 18 to 68). They are suitable for the production of shaped bodies by forming, sintering and, in particular, ram extrusion. As a result, they cannot meet the specific demands which are nowadays made of a molding powder for the preform free-sintering technique. 
     The preparation of a TFE polymer which is modified with PAVE and is suitable for the preform free-sintering technique is known from U.S. Pat. No. 3,855,191. Here, the polymerization is carried out at from 50° to 100° C., with inorganic persulfates being preferred as initiators. Although redox initiator systems are specified, salts of manganese acids are not mentioned. The desired low amorphous content of below 8% by weight, preferably below 6.5% by weight, is achieved by the use of a fluorinated dispersant which has no telogenic action. However, it has been found that these dispersants lead to lump formation during the polymerization, particularly at lower temperatures, as they are used according to the invention. Thus, a controlled reaction up to a desired solids content of about 30% by weight is no longer ensured. 
     It has furthermore been found that the specified lump formation occurs when using the fluorinated dispersants, particularly at a relatively low salt content in the polymerization liquid. However, the process of the invention allows low salt contents which not only simplify the disposal of waste water, but also have a positive influence on the product properties. 
     The polymerization carried out according to the invention gives a raw polymer which is very readily millable. The considerably improved millability is evident in a more than doubled throughput and/or a lower energy consumption of the mill. 
     It has furthermore been found that the ready millability of the raw polymers is coupled with advantageous mechanical and electrical properties. The molding powders thus obtained have a high pressability or deformability. For the purposes of the present invention, this means the alteration of the gravimetrically determined densities of the molding powder pressed under various high pressures without sintering, i.e. in the form of the so-called green body (U.S. Pat. No. 3,245,972, column 2, lines 28 to 37). Increasing pressability or deformability improves the technical properties of the sintered material, because the contact between the individual particles is thereby more readily ensured. 
     The shaped bodies produced from the products obtained according to the invention have a combination of valuable properties, namely, in particular, a high tensile strength with good elongation at break and a high electrical breakdown resistance. 
     The good millability and also the improved properties of the final products is probably caused by an improved grain structure of the polymer. This is evident in a drastic increase in the specific surface area. It has been found that this grain improvement is significantly influenced in the desired direction by relatively high TFE pressures, for example in the range from 15 to 25 bar. However, for technical reasons, a pressure range from 5 to 15 bar is preferred, since a higher TFE pressure leads to a higher loss of the expensive PAVE and, in addition, the explosion risk inherent in the system is increased at high pressures. 
     The desired influence on the grain structure is, according to the invention, achieved principally by means of the low polymerization temperatures. As mentioned, a low salt content in the polymerization medium is also advantageous. With the initiator used according to the invention, the polymerization temperature can be reduced to about 10° C., without the space-time yield (at comparable molecular weight and the same degree of modification) being unjustifiably reduced. This is surprising since the polymerization is considerably slowed by PAVE. 
     The initiators of the invention have a strongly temperature-dependent decomposition rate. Therefore, with falling polymerization temperature an increasing proportion of the total amount of initiator is initially charged at the beginning of the polymerization and the remainder is metered in, preferably continuously over the whole duration of the polymerization. The metered addition is advantageously controlled in such a way that the polymerization rate for a constant degree of incorporation of the PAVE over time does not decrease. 
     The polymerization can also be carried out by the process known from U.S. Pat. No. 5,153,285, in which a mixture of TFE and inert gas is injected under pressure prior to the polymerization and the total pressure of the injected mixture is from 5 to 50 bar, with the concentration of the TFE in this mixture being from 30 to 70 mol % and being maintained in this range by appropriate further injection during the polymerization. 
     If a free-flowing product is desired, the milled product obtained according to the invention can be granulated in a known manner. The agglomeration process known from U.S. Pat. No. 4,439,385 is suitable. 
     The invention is illustrated by the following examples. Percentages are by weight. 
    
    
     EXAMPLES 
     A 150 l reactor is charged with 100 l of deionized water and the amount of ammonium oxalate (AmOx) given in Table 1 is added. The contents of the reactor are freed of atmospheric oxygen by alternate evacuation and flushing with nitrogen. TFE is injected up to a pressure of 10 bar and the total pressure is increased to 15 bar by injection of nitrogen. This pressure is kept constant over the whole polymerization time by further injection of TFE. The amount of PPVE given in Table 1 is metered into the reactor and the contents of the reactor are brought to the temperature given in Table 1. This temperature is likewise kept constant over the whole duration of the polymerization. The polymerization is started by rapid metered addition (within 5 minutes) of the amount of potassium permanganate given in Table 1 under &#34;initiation&#34; dissolved in 300 ml of water. The reaction starts virtually instantaneously. After about 20 minutes, an aqueous solution of the amount of potassium permanganate given in Table 1 and also the further amount of PPVE are continuously metered in. 
     After the desired amount of TFE has been introduced, the reaction is stopped by the metering-in of initiator, PPVE and TFE being interrupted. After a further period of about 20 minutes, the pressure drops to about 6 bar. The contents of the reactor are then cooled to room temperature and are substantially freed of the residual monomers by repeated evacuation. 
     The product obtained is washed three times with deionized water, dried for 10 hours at 220° C. and milled in a spiral-jet mill. The average particle size d 50  of the milled product is about 20 μm. The further properties of the milled powder are given in Table 1. These properties were determined as follows: 
     The amorphous content is determined by IR spectroscopy on 100 μm films by measurement of the absorption at 778 and 2353 cm -1  in accordance with the method given in U.S. Pat. No. 3 855 191, column 5. 
     The PPVE content is likewise determined by IR spectroscopy on 100 μm films by measurement of the absorption at 995 and 2353 cm -1  in accordance with the relationship % PPVE content=0.95·A 995  /A 2353 . 
     The specific surface area is determined by measurement of the nitrogen adsorption in accordance with the method described by F. M. Nelson and F. T. Eggertson [Anal. Chem. 30, 1387 (1958)]. 
     The millability of the raw polymer in the spiral-jet mill was measured by the throughput amount per hour at a milling-air pressure of 6 bar and with the same proportion of particles larger than 33 μm, measured by sieving. 
     The molecular weight given in Table 1 (number average) was estimated, under the plausible assumption that the initiator used is practically quantitatively reacted under the reaction conditions indicated, in accordance with the following relationship: 
     M n  =2·100·m p  /I 0 , 
     where m p  is the amount of TFE reacted in mole, I 0  is the amount of initiator used in mole, the factor 100 is the molecular weight of TFE and the factor 2 represents a combination termination. 
     The standard specific gravity is determined in accordance with ASTM testing standard D-1457-69. 
     Table 1 also shows, under &#34;final properties&#34;, the tensile strength (TS), the elongation at break (EB) and the electrical breakdown resistance (EBR). These properties are determined on films which are produced as follows: 
     a) washing of the raw polymer with deionized water, 
     b) predrying in a fluidized bed at temperatures up to 130° C., 
     c) further drying for 4 hours at 220° C., 
     d) milling in an air-jet mill to a d 50  of about 20 μm, 
     e) pressing at 350 bar into a cylindrical, 13 kg block about 208 mm in both height and diameter, 
     f) sintering at 380° C. in accordance with a temperature program and 
     g) shaving off a film having a thickness of 100 μm in 200 μm steps. 
     Samples of the 100 μm thick films from the middle zone of the block are used for determining the tensile strength and elongation to break in accordance with DIN 53455 (strip method) and the electrical breakdown resistance in accordance with DIN 53481. 
     Table 2 shows comparative examples. Since the disintegration rate of the initiators used according to the invention becomes so high at temperatures above 60° C. that a readily reproducible polymerization can be achieved only with difficulty, ammonium persulfate (APS) was used as initiator. Besides ammonitunoxalate, ammonium carbonate (AmCb) was also used as buffer substance. The molecular weight was estimated using the following relationship: 
     M n  =100·m p  /[I 0  (1-e-k d  ·t)] 
     where m p  is the molar amount of TFE reacted, I 0  is the amount of initiator used in mole, k d  is the decomposition constant of ammonium persulfate and t is the polymerization time. This relationship assumes that the persulfate disintegrates into two initiator free radicals. 
     The value used for the disintegration constant k d  was 1.2·10 -5  sec -1  at 70 ° C. and 0.5·10 -5  sec -1  at 63 ° C. [I. M. Kolthoff, I. H. Miller, J. Am. Chem. Soc. 37 (1951) 3055]. 
     A comparison of the average values from the Tables 1 and 2 gives the following property profile: 
     The product of the process of the invention has, at comparable molecular weight and degree of modification, a significantly higher specific surface area, a drastically improved millability, an electrical breakdown resistance increased by 30% and a tensile strength increased by 10 N/mm 2 , with only slightly decreased elongation at break. 
     
                                           TABLE 1                                 
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Process parameters                                                        
                 KMnO.sub.4    Metered                                    
                 subse-   PPVE addition                                   
   Temper-  KMnO.sub.4                                                    
                 quently  initially                                       
                               rate  Run                                  
   ature                                                                  
        AmOx                                                              
            initiation                                                    
                 metered                                                  
                      TFE charged                                         
                               [g] PPVE/                                  
                                     time                                 
Ex.                                                                       
   [°C.]                                                           
        [g] [mg] in [mg]                                                  
                      [kg]                                                
                          [g]  [kg] TFE                                   
                                     [h]                                  
__________________________________________________________________________
1  55   1.5 50   780  42.0                                                
                          30.0 2.5   3.9                                  
2  55   1.5 35   800  50.0                                                
                          35.0 2.0   5.4                                  
3  40   1.5 30   780  50.7                                                
                          30.0 2.5   5.3                                  
4  40   1.5 40   820  51.3                                                
                          30.0 2.5   5.2                                  
5  40   3.0 40   620  51.0                                                
                          30.0 2.5   4.0                                  
6  40   1.5 300  570  52.5                                                
                          70.0 1.0   4.5                                  
7  40   1.5 300  520  52.4                                                
                          70.0 1.0   4.8                                  
8  40   1.5 70   800  48.4                                                
                          60.0 2.0   5.0                                  
9  35   1.5 20   730  50.8                                                
                          30.0 2.5   5.1                                  
10 35   5.0 30   910  51.7                                                
                          45.0 2.5   4.9                                  
11 20   1.5 300  570  52.0                                                
                          60.0 2.5   5.1                                  
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Powder properties                                                         
PPVE    Amor-                                                             
            Specific       Standard                                       
                                Final properties                          
   incorpor-                                                              
        phous                                                             
            surface                                                       
                 Milla-    specific                                       
                                TS    EBR                                 
   ation                                                                  
        content                                                           
            area bility                                                   
                     M.sub.n × 10.sup.-7                            
                           gravity                                        
                                [N/                                       
                                   EB [kV/                                
Ex.                                                                       
   [%]  [%] [m.sup.2 /g]                                                  
                 [kg/h]                                                   
                     [g/mol]                                              
                           [g/cm.sup.3 ]                                  
                                mm.sup.2 ]                                
                                   [%]                                    
                                      mm]                                 
__________________________________________________________________________
1  0.08 5.4 4.3  10  1.6   2.177                                          
                                45.8                                      
                                   635                                    
                                      119                                 
2  0.07 3.6 3.7  12  1.9   2.163                                          
                                46.4                                      
                                   665                                    
                                      121                                 
3  0.09 5.9 2.7  11  2.0   2.159                                          
                                44.0                                      
                                   605                                    
                                      130                                 
4  0.10 6.0 2.9  12  1.9   2.158                                          
                                43.6                                      
                                   590                                    
                                      120                                 
5  0.08 5.9 3.2  13  2.5   2.160                                          
                                42.2                                      
                                   615                                    
                                      129                                 
6  0.09 6.2 3.1  12  1.9   2.162                                          
                                47.3                                      
                                   625                                    
                                      130                                 
7  0.08 6.3 3.3  14  2.0   2.161                                          
                                48.2                                      
                                   640                                    
                                      139                                 
8  0.08 5.7 2.9  11  1.8   2.163                                          
                                42.4                                      
                                   670                                    
                                      120                                 
9  0.09 5.7 3.3  11  2.2   2.157                                          
                                51.5                                      
                                   595                                    
                                      138                                 
10 0.10 6.8 3.4  12  1.8   2.161                                          
                                46.5                                      
                                   625                                    
                                      130                                 
11 0.09 7.6 3.8  10  1.9   2.155                                          
                                48.9                                      
                                   555                                    
                                      134                                 
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                                           TABLE 2                                 
__________________________________________________________________________
Process parameters                  Powder                                
                           Metered  properties                            
         Buffer       PPVE addition PPVE Amor-                            
    Temper-                                                               
         substance    initially                                           
                           rate  Run                                      
                                    incorpor-                             
                                         phous                            
Comp.                                                                     
    ature                                                                 
         amount/                                                          
                APS                                                       
                   TFE                                                    
                      charged                                             
                           [g] PPVE/                                      
                                 time                                     
                                    ation                                 
                                         content                          
Ex. [°C.]                                                          
         type   [g]                                                       
                   [kg]                                                   
                      [g]  [kg] TFE                                       
                                 [h]                                      
                                    [%]  [%]                              
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1   70   10                                                               
           g/AmCb                                                         
                5.0                                                       
                   50 35.0 1.7   5.3                                      
                                    0.09 5.8                              
2   70   20                                                               
           g/AmCb                                                         
                5.0                                                       
                   50 70.0 0.6   5.2                                      
                                    0.10 6.3                              
3   70   20                                                               
           g/AmCb                                                         
                4.0                                                       
                   50 60.0 0.7   5.2                                      
                                    0.10 6.1                              
4   70   3.2                                                              
           g/AmOx                                                         
                3.8                                                       
                   50 35.0 1.7   5.0                                      
                                    0.09 7.1                              
5   70   7.5                                                              
           g/AmOx                                                         
                4.6                                                       
                   50 70.0 0.6   5.0                                      
                                    0.10 7.7                              
6   63   7.0                                                              
           g/AmOx                                                         
                7.6                                                       
                   50 60.0 0.7   4.7                                      
                                    0.11 7.8                              
7   63   7.0                                                              
           g/AmOx                                                         
                7.6                                                       
                   50 35.0 1.7   4.7                                      
                                    0.09 7.6                              
8   63   7.5                                                              
           g/AmOx                                                         
                7.6                                                       
                   50 70.0 0.6   4.7                                      
                                    0.12 7.5                              
__________________________________________________________________________
Powder properties                                                         
Specific               Standard                                           
surface    Milla-      specific                                           
                             Final properties                             
Comp.                                                                     
     area  bility                                                         
                M.sub.n × 10.sup.-7                                 
                       gravity                                            
                             TS    EB  EBR                                
Ex.  [m.sup.2 /g]                                                         
           [kg/h]                                                         
                [g/mol]                                                   
                       [g/cm.sup.3 ]                                      
                             [N/mm.sup.2 ]                                
                                   [%] [kV/mm]                            
__________________________________________________________________________
1    1.4   5.3  1.3    2.171 35.6  675 94                                 
2    1.5   5.5  1.3    2.17  36.1  655 98                                 
3    1.4   5.1  1.7    2.169 34.8  695 95                                 
4    1.5   4.3  1.8    2.17  32.8  705 99                                 
5    1.5   4.1  1.5    2.173 36.6  690 101                                
6    1.3   5.0  1.9    2.171 35.4  720 99                                 
7    1.4   4.8  1.9    2.169 37.3  665 97                                 
8    1.3   5.1  1.9    2.164 34.5  690 103                                
__________________________________________________________________________