EP1068248A1 - Perfluoroelastomer compositions - Google Patents

Perfluoroelastomer compositions

Info

Publication number
EP1068248A1
EP1068248A1 EP99908238A EP99908238A EP1068248A1 EP 1068248 A1 EP1068248 A1 EP 1068248A1 EP 99908238 A EP99908238 A EP 99908238A EP 99908238 A EP99908238 A EP 99908238A EP 1068248 A1 EP1068248 A1 EP 1068248A1
Authority
EP
European Patent Office
Prior art keywords
cure
peroxide
vinyl ether
perfluoroelastomer
site component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99908238A
Other languages
German (de)
English (en)
French (fr)
Inventor
Werner M. Grootaert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dyneon LLC
Original Assignee
Dyneon LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dyneon LLC filed Critical Dyneon LLC
Publication of EP1068248A1 publication Critical patent/EP1068248A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • This invention relates to peroxide-curable perfluoroelastomer compositions which have excellent processability, and which when cured, have excellent physical properties.
  • Perfluoroelastomers are polymeric materials which exhibit outstanding high temperature tolerance and chemical resistance. Consequently, such compositions are particularly adapted for use as seals and gaskets in systems in which elevated temperatures and/or corrosive chemicals are encountered. They are useful in industries such as, chemical processing, semiconductor, aerospace, petroleum, etc.
  • perfluoropolymers are largely attributable to the stability and inertness of the copolymerized perfluorinated monomer units which make up the major portion of the polymer backbone, e.g., tetrafluoroethylene and perfluoro(alkyl vinyl) ethers.
  • perfluoropolymers are typically crosslinked, i.e. vulcanized.
  • a small percentage of a cure site monomer is copolymerized with the perfluorinated monomer units.
  • Cure site monomers containing at least one bromo or iodo group are known. Such cure site monomers, when combined with a peroxide and a coagent, will provide a suitably cured composition.
  • Perfluoroelastomers are very expensive materials, and therefore are only used in situations where no other material will do the job. In view of the very high raw material costs, scrap rates during the molding operation must be kept to a minimum.
  • perfluoroelastomers are known to be very difficult to process with respect to compounding, flow characteristics and mold release.
  • conventional initiators are used to produce the polymers (e.g., persulfates) the polymeric end groups are typically of an ionic and/or acidic nature. These ionizable polymer end-groups, that are normally present, are prone to undesirable reactions with some commonly used additives, (e.g., acid acceptors).
  • acid acceptors are zinc oxide, calcium hydroxide, calcium carbonate, magnesium oxide, etc. They are used in the compound formulation to bind any HF or other acids that might be generated at the high temperatures where perfluoroelastomers must function. Perfluoroelastomer compounds that show very good processing characteristics are much desired. Because many applications for these polymers also require good sealing capabilities, the steps to improve processability are preferrably not detrimental to critical physical properties such as compression set resistance.
  • the perfluoroelastomers compounds of this invention employ a perfluoroelastomer that is prepared using an initiator combination of an oxidizer and a perfluoroalkyl sulfinate of type RfSO 2 Na.
  • the copolymers prepared in this manner surprisingly can be processed like other elastomer gums. They are easy to process on conventional 2 roll mills, or mixing devices, i.e. the mills or mixing devices need not be heated above room temperature. Their compound viscosity does not increase when acid acceptors, such as Ca(OH) , are added.
  • the perfluoroelastomers also show improved physical properties (e.g. compression set resistance).
  • One embodiment of the invention provides a peroxide curable perfluoroelastomer compound that is easily processable and is essentially free of ionizable end groups.
  • essentially free of such groups it is meant that less than 10% of these end groups are ionizable groups.
  • the compound of this embodiment comprises:
  • the invention provides a peroxide curable perfluoroelastomer compound that is easily processable comprising:
  • the present invention also provides a method for improving the processability of perfluoroelastomers, comprising: polymerizing, under free-radical conditions, an aqueous emulsion or suspension of a polymerizable mixture comprising a perfluoroolefin and a perfluoroalkyl vinyl ether or a perfluoroalkoxy vinyl ether and mixtures thereof, a halogen-containing cure-site component capable of participation in a peroxide cure reaction, a fluoroaliphatic-radical containing sulfinate, and an oxidizing agent capable of oxidizing said sulfinate to a sulfonyl radical, with the proviso that the cure site component contains substantially no nitrile groups.
  • the present invention also provides a method for improving the processability of perfluoroelastomers, comprising: polymerizing, under free-radical conditions, an aqueous emulsion or suspension of a polymerizable mixture comprising a perfluoroolefin and a perfluoroalkyl vinyl ether or a perfluoroalkoxy vinyl ether and mixtures thereof, a bromine- or iodine-containing cure-site component, a fluoroaliphatic-radical containing sulfinate, and an oxidizing agent capable of oxidizing said sulfinate to a sulfonyl radical.
  • the invention further relates to cured and uncured articles made from such curable compounds. DETAILED DESCRIPTION
  • compositions of the present invention comprise peroxide curable perfluoroelastomers which are characterized by improved processability and less reactivity to bases.
  • These compositions comprise a) a perfluoroelastomer having copolymerized units of a perfluoroolefin, a perfiuorovinyl ether and a cure site component having at least one bromine- or iodine-containing moiety, and b) a compound which acts as a curative for the perfluoroelastomer.
  • the perfluoroelastomers are substantially free of ionizable end groups, such as those reactive with bases. This does not preclude the presence of cure sites in the perfluoroelastomers needed for crosslinking.
  • Suitable perfluorinated olefins useful in the invention include tetrafluoroethylene and hexafluoropropylene.
  • perfluoro(alkyl vinyl) ethers are those wherein n is 0 or 1 and Rf contains 1-3 carbon atoms.
  • perfluorinated ethers include perfluoro(methyl vinyl) ether, perfluoro(ethyl vinyl) ether, and perfluoro(propyl vinyl) ether.
  • Other useful monomers include compounds of the formula
  • CF 2 CFOCF 2 OCF 2 CF 2 CF 3
  • CF 2 CFOCF 2 CF 3
  • CF 2 CFO(CF 2 ) 3 OCF 3
  • CF 2 CFOCF 2 CF 2 OCF 3 .
  • Mixtures of perfluoro(alkyl vinyl) ethers and perfluoro(alkoxy vinyl) ethers may also be used.
  • Preferred copolymers are composed of tetrafluoroethylene and at least one perfluoro(alkyl vinyl) ether as principal monomer units.
  • the copolymerized perfluorinated ether units constitute from about 15-50 mole percent of total monomer units in the polymer.
  • the cure site component used in the present invention is a halogen containing material that is capable of participation in a peroxide cure reaction.
  • the halogen is bromine or iodine.
  • Suitable cure-site components include terminally unsaturated monoolefins of 2 to 4 carbon atoms such as bromodifluoroefhylene, bromotrifluoroethylene, iodotrifluoroethylene, and
  • CF 2 CFOCF 2 CF2CF 2 OCF 2 CF 2 Br.
  • all or essentially all of these components are ethylenically unsaturated monomers.
  • Other useful cure-site components are brominated or iodinated chain transfer agents and initiators. Examples of useful chain transfer agents include perfluoroalkyl bromides or iodides. Examples of useful initiators include
  • Suitable peroxide curatives for use in the invention are those which generate free radicals at curing temperatures.
  • a dialkyl peroxide or a bis(dialkyl peroxide) which decomposes at a temperature above 50° C is especially preferred.
  • a di-tertiarybutyl peroxide having a tertiary carbon atom attached to peroxy oxygen is particularly preferred.
  • the most useful peroxides of this type are 2,5-dimethyl-2,5- di(tertiarybutylperoxy)hexyne-3 and 2,5-dimethyl-2,5- di(tertiarybutylperoxy)hexane.
  • peroxides can be selected from such compounds as dicumyl peroxide, dibenzoyl peroxide, tertiarybutyl perbenzoate, ⁇ , ⁇ '-bis(t-butylperoxy-diisopropylbenzene), and di[l,3-dimethyl-3-(t- butylperoxy)-butyl]carbonate.
  • dicumyl peroxide dibenzoyl peroxide
  • tertiarybutyl perbenzoate ⁇ , ⁇ '-bis(t-butylperoxy-diisopropylbenzene
  • di[l,3-dimethyl-3-(t- butylperoxy)-butyl]carbonate Generally, about 1-3 parts of peroxide per 100 parts of perfluoroelastomer is used.
  • Another material which is usually blended with the composition as a part of the curative system is a coagent composed of a polyunsaturated compound which is capable of cooperating with the peroxide to provide a useful cure.
  • These coagents can be added in an amount equal to 0.1 and 10 parts per hundred parts perfluoroelastomer, preferably between 2-5 parts per hundred parts perfluoroelastomer.
  • Examples of useful coagents include triallyl cyanurate; triallyl isocyanurate; tri(methylallyl isocyanurate; tris(diallylamine)-s- triazine; triallyl phosphite; N,N-diallyl acrylamide; hexaallyl phosphoramide; N,N,N',N'- tetraalkyl tetraphthalamide; N,N,N',N'- tetraallyl malonamide; trivinyl isocyanurate; 2,4,6- trivinyl methyltrisiloxane; and tri(5-norbornene-2-methylene)cyanurate. Particularly useful is triallyl isocyanurate.
  • additives include the bis-olefins disclosed in EPA 0 661 304 Al, EPA 0 784 064 Al and EPA 0 769 521 Al.
  • Additives such as carbon black, stabilizers, plasticizers, lubricants, fillers, and processing aids typically utilized in perfluoroelastomer compounding can be incorporated into the compositions of the present invention, provided they have adequate stability for the intended service conditions. In particular, low temperature performance can be enhanced by incorporation of perfluoropolyethers (cf.U.S. Pat No. 5,268,405).
  • Carbon black fillers are used in elastomers as a means to balance modulus, tensile strength, elongation, hardness, abrasion resistance, conductivity, and processability of the compositions. Suitable examples include MT blacks (medium thermal black) designated N-991, N-990, N-908, and N-907, and large particle size furnace blacks. When used, 1-70 phr of large size particle black is generally sufficient. In addition, fluoropolymer fillers may also be present in the composition.
  • the fluoropolymer filler can be finely divided, easily dispersed plastic fluoropolymer that is solid at the highest temperature utilized in fabrication and curing of the perfluoroelastomer composition.
  • solid it is meant that the fluoroplastic, if partially crystalline, will have a crystalline melting temperature above the processing temperature(s) of the perfluoroelastomer(s).
  • micropowders are commonly called micropowders or fluoroadditives. Micropowders are ordinarily partially crystalline polymers.
  • the method of this invention comprises the use of perfluorosulfinate and an oxidizing agent in a free-radical polymerization process.
  • the polymerization process includes free-radical polymerization of monomers alone or as solutions, emulsions, or dispersions in an organic solvent or water. Polymerization in an aqueous emulsion or suspension is often preferred because of the rapid and nearly complete conversion of monomers, easy removal of the heat of polymerization, and ready isolation of the polymer.
  • Emulsion or suspension polymerization typically involves polymerizing monomers in an aqueous medium in the presence of an inorganic free-radical initiator system and surfactant or suspending agent.
  • Aqueous emulsion polymerization can be carried out continuously under steady- state conditions in which, for example, monomers, water, surfactants, buffers and catalysts are fed continuously to a stirred reactor under optimum pressure and temperature conditions while the resulting emulsion or suspension is removed continuously.
  • An alternative technique is batch or semibatch polymerization by feeding the ingredients into a stirred reactor and allowing them to react at a set temperature for a specified length of time or by charging ingredients into the reactor and feeding the monomer into the reactor to maintain a constant pressure until a desired amount of polymer is formed.
  • R 3 f represents a monovalent fluoroaliphatic radical having, for example, from 1 to 20 carbon atoms, preferably 4 to 10 carbon atoms
  • R 2 f represents a polyvalent, preferably divalent, fluoroaliphatic radical having, for example, from 1 to 20 carbon atoms, preferably from 2 to 10 carbon atoms
  • M represents a hydrogen atom or cation with valence x, which is 1 to 2, and is preferably 1
  • n is 1 to 4, preferably 1 or 2.
  • R 3 f is a fluorinated, stable, inert, non- polar, saturated moiety. It can be straight chain, branched chain, and, if sufficiently large, cyclic, or combinations thereof, such as alkyl cycloaliphatic radicals. Generally, R 3 f will have 1 to 20 carbon atoms, preferably 4 to 10, and will contain 40 to 83 weight percent, preferably 50 to 78 weight percent fluorine. The preferred compounds are those in which the R 3 group is fully or substantially completely fluorinated, as in the case where R 3 f is perfluoroalkyl, C n F 2n+ ⁇ , where n is 1 to 20.
  • R 2 f is a fluorinated, stable, inert, non-polar, saturated moiety. It can be straight chain, branched chain, and, if sufficiently large, cyclic or combinations thereof, such as alkylcycloaliphatic diradicals. Generally, R 2 f will have 1 to 20 carbon atoms, preferably 2 to 10. The preferred compounds are those in which the R 2 f group is perfluoroalkylene, C n F 2n , where n is 1 to 20, or perfluorocycloalkyl, C n F 2n , where n is 5 to 20.
  • the skeletal chain of carbon atoms can be interrupted by divalent oxygen, hexavalent sulfur or trivalent nitrogen hetero atoms, each of which is bonded only to carbon atoms, but preferably where such hetero atoms are present, such skeletal chain does not contain more than one said hetero atom for every two carbon atoms.
  • An occasional carbon-bonded hydrogen atom, iodine, bromine, or chlorine atom may be present; where present, however, they preferably are present not more than one for every two carbon atoms in the chain.
  • R 3 f or R 2 f is or contains a cyclic structure, such structure preferably has 6 ring member atoms, 1 or 2 of which can be said hetero atoms, e.g., oxygen and/or nitrogen.
  • R 3 radicals are fluorinated alkyl, e.g., C4F9--, C 6 F 1 -, C 8 F 17 -, alkoxyalkyl, e.g., C 3 F 7 OCF 2 -.
  • R 2 f are fluorinated alkylene, e.g., ⁇ C Fg— , — C 8 F 16 ⁇ .
  • R 3 f is designated as a specific radical, e.g., C 8 F ⁇ 7 ⁇ , it should be understood that this radical can represent an average structure of a mixture, e.g., CgF ⁇ -- to CI Q F 2 I--, which mixture can also include branched structures.
  • fluoroaliphatic sulfinate compounds useful in the method of this invention include the following: CF 3 SO 2 Na
  • Combinations of monosulfinates, disulfinates, and trisulfinates can be used, depending on whether it is desired to use sulfinate as an initiator, a monomer, or both.
  • polyvalent sulfinates such as those represented by Formula VII
  • the sulfinate is a monomer and the fluorinated moiety is incorporated into the polymer backbone.
  • monosulfinates When monosulfinates are used the fluorinated moiety is incorporated as a polymer end group.
  • the amount of fluoroaliphatic sulfinate used in the method(s) of the invention can vary, depending, for example, on the molecular weight of polymer desired.
  • the amount of fluoroaliphatic sulfinate is from 0.01 to 50 mole %, and most preferably from 0.05 to 10 mole %, of sulfinate compound based on total quantity of monomers.
  • other reducing agents can be present, such as sodium, potassium or ammonium sulfites, bisulfite, metabisulfite, hyposulfite, thiosulfite, phosphite, sodium or potassium formaldehyde sulfoxylate or hypophosphite.
  • Activators such as ferrous, cuprous, and silver salts, may also be present.
  • the oxidizing agent used in the method of the invention is water soluble and is capable of converting the sulfinate to a sulfonyl moiety.
  • the sulfonyl radical produced in the method of the invention is believed to eliminate SO 2 and form a fluorinated radical that initiates the polymerization of the ethylenically unsaturated monomers.
  • useful oxidizing agents are known as taught in U.S. Patent 5,285,002.
  • Representative examples of such useful oxidizing agents are sodium, potassium, and ammonium persulfates, perphosphates, perborates, percarbonates, bromates, chlorates and hypochlorites.
  • Other useful oxidizing agents include cerium IV compounds such as (NH 4 ) 2 Ce(NO 3 )g. It is understood that this list of oxidizing agents is exemplary only.
  • oxidizing agents useful in the invention based upon this disclosure.
  • the amount of oxidizing agent used can vary depending on the particular oxidizing agent and sulfinate employed. Typically an equimolar amount or less (based on the amount of sulfinate) is used.
  • the curable compositions of the present invention may be prepared by mixing a perfluoroelastomer, a peroxide curative, and other additives in conventional rubber processing equipment.
  • Such equipment includes rubber mills, internal mixers, such as
  • compositions containing perfluoroelastomer Prior to the present invention, it was difficult to prepare compositions containing perfluoroelastomer. Typically the compositions required the use of heated processing equipment to keep the compositions from forming crumbly masses.
  • the perfluoroelastomer compounds of this invention do not require the use of heated rolls or processing equipment during compounding. They can be prepared at ambient temperatures without forming a crumbly mass. The substantial lack of reactive end groups
  • the curable compositions of the present invention are useful in production of articles such as gaskets, tubing, and seals. Such articles are produced by molding a compounded formulation of the curable composition with various additives under pressure, curing the part, and then subjecting it to a post cure cycle. During the molding step, the perfluoroelastomers of the invention demonstrate an additional advantage. Lower viscosity is evidenced by faster mold filling or the lower pressures required. Improved mold release is apparent when removing the press cured part or injection molded part from the mold.
  • the cured compositions have excellent thermal stability and chemical resistance. They are particularly useful in applications such as seals and gaskets for manufacturing semiconductor devices, and in seals for high temperature automotive uses.
  • Mooney viscosity was determined by ASTM D 1646-96 (ML 1+10@121°C). Results are reported in Mooney units.
  • Cure Rheology Tests were run on compounded admixtures using a Monsanto Moving Die Rheometer (MDR) Model 2000 in accordance with ASTM D 5289-95 at 177°C, no preheat, 12 minute elapsed time (unless otherwise specified) and a 0.5° arc. Values were obtained for Minimum torque (ML), Maximum torque (MH), i.e., highest torque attained during specified period of time when no plateau or maximum was obtained, were measured. Also reported were: t s 2 (time for torque to increase 2 units above ML), t'50 (time for torque to reach ML + 0.5[MH-ML]), and t'90 (time for torque to reach ML + 0.9[MH-MH]). Torque is reported as deci Newton meters (dNm).
  • Press-cured samples 150 x 150 x 2.0 mm sheets, unless otherwise noted) were prepared for physical property determination by pressing at about 6.9 MegaPascals (MPA) for the indicated amount of time and temperature.
  • MPA MegaPascals
  • Post-cured samples were prepared by placing a press-cured sample in a circulating air oven. The oven was maintained at the indicated temperatures and the samples treated for the indicated amount of time.
  • fluoropolymers were prepared in a manner similar to Example 1 of U.S. Patent No. 5,285,002 except the monomers and other ingredients used are as listed below in gram weight quantities.
  • the monomers used were tetrafluoroethylene (TFE), perfluoromethyl vinyl ether (PMVE) and bromotrifluoroethylene (BTFE).
  • TFE tetrafluoroethylene
  • PMVE perfluoromethyl vinyl ether
  • BTFE bromotrifluoroethylene
  • NH 4 ) 2 S 2 O 8 was identified as APS.
  • the fluorochemical sulfinate (C 4 F 9 SO 2 Na) was prepared as discussed in U.S. Patent No. 5,285,002.
  • the Mooney Viscosity (MLl+10 @ 121° C) of Comparative Polymer A was 76 and for Polymer A was 96.
  • One hundred parts by weight of each polymer gum was compounded by adding 15 parts by weight (phr) N990 carbon black, 5 phr zinc oxide, 1.5 phr LupercoTM 101 XL organic peroxide from Atochem and 2 phr triallylisocyanate-Dry Liquid Concentrate (TAIC-DLC; 72% active), available from Harwick, to each polymer gum.
  • Polymer A was compounded in a conventional manner on a two-roll rubber mill.
  • the Comparative Polymer A had to be compounded on a heated (50-70° C) two-roll mill because it was crumbly and turned powdery if it was compounded in a conventional manner (i.e., using standard or unheated conditions).
  • Table 1 shows the rheological data obtained from the MDR testing.
  • Comparative Compound A showed a significant increase in ML (a measure of compound viscosity) compared to the Compound
  • Polymer A was lower than that of Polymer A, the addition of the fillers, acid acceptors and
  • Comparative Compound A was press cured at 150°C for 10 minutes followed by post curing for 16 hours at 150°C and further post curing for 8 hours at 200°C.
  • Compound A was press cured at 177°C for 10 minutes followed by post curing at 200°C for 20 hours. Attempts to cure and post cure the Comparative Compound A in the same manner as Compound A failed due to warping and formation of fissures in the test sample.
  • Polymer B was prepared in a manner similar to Polymer A except that no BTFE was used, 4 g of APS and 5.4 g C F 9 SO 2 Na were used, and the polymerization was run at 11.6 bar pressure.
  • Comparative Polymer B was prepared in a manner similar to that of Polymer B except that no sulfinate was used, only 1 g of APS was used, and the polymerization was run at 11.0 bar pressure.
  • the Mooney Viscosity (MLl+10 @ 121° C) of Polymer B was 38 and Comparative Polymer B was 73.
  • Comparative Polymer B was milled with 15 phr MT N990 carbon black and 6 phr Ca(OH) 2 . The combiniation of ingredients started to exotherm and formed a crumbly
  • Polymer B was compounded with the same additives as was Comparative Compound B. The combination of ingredients remained as a viscous sheet on the mill and showed less then 1.1 dNm torque rise over 8 minutes on the MDR at 177° C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP99908238A 1998-03-23 1999-02-18 Perfluoroelastomer compositions Withdrawn EP1068248A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US7906198P 1998-03-23 1998-03-23
US79061P 1998-03-23
PCT/US1999/003490 WO1999048939A1 (en) 1998-03-23 1999-02-18 Perfluoroelastomer compositions

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EP1068248A1 true EP1068248A1 (en) 2001-01-17

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EP (1) EP1068248A1 (enExample)
JP (1) JP2002507640A (enExample)
KR (1) KR100612706B1 (enExample)
CN (1) CN100441605C (enExample)
BR (1) BR9908975A (enExample)
CA (1) CA2324954A1 (enExample)
WO (1) WO1999048939A1 (enExample)

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JP2002507640A (ja) 2002-03-12
CA2324954A1 (en) 1999-09-30
WO1999048939A1 (en) 1999-09-30
KR20010034623A (ko) 2001-04-25
KR100612706B1 (ko) 2006-08-16
BR9908975A (pt) 2000-12-05
CN100441605C (zh) 2008-12-10

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