Tetrafluoroethylene copolymer

Abstract

A polymerization process for producing a copolymer of tetrafluoroethylene and perfluorobutylethylene, prepared by an aqueous dispersion polymerization technique, and the resin produced thereby, are provided. This copolymer contains a relatively small amount, between about 0.02 weight percent and about 0.6 weight percent, of comonomer polymerization units. The copolymer is believed to be comprised of a core-shell structure wherein the polymerized comonomer units reside primarily within the core. The primary particle size of the copolymer ranges from 0.175 microns to and including 0.203 microns and the standard specific gravity is less than 2.143. This copolymer possesses a unique combination of very small particle size coupled with high molecular weight, a combination not heretofore achieved in tetra-fluoroethylene polymers of the dispersion or fine powder type. The process of this invention is characterized by permanganate initiation and the entire reaction is carried out in the absence of zinc chloride or other ionic strength enhancer. The addition of initiator must be stopped well before completion of the reaction, preferably at or before the mid-point of the complete reaction.

What is claimed is:  
     
         1 . A process for the copolymerization of a tetrafluoroethylene copolymer of the dispersion/fine powder type, said copolymer containing essentially from 99.4% by weight to 99.98% by weight tetrafluoroethylene monomer units and from 0.02% by weight to 0.6% by weight copolymerized perfluorobutylethylene comonomer units, comprising: 
 (a) copolymerizing said monomer and comonomer in a pressurized reactor, and    (b) initiating said copolymerization by adding potassium permanganate (KMnO 4 ),    (c) carrying out the entire reaction in the absence of any ionic strength enhancer, and    (d) stopping the addition of (KMnO 4 )initiator at a point in the reaction no further than 80% of the reaction completion.    
     
     
         2 . The process of  claim 1  including adding the comonomer as a precharge in the copolymerization reaction.  
     
     
         3 . The process of  claim 1  including adding the comonomer incrementally and intermittently, from the beginning of the reaction through only a portion of the complete reaction.  
     
     
         4 . The process of  claim 1  including stopping the addition of KMnO 4  initiator at a point in the reaction no further than 60% of the reaction completion.  
     
     
         5 . The process of  claim 1  including stopping the addition of KMnO 4  initiator at a point in the reaction no further than 50% of the reaction completion.  
     
     
         6 . The process of  claim 1  for the copolymerization of a tetrafluoroethylene copolymer of the dispersion/fine powder type, wherein: 
 said polymerized comonomer units are present in an amount from 0.02% by weight to 0.6% by weight, based upon total copolymer weight; and  
 said copolymer has a raw dispersion primary particle size (RDPS) in the range between 0.175 microns to and including 0.203 microns and has a standard specific gravity (SSG) of less than 2.143.  
 
     
     
         7 . The process of  claim 6  wherein said copolymer has a RDPS in the range between 0.175 microns to and including 0.203 microns and has a SSG of less than 2.140.  
     
     
         8 . The process of  claim 6  including adding the comonomer as a precharge in the copolymerization reaction.  
     
     
         9 . The process of  claim 6  including adding the comonomer incrementally and intermittently, from the beginning of the reaction through only a portion of the complete reaction.  
     
     
         10 . The process of  claim 6  including stopping the addition of KMnO 4  initiator at a point in the reaction no further than 60% of the reaction completion.  
     
     
         11 . The process of  claim 6  including stopping the addition of KMnO 4  initiator at a point in the reaction no further than 50% of the reaction completion.  
     
     
         12 . A tetrafluoroethylene copolymer of the dispersion/fine powder type, containing polymerized tetrafluoroethylene monomer units, and copolymerized perfluorobutylethylene comonomer units, wherein: 
 (a) said copolymerized comonomer units are present in an amount from 0.02% by weight to 0.6% by weight, based upon total copolymer weight; and    (b) said copolymer has a raw dispersion primary particle size (RDPS) in the range between 0.175 microns to and including 0.203 microns and has a standard specific gravity (SSG) of less than 2.143.    
     
     
         13 . The copolymer of  claim 12  wherein said comonomer units are present in an amount from 0.05% by weight to 0.5% by weight.  
     
     
         14 . The copolymer of  claim 12  wherein the RDPS is within the range between 0.178 microns and 0.200 microns and has a SSG of less than 2.140.  
     
     
         15 . The copolymer of  claim 12  dispersed within an aqueous dispersion.  
     
     
         16 . The copolymer of  claim 12  in the form of fine powder.  
     
     
         17 . A tetrafluoroethylene copolymer of the dispersion/fine powder type, containing polymerized tetrafluoroethylene monomer units and copolymerized perfluorobutylethylene comonomer units, wherein: 
 (a) said copolymerized comonomer units are present in an amount from 0.05% by weight to 0.5% by weight, based upon total copolymer weight; and    (b) said copolymer has a RDPS between 0.178 microns and 0.200 microns and has a SSG of less than 2.140.    
     
     
         18 . The copolymer of  claim 17  dispersed within an aqueous dispersion.  
     
     
         19 . The copolymer of  claim 17  in the form of fine powder.  
     
     
         20 . The copolymer of  claim 12  shaped into the form of expanded beading having a break strength of at least 7.9 lbs.  
     
     
         21 . The copolymer of  claim 17  shaped into the form of expanded beading having a break strength of at least 9.0 lbs.  
     
     
         22 . The copolymer of  claim 20  having a break strength of at least 11.0 lbs.