PROCESSING ADDITIVES FOR TETRAFLUOROETHYLENE POLYMERS

Abstract: A composition comprising a blend of tetrafluoroethylene polymers and selected poly(2,2-dialkylpropiolactones) and a mixture of such blend with one or more additional materials, especially particulate carbon, is disclosed. Such blends and mixtures are useful as molding compounds. Also provided is a process for the production and use of such blends and mixtures and their pyrolysis to give polytetrafluoroethylene parts.

Description: TITLE PROCESSING ADDITIVES FOR TETRAFLUOROETHYLENE POLYMERS FIELD OF INVENTION A blend of tetrafluoroethylene polymers and polymers of selected poly(2,2-dialkylpropiolactones) , and mixtures of such blends with one or more other materials, especially particulate carbon, is disclosed. Also disclosed is a process for making the blends and mixtures. Such blends and mixtures are useful to improve processing of tetrafluoroethylene polymers, and readily undergo pyrolysis to give tetrafluoroethylene polymer parts with improved physical properties. B CKGROUND QF THE INVENTION Fabrication of polytetrafluoroethylene (PTFE) and some copolymers of tetrafluoroethylene, including those containing particulate carbon and other materials, is often difficult, due to the fact that even above their melting points they flow little if at all. Thus, typical plastics melt processing techniques are often useless with such polymers. Previous attempts have been made by others to make these polymers more processible, in order to make useable parts. It is well known in the art to use particulate carbon to improve the physical properties of polymers and polymer parts, and to impart electrical conductivity to such polymers and parts. Thus U.S. Patent 2,685,707 and J. F. Lontz, et al., Ind. Eng. Chem., vol. 44. pp. 1805-1810 report that many low molecular weight organic compounds such as hydrocarbons and esters can be used as "lubricants" to aid in the forming of parts from particulate PTFE. The lubricants are removed typically by volatilization and/or sintering, and a solid part is produced by sintering the remaining PTFE. " U.S. Patents 3,407,249 and 3,679,614 report that porous PTFE parts are produced by mixing particulate PTFE with poly(methyl methacrylate) (PMMA) and other compounds. The PMMA and other compounds ' can * be removed by use-of solvents for the PMMA such as acetone. U.S. Patents 2,985,918 and 3,054,761 describe a process for making and using a composition comprising PTFE and PMMA. This mixture may be sintered to volatilize and decompose the PMMA, and to sinter the PTFE, so that a porous PTFE article is produced. British Patent 1,390,100 describes a mixture of a polyolefin such -as polyethylene, PTFE and for example carbon black or bronze powder. The polyolefin is believed to act as a processing aid. Japanese Patent Application 49/039642 discloses PTFE containing powdered graphite. Japanese Patent Application 49/11912 discloses a dispersion in water of a mixture of PTFE and conductive carbon, which can be used to make a conductive coating. Japanese Patent Application 58/25368 describes a paste containing, among other items, PTFE aqueous dispersion and an electrically conductive powder such as graphite or carbon black. This too can be used to make electrically conductive coatings. Among the desired properties a material should impart to PTFE in order to help form PTFE parts, are, easy mixing of the components, good green strength of the mixture so parts of the mixture will not deform readily, especially under sintering conditions, and clean sintering of the processing aid (lubricant) so that the remaining PTFE part is free of impurities (e.g., ash and char) and has a minimum amount of porosity. It is the object of this invention to provide such a composition and a process for making and using it. None of the above references teaches the use of poly(2,2-dialkylpropiolactones) as processing aids or lubricants for PTFE. SUMMARY OF THE INVENTION A blend of polymers containing tetrafluoroethylene polymer (TFEP) and selected poly(2,2-dialkylpropio- lactones) (PDAP) and a mixture of such blend with other materials, especially particulate carbon, is provided. Such polymer blends or mixtures are useful for producing moldings and extrusions of TFEP which have improved physical properties and.may be electrically conducting. After a molding or extrusion part is formed, the PDAP may be removed from the part by pyrolysis; the PDAP is readily and cleanly pyrolyzed from the TFE containing polymer or polymer mixture. Also provided is a process for making, and optionally pyrolyzing, the blend and parts thereof. DETAILS OF THE INVENTION This invention provides a polymer blend comprising about 5% to about 50% by weight of a first polymer with repeat units of the formula -(-CH 2 -CR 1 R 2 -C(0)0-)-, and about 95% to about 50% by weight of a tetrafluoro¬ ethylene polymer, wherein R 1 and R 2 are independently chosen alkyl groups, and provided that the total number of carbon atoms in R 1 and R 2 is about 20 or less. This invention also provides a composition comprising about 5% to about 50% by weight of a first polymer with repeat units of the formula -(-CH 2 -CR 1 R 2 -C(0)0-)-, about 95% to about 50% by weight of a tetrafluoroethylene polymer, and about 1% to about 233% by weight of said tetrafluoroethylene polymer of particulate carbon, wherein R 1 and R 2 are independently chosen alkyl groups, and provided that the total number of carbon atoms in R 1 and R 2 is about 20 or less. By the term "tetrafluoroethylene polymer" (herein TFEP) is herein meant a polymer of tetrafluoroethylene in which up to about 20 mole percent of the tetrafluoroethylene monomer may be substituted by other fluorinated monomers. Suitable fluorinated monomers include, but are not limited to, hexafluoropropylene, perfluoro(methyl vinyl ether), vinylidene fluoride and chlorotrifluoroethylene. Polymers of the formula -(-CH 2 -CR 1 R 2 -C(0)0-)- (herein PDAP) are preferably prepared by anionic polymerization (using tetraalkylammonium carboxylates as initiators) of 2,2-dialkylsubstituted -beta-propiolactones as disclosed in . H. Sharkey in Ring Opening Polymerization, J. E. McGrath Ed., ACS Symposium Series 286, American Chemical Society, Washington, D. C, p. 373 and references cited therein. The monomeric beta- propiolactones are prepared by procedures described by D. B. Johns, et al., in Ring-Opening Polymerization, Vol. 1, K. J. Ivin and T. Saegura, Eds., Elsevier Applied Science Publishers, New York, NY 1984, Chap. 7. In addition to the polymerization of 2,2-dialkyl- substituted-beta-propiolactones, the polymers of this invention can also be produced by the polymerization of the cyclic carbonate of 2,2-dialkyl-substituted-3- hydroxypropionic acid, or of the free hydroxy acid itself. Such polymers are often referred to as poly(2,2- dialkylpropiolactones) . In preferred PDAPs, R 1 and R 2 contain about 10 carbon atoms or less. In an especially preferred PDAP R 1 is methyl and R 2 is n-propyl. It is also preferred if the PDAP has a melting point below about 200°C. The molecular weight of the PDAP should not be too high or too low. The degree of polymerization should be at least about 70 to provide sufficient green strength to the blend. Although no upper limit is known for the PDAP molecular weight, very high degrees of polymerization (>10,000) will unnecessarily increase the viscosity of the (melted) blends. A preferred degree of polymerization range for the PDAP is about 100 to about 5,000. In preferred blends the PDAP is about 10% to about 30% by weight and the TFEP is about 90% to about 70% by weight. " In especially preferred blends the PDAP is about 15% to about 25% by weight and the TFEP is about 85% to about 75% by weight. These blends and mixtures are useful as molding resins which have high green strength and (for those that contain conductive carbon) are electrically conductive. The electrical conductivity makes these compositions especially useful in electrical applications, such as for shielding electric and magnetic fields, and for parts where conductivity is an advantage, as to form an electrical ground. It is well known in the art that many TFEPs (including their PC containing compositions) are difficult to process, exhibiting very high melting points, and even above their melting points, have very poor flow characteristics. These blends and mixtures allow the processing of TFEPs into useful objects by methods such as extrusion and injection.molding (infra). .In addition, if desired, the PDAP in the mixture is easily and cleanly pyrolyzed from the mixture to give objects (infra) containing TFEP as the sole polymer. The mixtures may be made by the processes described below. Other materials commonly present in or added to the polymers may also be present, such as, but not limited to fillers and reinforcing agents such as "particulate carbon" (PC), pigments and antioxidants, as long as the above proportions of TFEP and PDAP are maintained. Where PC is added, up to 20% by weight (of the TFEP and PC combined) of the other materials, such as fillers, pigments and antioxidants, as long as the above proportions of TFEP, PDAP and PC are maintained. By the term "particulate carbon" (PC) is meant herein the types of carbon, usually in the form of small particles or fibers, that are typically used as fillers and/or reinforcing agents for polymers. Such materials include, but are not limited to, carbon black, acetylene black, powdered graphite and carbon fibers. An especially preferred form of particulate carbon is one that is "conductive carbon". By the term "conductive carbon" herein is meant small particles of carbon that are electrically conducting. Such materials include, but are not limited to, selected carbon blacks, powdered graphite and carbon fibers (CF) . Carbon fibers are the preferred form of particulate carbon. Especially preferred are carbon fibers, or fragments thereof, described in Claim 1 of U.S. Patent 4,861,653 as follows: "1. A bat of randomly disposed carbon fibers, said fibers predominantly having in cross- section a width of less than about 12 micrometers and a fracture surface exhibiting a lamellar microstructure composed of lamellae arranged in an isoclinic relationship and * disposed in a direction generally parallel to an axis of the fiber cross-section, the - lamellae extending to the periphery of the fiber cross-sections." These and other especially preferred carbon fibers have a lamellar microstructure and a distribution of diameters from about 1 micrometer to more than 10 micrometers, with a number average diameter of about 8 micrometers, and are electrically conducting. These fibers are heat treated in an inert atmosphere to above 1600°C, more preferably 2400°C. It is preferred if the amount of PC present is about 5% to about 100% by weight of the TFEP, most preferably about 10% to about 67% by weight of the TFEP present. The calculation of the amount of PC in the mixture is based on the amount of TFEP in the mixture. For example, 233% PC in the mixture means that there is 2.33 times the amount of PC than TFEP, and 1% PC means there is 0.01 times the amount of PC in the mixture as TFEP. Also provided in this invention is a process of making polymeric parts, comprising: (a) mixing about 5% to about 50% by weight of a first polymer with repeat units of the formula -(-CH2-CR 1 R 2 -C(0)0-)-, with about 95% to about 50% by weight of a tetrafluoroethylene polymer, wherein R 1 and R 2 are independently chosen alkyl groups, and provided that the total number of carbon atoms in R 1 and R 2 is about 20 or less, to form a blend; (b) melt blending said blend at a temperature above the glass transition temperature and melting point of said first polymer but below about 270°C; and (c) forming said blend into a shaped part. The definition of the tetrafluoroethylene polymer is as given above. Preferred PDAPs and preferred proportions of TFEP and PDAP are as enumerated above. Mixing of the polymers may be accomplished in several ways. For example, simple dry powder blending may be used, although care should be exercised to obtain a uniform blend. A preferred mixing method is to dissolve the PDAP in a solvent such as methylene chloride, and adding this solution to an agitated slurry of the TFEP . The liquid used to make the slurry of TFEP should be miscible with the solvent for the PDAP, but should be a nonsolvent for the PDAP. While the resulting slurry is agitated, the solvents are evaporated to give a blend of the polymers. It has been found that some types of TFEP "powders" give blends -that are agglomerated at this point. They may be rendered into a more useful form (powders) by grinding, as with a mortar and pestle, a ball mill or a hammer mill. Certain types of PC, such as carbon fibers, may be degraded by grinding; they may be added by drying powder ' blending after the grinding operation. It has been found that so-called "granular TFEPs" give blends that are powders (or granular) at this point without the need for grinding. Such granular TFEPs are preferred and may be made by the processes described in: U.S. Patent 2,936,301; or U.S. Patent 3,766,133 followed*by deagglomeration in a mechanical mill. Such polymers are also described by American Society for Testing Material Specification D-4894-89, Type 3 Grade 1 and Type 2. The melt blending of the blend or mixture may be accomplished by a variety of methods known to those skilled in the art of polymer processing. For example, compression molding, that is applying pressure and heat in a hydraulic press may be used. A preferred method is a screw melter, such as in a screw extruder. This provides good mixing to provide a uniform mixture. The melt blending should be carried out at a temperature high enough to melt the PDAP, above its melting point, or if the polymer is not crystalline, above its glass transition temperature. The temperature should be kept below about 270°C to avoid decomposition of the PDAP and/or gross separation of the PDAP and the TFEP. After the mixture is melt blended the product may be pelletized in conventional ways for further processing into a shaped part, or may be formed directly from the melted state into a shaped part as by compression molding, extrusion through a die and injection molding. Further processing into a shaped part at a later time could also be by these methods, although melting of the PDAP may not be necessary to form a shaped part. For example, moderate heat and high pressure may cause the blend to flow by plastic deformation into a shaped part. However a melt process is preferred to form the shaped part . After the shaped part is formed, it may be used as is, having the "composite" properties of the blend's or the mixture's constituents. However, in order to improve certain properties such as solvent, chemical and high temperature resistance, it may be desirable to remove the PDAP so that essentially pure TFEP (plus any other nonvolatile ingredients such as filler and pigments) remains. This can be accomplished by the optional additional step of pyrolysis of a shaped part of the blend. This comprises the additional step of pyrolyzing the shaped -part from 275°C to about 400°C, preferably about 300°C to about 350°C until the PDAP is converted to volatile products. The pyrolysis may be carried out in air, or in an inert atmosphere such as nitrogen. Air is preferred. As is known to those skilled in the art, pyrolyses such as these may cause porosity in the resulting TFEP part. This porosity may be minimized by raising the temperature of the shaped part slowly as the decomposition point of the PDAP (>275°C) is approached and passed. Porosity that occurs may be reduced by densifying the pyrolyzed part. Densifying the part may be done by heating the part at about 350°C to about 400°C for an additional period after pyrolysis is completed. Such procedures are known in the art. It is also known in the art that the properties of the resulting pyrolyzed part may be affected by the manner in which the part is cooled after the pyrolysis or densification. The following Examples illustrate the invention. In these Examples various grades of Teflon Fluorocarbon Resin (Trademark of and available from E. I. du Pont de Nemours & Co., Inc., Wilmington, DE) are used. These grades, except as noted, are homopolymers of tetrafluoroethylene, and are so-called granular materials. Melt Index tests were performed according to ASTM D-1238 using a 15 kg weight, and except where noted were done at 200°C. Tensile strength (TS) , tensile modulus (TM) and percent tensile elongation to break (EB) were measured on an Instron tester at a crosshead speed of 2.54 cm/min at about 25°C, except where otherwise noted. By green strength is meant the properties of unpyrolyzed blend. Injection molding was done on a one-ounce (28 g) ram injection molding machine with a barrel temperature of 150°C, using a 3.2 x 12.7 x 127 mm flex bar mold. In all of the Examples, PDAP refers to poly(2-methyl-2-n-propylpropiolactone) . Ratios of components of mixtures of blends with carbon are by weight. EXAMPLE ~ Enough methanol was added to 80 g of Teflon 7A so that the Teflon was barely covered. To this was added over a period of 30 to 60 min one-quarter of a solution of 80 g of PDAP in methylene chloride. The Teflon slurry was agitated while the PDAP solution was being added. The slurry was agitated while the solvent was then evaporated with a stream of nitrogen. A fine powder was obtained. EXAMPLES 2-11 Using procedures similar to that in Example 1, various blends of Teflon with PDAP were prepared. The ratios of PDAP to Teflon were varied by adjusting the amounts of PDAP solution and Teflon used. These mixtures, and some of their melt indicies, are given in Table 1. The melt index tests produced rods approximately 2 mm in diameter which were further tested (see Example 12) . This Example illustrates pyrolyzing (sintering) of the polymer blends. Rods " from Examples 2, 6, and 7 (all contain 20% PDAP) were combined and used in this Example. These rods were heated in a furnace to 275°C at a rate of 2°C/min in an air atmosphere, and held at that temperature for 3 hr. The temperature was then raised to 380°C at a rate of l°C/min, and then held at 380°C for 3 hr. The recovered rods showed a loss of weight of 19.2 +/- 0.27% (9 samples), shrinkage .in the machine direction of 31.0 +/- 3.0% (6 samples), and little or no change in the transverse direction. Different rods were also pyrolyzed at 325°C in air by putting them into a furnace that was at 325°C. The rods turned brown in about * 5 min, and then appeared to be a black chary material after 10 min (total) . The color started to fade in 2-3 hr and white materials were obtained in 4 to 70 hr. The samples, which were not pyrolyzed completely,- had black spots all over, but especially at the surface. Physical properties of green (unpyrolyzed) rods, and the rods pyrolyzed at 380°C and 325°C are given in Table 2. *Crosshead speed 0.51 cm/min, EXAMPLE 13 By a procedure similar to that in Example 1, 200 g of a blend of PDAP (20%) and Teflon 7A (80%) was prepared. The sample was injection molded to form flex bars. Strips about 10 microns thick were cut along the machine direction from these bars. Some strips were placed in an oven at 325°C or 345°C under an air atmosphere. At 325°C the strips pyrolyzed cleanly in 12 hr. At 345°C the strips had pyrolyzed cleanly in less than 6 hr, but some strip edges had fibrillated. Good intact pyrolyzed strips were obtained at 325°C, these strips having shrunk about 30% in the machine direction. The physical properties of green (unpyrolyzed) strips and strips pyrolyzed at 325°C are given in Table 3. TABLE 3 Unpyrp-.yze'-- Pyrolyzed TS (psi) 1284 + 167 1887 + 101 TM (Kpsi) 26.1 ± 3.7 40.6 ± 2.7 EB (%) 32.2 ± 12.4 43.2 ± 9.0 EXAMPLE 14 To 270 g of Teflon 7A suspended in 500 ml of methanol was added a solution of 91.3 g of PDAP (inherent viscosity 0.32 in methylene chloride. The Teflon slurry was stirred vigorously as the PDAP solution was added over about 10 min. The slurry was agitated while the solvent was evaporated with a stream of nitrogen. A white powdery material weighing 357.7 g was obtained. The polymer blend was passed through an 80 mesh sieve, and then 15 g of the sieved powder was mixed with 10 g of chopped carbon fiber (as described in U.S. Patent 4,861,653, claim 1), and mixed on a roller mixer for 24 hr. This gives a mixture with 83% (of the amount of Teflon present) carbon fiber. Another mixture containing 31% (of the amount of Teflon present) carbon fiber, and 20 weight percent of PDAP (based on the total of the PDAP and Teflon present) was similarly produced. The mixtures were extruded from a capillary rheometer at temperatures between 120°C and 180°C to form rods. The viscosity dropped as the temperature increased. The flow characteristics at 150°C are given in Table 4. The physical properties of the extrudates, measured at 25°C, are given in Table 5. TS (psi) TM (Kpsi) EB (%) The rods were heated at 325°C for 24 to 60 hr in air in order to pyrolyze the PDAP. The weight and dimensional changes, and physical properties are summarized in Table 6. TABLE ~ % Carbon Fiber 31 83 Weight before pyrolyzing 1.1383 g 0.6428 g Weight after pyrolyzing 0.9234 g 0.5468 g Length before pyrolyzing 152.5 cm 82.5 cm Length after pyrolyzing 132.5 cm 67.3 cm TS (psi) 2600 ± 90 1700 ± 120 TM (Kpsi) 57 ± 12 27 + 4 EB (%) 30 + 5 24 + 6 The conductivities were measured by the four point measurement method using 1 to 30 microampere current. They are: As extruded: 31% carbon fiber nonconducting 83% carbon fiber 2.76xl0 -3 ohirT-icrrr 1 After heating (pyrolyzing) : 31% carbon fiber 1.94xl0 -2 ohm^cm -1 83% carbon fiber 1.17xl0 -2 ohm- 1 -1 Although preferred embodiments of the invention have been described hereinabove, it is to be understood that there is no intention to limit the invention to the precise constructions herein disclosed, and it is to be further understood that the right is reserved to all changes coming within the scope of the invention as defined by the appended claims.

Claims: CLAIMS 1. A polymer blend, comprising, about 5% to about 50% by weight of a first polymer with repeat units of the formula -(-CH 2 -CR 1 R 2 -C(O)O-)-, and about 95% to about 50% by weight- of a tetrafluoroethylene polymer, wherein R 1 and R 2 are independently chosen alkyl groups, and provided that the total number of carbon atoms in R 1 and R 2 is about 20 or less. 2. The composition of Claim 1 wherein there is added from about 1 % to about 233% by weight of said tetrafluoroethylene polymer of particulate carbon. 3. The composition as recited in Claim 2 wherein the said particulate carbon is a conductive carbon. 4. A composition as recited in Claim 1 or Claim 3 wherein said first polymer is present from about 10% to about 30% by weight, and said tetrafluoroethylene polymer is present from about 90% to about 70% by weight. 5. A composition as recited in Claim 4 wherein said first polymer is present from about 15% to about 25% by weight, and said tetrafluoroethylene polymer is present from about 85% to about 75% by weight. 6. A composition as recited in Claim 1 or Claim 3 wherein said total number of carbon atoms in said R 1 and R 2 is 10 or less. 7. The composition as recited in Claim 4 or Claim 6 wherein said R 1 is methyl and said R 2 is n-propyl. 8. The composition as recited in Claim 1, Claim 3 or Claim 5 wherein said first polymer has a melting point of about 200°C or less. 9. The composition as recited in Claim 1 or Claim 3 wherein said first polymer has a degree of polymerization of about 70 to about 20,000. 10. The composition as recited in Claim 9 wherein said first polymer has a degree of polymerization of about 100 to about 5,000. 11. The composition ' as recited in Claim 3 or Claim 7 wherein said conductive carbon is present from about 5% to about 100% by weight of said polytetrafluoroethylene ■ polymer. 12. The composition as recited in Claim.11 wherein said conductive carbon is present from about 10% to about 67% by weight of said polytetrafluoroethylene * polymer. 13. The composition as recited in Claim 3, Claim 5 or Clai -12 wherein said conductive carbon is carbon fiber. 14. The composition as recited in Claim 13 wherein the conductive carbon is carbon fiber or fragments thereof in the form of w a bat of randomly disposed carbon fibers, said fibers predominantly having in cross- section a width of less than about 12 micrometers and a fracture surface exhibiting a lamellar microstructure composed of lamellae arranged in an isoclinic relationship and disposed in a direction generally parallel to an axis of the fiber cross-section, the lamellae extending to the periphery of the fiber cross-sections". 15. A process of making polymeric parts, comprising: (a) mixing about 5% to about 50% by weight of a first polymer with repeat units of the formula -(-CH2-CR 1 R 2 -C(0)0-)-, with about 95% to about 50% by weight of a tetrafluoroethylene polymer, wherein R 1 and R 2 are independently chosen alkyl groups, and provided that the total number of carbon atoms in R 1 and R 2 is about 20 or less, to form a blend; (b) melt blending said blend at a temperature above the glass transition temperature and melting point of said first polymer but below about 270°C; and (c) forming said blend into a shaped part. 16. A process as recited in Claim 15 wherein said first polymer is present from about 10% to about 30% by weight, and said tetrafluoroethylene polymer is present from about 90% to about 70% by weight. 17. A process as recited in Claim 16 wherein said * first polymer is present from about 15% to about 25% by weight, and said tetrafluoroethylene polymer is present from about 85% to about 75% by weight. 18. A process as recited in Claim 15 wherein said total number of carbon atoms in said R 1 and R 2 is 10 or less. 19. The process as recited in Claim 15, Claim 16 or or Claim 17 wherein said R 1 is methyl and said R 2 is n- propyl. 20. The process as recited in Claim 15, Claim 16 or Claim 17 wherein said first polymer has a melting point of about 200°C or less'. 21. The process as recited in Claim 15 wherein said first polymer has a degree of polymerization of about 70 to about 5,000. 22. The process as recited in Claim 15 wherein said • forming is done by melt forming. 23. The process as recited in Claim 22 wherein said melt blending is done by a screw melter. 24. The process as recited in Claim 22 wherein said melt forming is done by a process selected from compression molding, extrusion through a die and injection molding. 25. The process as recited in Claim 15 or Claim 19 further comprising pyrolyzing said shaped part at a temperature from about 275°C to about 400°C, until said first polymer is volatilized. 26. The process as recited in Claim 25 wherein said pyrolysis is carried out at about 300°C to about 350°C. 27. The process as recited in Claim 15 or Claim 19 wherein said mixing is carried out by steps, comprising: (a) dissolving said first polymer in a solvent to form a solution; (b) slurrying said polytetrafluoroethylene polymer in a nonsolvent for said first polymer to form a slurry; (c) while agitating said slurry, adding said solution to said slurry; and (d) evaporating said solvent and said nonsolvent . 28. The process as recited in Claim 27 wherein said polytetrafluoroethylene polymer is a granular material. 29. The process as recited in Claim 15 or Claim 18 wherein said mixing is done by dry powder blending.

Inventors: KIM YOUNG HWAN, KIM, YOUNG, HWAN
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1991
Main classification: C08L27
IPC codes: B29C43, B29C45, B29C47, B29K27, C08J5, C08J9, C08K3, C08K7, C08L27, C08L87