WO2007120122A1 - Composition de fluoropolymere transformable a l'etat fondu contenant des nanoparticules - Google Patents

Composition de fluoropolymere transformable a l'etat fondu contenant des nanoparticules Download PDF

Info

Publication number
WO2007120122A1
WO2007120122A1 PCT/US2006/004179 US2006004179W WO2007120122A1 WO 2007120122 A1 WO2007120122 A1 WO 2007120122A1 US 2006004179 W US2006004179 W US 2006004179W WO 2007120122 A1 WO2007120122 A1 WO 2007120122A1
Authority
WO
WIPO (PCT)
Prior art keywords
fine particles
inorganic fine
melt processible
processible fluoropolymer
melt
Prior art date
Application number
PCT/US2006/004179
Other languages
English (en)
Other versions
WO2007120122A8 (fr
Inventor
Jeong Chang Lee
Original Assignee
Dupont-Mitsui Fluorochemicals Co Ltd.
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
Priority claimed from US11/343,569 external-priority patent/US7495049B2/en
Application filed by Dupont-Mitsui Fluorochemicals Co Ltd. filed Critical Dupont-Mitsui Fluorochemicals Co Ltd.
Priority to EP06850491A priority Critical patent/EP1979405A1/fr
Priority to PCT/US2006/004179 priority patent/WO2007120122A1/fr
Priority to CN2006800520620A priority patent/CN101336269B/zh
Publication of WO2007120122A1 publication Critical patent/WO2007120122A1/fr
Publication of WO2007120122A8 publication Critical patent/WO2007120122A8/fr

Links

Classifications

    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • the present invention relates to melt processible fluoropolymer compositions in which inorganic fine particles are dispersed at the primary particle level. More specifically, the present invention relates to a melt processible fluoropolymer composition obtained by melt-mixing a melt processible fluoropolymer and aggregated inorganic fine particles formed by the cohesive force of the inorganic fine particles, wherein the inorganic fine particles are dispersed in the fluoropolymer at the primary particle level.
  • melt processible fluoropolymers such as tetrafluoroethylene/perfluoro(alkyl vinyl ether) (PFA), tetrafluoroethylene/hexafluoropropylene (FEP), tetrafluoroethylene/ethylene (ETFE), have excellent heat resistance, chemical resistance, and low coefficients of friction.
  • PFA tetrafluoroethylene/perfluoro(alkyl vinyl ether)
  • FEP tetrafluoroethylene/hexafluoropropylene
  • ETFE tetrafluoroethylene/ethylene
  • the published Japanese Patent Application 2001-152030 describes a polymer composition, and the manufacture of the same, characterized by the fact that an additive selected from metals, metal salts, and inorganic compounds or a flame retardant is applied in advance to an inorganic porous body of average particle size 100 nm-1000 nm obtained by sintering an inorganic material such as porous glass or silicon dioxide (hereinafter this may be referred to as silica); this is mixed with a molten polymer so as to pulverize the inorganic porous body, and particles with the aforementioned additive or flame retardant of average particle size 10 nm-100 nm are dispersed in the polymer.
  • the porous glass described in the gazette contains covalently bonded of silicon and oxygen; significant energy is necessary to pulverize and disperse the porous glass. Hence pulverizing and dispersing, porous glass mixing with molten polymer is very difficult.
  • an inorganic porous body of average particle size 100 nm-1000 nm made by sintering aggregated inorganic fine particles comprising silica fine particles of average primary particle size 12 nm at 600°C-700°C only the surface layers fuse slightly and bond with each other due to surface fusion of silica particles (or aggregated silica particles) during sintering, and solidify into a skeleton with firm bonding (Resources and Material, vol 118, p.202, 2002).
  • the average particle size of the inorganic porous body after melt-mixing with polystyrene (PS) is 290 nm
  • the particle size distribution is broad at 40 nm-100,000 nm (100 ⁇ m)
  • pulverizing to the level of the original primary particle is not successful (Papers of the 13th Symposium of High Polymer Materials, p.10, 2003).
  • melt-mixing with polystyrene polymer there is a noticeable deterioration in the dynamic physical properties due to the presence of many sintered aggregates of incompletely pulverized or unpulverized inorganic fine particles of particle size 10 ⁇ m or greater.
  • the dispersed state of the nanofillers varies according to the polarity (hydrophilicity being a measure of polarity: more polar polymer is more hydrophilic; as polymer polarity decreases, the polymer becomes more hydrophobic) of the polymer.
  • polarity hydrophilicity being a measure of polarity: more polar polymer is more hydrophilic; as polymer polarity decreases, the polymer becomes more hydrophobic
  • the present inventors find that by melt-mixing a melt processible fluoropolymer and aggregated inorganic fine particles of low strength formed by the mutual cohesive force of the inorganic fine particles, the aggregated inorganic fine particles are physically pulverized and dispersed at the level of the original inorganic fine particles (which hereinafter may P 1 C " ⁇ V” U S Cl K / 11" 1 H 114 »
  • the present invention provides a melt processible fluoropolymer composition of excellent dynamic physical properties and dimensional stability wherein the inorganic fine particles are dispersed at the level of primary particles.
  • the present invention provides a melt processible fluoropolymer
  • composition dispersed with inorganic fine particles having excellent dynamic physical properties and dimensional stability obtained by melt- mixing a melt processible fluoropolymer and aggregated inorganic fine particles of low strength, wherein the aggregate structure is formed due to the relatively weak mutual cohesive force of the adjacent inorganic fine
  • the present invention provides a melt processible fluoropolymer composition of excellent dynamic physical properties and dimensional stability wherein the inorganic fine particles are pulverized and dispersed evenly in the melt processible fluoropolymer to the primary particle level at
  • the present invention provides a composition of melt processible fluoropolymer and inorganic fine particles of average particle size 1 ⁇ m or less, said inorganic fine particles being dispersed in said fluoropolymer, said composition being obtained by melt-mixing said melt processible
  • melt processible fluoropolymer composition wherein said aggregated inorganic fine particles are in the size range of 50 ⁇ m to 400 ⁇ m.
  • the aforementioned melt processible fluoropolymer composition wherein the collapse strength of the aforementioned aggregated inorganic fine particles is 1.5 MPa or less, is a preferred embodiment of the present invention.
  • the aforementioned melt processible fluoropolymer composition wherein the compressive load of the aforementioned aggregated inorganic fine particles is 40 mN or less, is a preferred embodiment of the present
  • melt processible fluoropolymer composition wherein the 80% or more of the inorganic fine particles dispersed in the polymer have a particle size of 600 nm or less, is a preferred embodiment of the present invention.
  • melt processible fluoropolymer composition wherein the aforementioned inorganic fine particles are selected from at least one of the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, and compound oxide of zinc oxide and antimony pentoxide, is a preferred embodiment of the present invention.
  • the aforementioned melt processible fluoropolymer composition wherein the aforementioned inorganic salt is selected from at least one of the group consisting of ammonium salts, alkaline earth metal salts, or alkali metal salts of hydrohalic acid, phosphoric acid, sulfuric acid, nitric acid, and molybdic acid, is a preferred embodiment of the present invention.
  • the aforementioned melt processible fluoropolymer composition wherein the aforementioned inorganic salt is selected from at least one of the group consisting of potassium bromide, potassium chloride, ammonium molybdate, sodium dihydrogen phosphate, calcium chloride, and ammonium bromide, is a preferred embodiment of the present invention.
  • the aforementioned melt processible fluoropolymer composition wherein the aforementioned drying is carried out at a drying temperature such that the ratio (To/Tm) of the indicated drying temperature (To) to the melting point (Tm) of the inorganic fine particles is 0.23 or less, said temperatures being in degrees Kelvin.
  • the aforementioned melt processible fluoropolymer composition wherein the aforementioned melt processible fluoropolymer is selected from at least one of the group consisting of polymers or copolymers of monomers selected from at least one of the group consisting of tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoro(alkyl vinyl ether), vinylidene fluoride, and vinyl fluoride or copolymers of these monomers and ethylene or propylene, is a preferred embodiment of the present invention.
  • the aforementioned melt processible fluoropolymer composition wherein the MFR of the aforementioned melt processible fluoropolymer composition is at least 50% of the MFR of the melt processible fluoropolymer, is a preferred embodiment of the present invention.
  • melt processible fluoropolymer composition wherein the elongation of the aforementioned melt processible fluoropolymer composition is at least 50% of the elongation of the melt processible fluoropolymer, is a preferred embodiment of the present invention.
  • Fig. 1 is an electron micrograph of aggregated silica fine particles (not sintered) used in the present invention.
  • Fig. 2 is an electron micrograph of silica fine particles fired at 600 0 C used in Comparative Example 1.
  • Fig. 3 is a conceptual diagram describing the dispersed state of the silica particles pulverized and dispersed in the melt-mixing process and the procedure for producing the aggregated silica fine particles used in the present invention.
  • Fig. 4 is an electron micrograph of the separated section of a sample of the melt processible fluoropolymer composition of Example 2.
  • Fig. 5 is an electron micrograph of the separated section of a sample of the melt processible fluoropolymer composition of Comparative Example 1.
  • Fig. 6 is an electron micrograph of the separated section of a sample of the melt processible fluoropolymer composition of Comparative Example 2.
  • Fig. 3 shows (1) a mixed solution of colloidal silica (sol) and potassium bromide in which (2) represents the primary silica particles and (3) potassium bromide.
  • Aggregate (4) is the result of drying the mixed solution.
  • the aggregate (5) of silica fine particles remains after the potassium bromide has been washed out, leaving the empty volume (6).
  • (7) represents the cross-section of the melt processible fluoropolymer composition wherein the aggregated silica fine particles of the present invention have been pulverized during melt-mixing and are thereby dispersed at the primary particle level in the fluoropolymer matrix.
  • a melt processible fluoropolymer composition is provided having excellent dynamic physical properties and dimensional stability wherein the inorganic fine particles are dispersed at the level of the primary particles.
  • a melt processible fluoropolymer composition having excellent dynamic physical properties and dimensional stability while maintaining to some extent the elongation and melt moldability of the melt processible fluoropolymer obtained by melt-mixing a melt processible fluoropolymer and aggregated inorganic fine particles through shear stress, and physically pulverizing and dispersing the aggregate in the melt processible fluoropolymer to level of the original inorganic fine particles.
  • a melt processible fluoropolymer can be processed to form a nanocomposite because it is possible to disperse the inorganic fine particles in the melt processible fluoropolymer at the nanolevel.
  • the molded melt processible fluoropolymer nanocomposite product provided according to the present invention has excellent dynamic physical properties, dimensional stability, fire resistance, melt moldability, and abrasion/wear proof characteristics. It has utility in various molded products.
  • the present invention provides a melt processible fluoropolymer composition having excellent dynamic physical properties and dimensional stability wherein the inorganic fine particles are dispersed in the fluoropolymer at the level of the primary particles by melt-mixing the melt processible fluoropolymer and aggregated inorganic fine particles and physically pulverizing and dispersing the aggregate.
  • the present invention provides a composition of melt processible fluoropolymer wherein the inorganic fine particles are dispersed in the polymer at average particle size of 1 ⁇ m or less this being obtained by melt-mixing a melt processible fluoropolymer and aggregated inorganic fine particles formed by the cohesive force of the inorganic fine particles.
  • the aggregated inorganic fine particles formed through the mutual cohesive force of the inorganic fine particles according to the present invention is an aggregate formed through the mutual cohesive force of the inorganic fine particles without the inorganic fine particles melting on the surface and therefore without the fine particles showing interparticle fusion.
  • the melt processible fluoropolymer can be selected from the polymers known as melt processible fluoropolymer.
  • copolymers the result of polymerizing two or more monomers
  • tetrafluoroethylene/perfluoro(alkyl vinyl ether) hereinafter referred to as PFA
  • PFA tetrafluoroethylene/hexafluoropropylene copolymer
  • EPE tetrafluoroethylene/hexafluoropropylene/perfluoro(alkyl vinyl ether)
  • ETFE tetrafluoroethylene/ethylene
  • PVDF polyvinylidene fluoride
  • PCTFE polychlorotrifluoroethylene
  • ECTFE chlorotrifluoroethylene/ethylene copolymer
  • the alkyl group of perfluoro(alkyl vinyl ether) have one to five carbon atoms, preferably from one to three carbon atoms.
  • melt processible fluoropolymer in the present invention it is possible to use coagulated particles of melt processible fluoropolymer obtained by coagulating an aqueous dispersion of the aforementioned melt processible fluoropolymers, or it is possible to use pellets created by melt extrusion of these aggregated particles.
  • melt processible fluoropolymer composite wherein the inorganic fine particles are dispersed in the melt processible fluoropolymer of the present invention can maintain elongation and the melt moldability of the melt processible fluoropolymer to a large extent even if 15 weight % of weakly aggregated inorganic fine particles is incorporated.
  • melt viscosity or the molecular weight of these melt processible fluoropolymers there is no particular restriction to the melt viscosity or the molecular weight of these melt processible fluoropolymers, and an appropriate range can be selected according to the application objective. For example, about a melt flow rate (MFR) of 7-40g/10 minutes is preferred for injection molding.
  • a colloidal solution (hereinafter this may be referred to as sol) of inorganic fine particles such as silicon dioxide, titanium dioxide, zeolite, zirconium oxide, alumina, antimony pentoxide, silicon carbide, aluminum nitride, silicon nitride, barium titanate, aluminum borate, boron nitride, lead oxide, zinc oxide, tin oxide, cerium oxide, magnesium oxide, cerium zirconate, calcium silicate, zirconium silicate, can be cited. It is preferable for these inorganic fine particles to be nano inorganic fine particles, that is particles 1 ⁇ m or less in size. These inorganic fine particles can be used of one kind or a combination of two or more kinds.
  • Preferred aggregated inorganic fine particles according to the present invention are aggregated inorganic fine particles obtained by mixing a dissolved inorganic salt and a sol of nano inorganic fine particles and preparing a solid material of inorganic salt and nano inorganic fine particles by drying the mixed solution, eluting and removing (washing out) the inorganic salt from the solid material using a solvent, and then drying.
  • Preferred aggregated inorganic fine particles according to the present invention are aggregated inorganic fine particles formed through and held together by the mutual cohesive force of the inorganic fine particles, and dried at a temperature below that at which mutual surface fusion of the inorganic fine particles occurs, preferably, a temperature where formation of necks ⁇ unctions) between particles to be described below does not occur.
  • the temperature where mutual surface fusion of the inorganic fine particles does not occur refers to a temperature which is lower than the temperature where surface fusion occurs significantly, this fusion temperature differing according to the type of inorganic fine particles used.
  • This upper limit can be selected by determining the temperature at which significant surface fusion of the inorganic fine particles occurs.
  • Whether mutual surface fusion of the inorganic fine particles occurs or not can be determined by observing the electron micrograph of the aggregated inorganic fine particles after drying, and checking that mutual surface fusion of the inorganic fine particles is not seen.
  • the aggregated inorganic fine particles obtained by removing the inorganic salt with a solvent and drying according to the present invention are normally obtained as aggregated coarse particles with a large particle size, or as a lump.
  • the particle size of the aggregated inorganic fine particles in the present invention a range of average particle size of 50 ⁇ m-400 ⁇ m, preferably 70 ⁇ m-300 ⁇ m, more preferably 75-300 ⁇ m, is preferred from the standpoint of ease of feeding into the hopper of the extruder. Particle size is determined as described in the example. When pulverizing and classifying the aggregate, it is preferable to carry out this process so that the average particle size falls in the aforementioned range.
  • the solvent for eluting the inorganic salt from the solid material of inorganic fine particles and inorganic salt can be the same or different from the solvent used in the mixed solution of inorganic fine particles and inorganic salt. However, it is preferable for it to be inactive with respect to the inorganic fine particles.
  • this solvent polar solvents, which are poor solvents with respect to the inorganic fine particles, and good solvents with respect to the inorganic salt, can be appropriately selected and used. Water is one example of a preferred solvent.
  • Inorganic salt is eluted and removed using a solvent that elutes the inorganic salt from the solid material; hence it has the role of a hole-forming agent with respect to the obtained aggregate.
  • a method that uses at least one kind selected from silica sol, titanium dioxide sol, alumina sol, zeolite sol, and sol of compound oxide of zinc oxide and antimony pentoxide as the nano inorganic fine particles, uses water as the solvent, and uses a water soluble inorganic salt as the inorganic salt, can be cited.
  • water soluble inorganic salt ammonium salts, alkaline earth metal salts, or alkali metal salts of hydrohalic acid, phosphoric acid, sulfuric acid, nitric acid, and molybdic acid, preferably, potassium nitrate, potassium iodide, ammonium molybdate, sodium dihydrogen phosphate, potassium bromide, potassium chloride, calcium chloride, copper chloride, and calcium nitrate can be cited.
  • These inorganic salts can be used individually or by combining two or more kinds. From among the aforementioned methods, the method that uses silica sol as the source of nano inorganic fine particles is preferred. If the solvent used is of high purity, aggregated inorganic fine particles of high purity can be obtained.
  • the aforementioned aggregated inorganic fine particles can be a silica aggregate obtained by dispersing, dissolving, and drying aqueous mixture of a silica sol, an inorganic salt which is the hole forming agent, and an "agent for substitution", for example, MgO or Mg(OH) 2 , in an aqueous solution, that is a compound or salt that can be later exchanged to introduce another material on the surface of the silica.
  • the dried mixture is immersed in an aqueous additive solution of another compound or salt, for example, palladium hydroxide, palladium exchanging with the magnesium ion on the silica surface.
  • another compound or salt for example, palladium hydroxide, palladium exchanging with the magnesium ion on the silica surface.
  • the inorganic salt which is the hole forming agent is removed, and the aforementioned agent for substitution may be exchanged with other metal and inorganic compounds, which can be designated as "additive(s)". If no exchange is made, the magnesium compound is the « « « « ⁇ ' USOB /OM-J.79 additive. It should be noted that if the sintering described in the aforementioned Japanese Patent Application is carried out, the preferred aggregate according to the present invention cannot be obtained.
  • inorganic compounds 5 such as magnesium hydroxide, aluminum hydroxide, antimony trioxide, and metals such as palladium, copper, magnesium, iron, aluminum, tin, nickel, cobalt, titanium, platinum, gold, and silver, can be used. Because the additive is dispersed over the high surface area of the silica particles, activity is increased. So that, for example, an additive that is a flame
  • the strength of the aggregated inorganic fine particles of low strength formed through the mutual cohesive force of the nano inorganic fine particles obtained according to the present invention changes according to the type and particle size of the nano inorganic fine particle
  • the strength of the aggregated inorganic fine particles can be controlled by adjusting these conditions.
  • melt processible fluoropolymer to disperse the inorganic fine particles in the polymer, the average particle size of the aggregated inorganic fine particles dispersed in the melt processible fluoropolymer, and the dispersed state, change according to the type of melt-mixing device used, the type of fluoropolymer to be melted
  • melt-mixing conditions temperature and rotation rate of the screw(s), and design of the screw(s)
  • the desired melt processible fluoropolymer composition can be obtained by controlling both the melt-mixing conditions and the preparation of the aggregated inorganic fine particles.
  • a surprising aspect of this invention is that the aggregate inorganic fine particles disperse so well in fluoropolymers.
  • Fluoropolymers have little affinity for polar materials such as silica, or the other inorganic fine particles disclosed herein. It would not have been unreasonable to expect that the inorganic fine particles would resist dispersion into the fluoropolymer, or to put it the other way around, that fluoropolymer would resist dispersion of the inorganic fine particles, with the result that the inorganic fine particles would agglomerate in the fluoropolymer.
  • the particles disperse well in fluoropolymer, contributing increased tensile modulus and increased elongation without reducing melt processibility by excessively increasing melt viscosity (reducing melt flow rate).
  • the strength is the sum of the adhesive forces between the particles functioning at the contact points of the many silica primary particles forming the porous body; hence it is determined primarily according to the porosity of the porous silica body and the silica primary particle size (Chemie lngenieurtechnik, vol 42, p.538, 1970).
  • the content of the inorganic salt is increases to increase the porosity, or use of silica fine particles of large average primary particle size, is favorable.
  • the average primary particle size should be 50 nm or greater, preferably 90 nm or greater, more preferably, 110 nm or greater, but less than 1 ⁇ m, preferably no greater than 600 nm, and more preferably no greater than 400 nm. If the porosity is the same the strength of the aggregate is inversely proportional to the primary particle size, and if the average primary particle size is small, the strength of the aggregate becomes greater and there is a tendency for it not to be completely pulverized in the melt-mixing process. Also, when using aggregated inorganic fine particles of the same strength, melt-mixing at a greater shear stress enables uniform pulverization and dispersion of the nano inorganic fine particles of the aggregated inorganic fine particles in the thermoplastic polymer.
  • the inorganic salt used according to the present invention has the role of a hole forming agent with respect to the aggregated nano inorganic fine particles; hence the strength of the aggregated inorganic fine particles changes even according to the content of the inorganic salt.
  • the content of the inorganic salt in the aggregated inorganic fine particles should be 1-90 volume %, preferably 50-85 volume %, more preferably 60-80 volume %, on a dry basis.
  • the aggregated inorganic fine particles of the present invention are subjected to two drying steps in the course of their preparation.
  • the first drying step occurs when a solid material of nano inorganic fine particles and inorganic salt is prepared by mixing the inorganic salt and the nano inorganic particle sol dispersed in water and then dried.
  • the second drying step occurs after removing the inorganic salt by using a solvent for eluting the inorganic salt from the solid material of nano inorganic fine particles and inorganic salt, when the remaining solid is dried to remove residual solvent.
  • the drying temperature should be below that at which interparticle surface fusion of the inorganic fine particles occurs as described above and, preferably, a temperature below that at which formation of necks occurs.
  • the melting point at the surface of the nano inorganic fine particles is lower than the bulk melting point of the inorganic fine particles; hence if, in either drying step, the drying temperature becomes too high, a portion of the surface of the nano inorganic fine particles fuses and the strength of the aggregated inorganic fine particles increases due to the mutual fusion of the adjacent nano inorganic fine particles.
  • inorganic fine particles generally have a crystal structure defect on the particle surface when formed, and this type of defect is thermally unstable; hence rapid rearrangement and movement occurs when heated, and bonding junctions (necks) are formed at the contact points of adjacent inorganic fine particles.
  • the strength of the aggregated inorganic fine particles increases with the increase in neckmpf ,,. w , . 1, 'Ii formation.
  • the principal cause for the neck formation is considered to be mutual surface fusion of adjacent inorganic fine particles.
  • Neck formation starts when either drying temperature is such that the ratio (To/Tm) of the indicated drying temperature (To) to the melting point (Tm) of the inorganic fine particles exceeds 0.23, said temperatures being in degrees Kelvin.
  • the ratio of the drying temperature to the melting point of the inorganic fine particles, in degrees Kelvin be 0.23 or less. Therefore, if the inorganic fine particles are silica, it is preferable to carry out the drying steps at 150 0 C or less, preferably 120°C or less. It is not necessary that both drying steps be carried out at the same temperature.
  • the compressive load measured when the particle size is about 150 ⁇ m, be 40 mN or less, preferably 35 mN or less. It is understood that the relation of strength of the aggregate to the dispersibility of the aggregate depends also on the structure of the melt-mixing device (structure of the screw and the assembly) used, the type of polymer that is melted and mixed, the melt-mixing conditions (temperature and the rotation speed of the screw).
  • the collapse strength (St) of the aggregated inorganic fine particles according to the present invention should be 1.50 MPa or less, preferably 1.40 MPa or less.
  • the calculation of collapse strength compensates for the effect of difference in particle size as will be described below.
  • the amount of the aforementioned aggregated inorganic fine particles with respect to the melt processible fluoropolymer is 0.3-70 weight %, preferably 0.5-50 weight %, more preferably 1-30 weight %, based on the combined weights of inorganic fine particles and fluoropolymer.
  • optimum mixing ratio also depends on the intended application of the melt processible fluoropolymer composition.
  • the melt processible fluoropolymer composition obtained according to the present invention is a melt processible fluoropolymer composition wherein 1000 nm (1 ⁇ m) or less, preferably 600 nm or less, more preferably 400 nm or less (primary particle size) aggregated inorganic finerough il" Ii Ii ..' ⁇ • Ii Ii m; I i K . particles are dispersed in a polymer obtained by melt-mixing the aforementioned aggregated inorganic fine particles and a melt processible fluoropolymer.
  • melt-mixing the aggregated inorganic fine particles according to 5 the present invention and a melt processible fluoropolymer it is possible to obtain a melt processible fluoropolymer composition wherein almost all the fine particles are dispersed at the nano level, that is as primary particles.
  • the state wherein the inorganic fine particles are dispersed in the melt processible fluoropolymer can be observed with an electron micrograph of
  • composition is prepared by cooling test piece in liquid nitrogen and breaking it. Three areas of the surface exposed by the break are optionally selected randomly with an electron microscope, and the size of the pulverized aggregated inorganic fine particles and primary particles are observed. A distribution chart of the size of the particles observed in
  • the composite and the number thereof is prepared (the particle size on the lateral axis using a logarithmic scale), and the particle size with the greatest ratio of inorganic fine particles is considered as the average particle size.
  • This average particle size can be compared to the size of the primary particles in the sol of inorganic particles from which the
  • a preferred melt processible fluoropolymer composition has 80% or more, preferably II-" IL,,,, Ii , • ⁇ ' ⁇ IJl 5 O g / ⁇ £"!,
  • mofe ' preferably 95% or more of the number of inorganic fine particles measured by observing the micrograph in the aforementioned range of 1 ⁇ m or less, preferably 600 nm or less, and more preferably 400 nm or less.
  • the polymer nanocomposite of the present invention wherein the inorganic fine particles are dispersed in the polymer at the nanolevel has the merit of improved physical properties at a lower concentration of the aggregated inorganic fine particles is mixed than would be used in the conventional fluoropolymer compound mixture. This improvement is due
  • the melt-mixing temperature of the twin screw extruder should be set keeping in mind the increase the polymer temperature caused by internal heating due to the
  • melt temperature not exceed the melting point of the fluoropolymer by more than about 50°C.
  • molded products since molded products requiring dynamic physical properties and dimensional stability are the objective, applications in various anticipated fields are possible due to the particles being dispersed evenly at the nanolevel, and are not restricted in particular by the present invention.
  • Examples are tubes, sheets, rods, fibers, packing, linings, wire insulation, including primary wire insulation, and cable covers, as well as containers such as trays, and vessels, and pipes, for use in the semi-conductor and biochemical industries.
  • Molding methods are those known in the thermoplastic processing art, including extrusion molding, compression molding, rotomolding, including rotolining, and blow molding.
  • a differential scanning calorimeter (Pyris 1 model DSC, made by Perkin Elmer Co.) was used. 10 mg of the sample powder was weighed, placed in an aluminum pan, crimped, and placed in the DSC. The temperature was increased from 150°C to 360°C at 10°C/minute. The melt peak temperature (Tm) is taken as the maximum of the melting endotherm.
  • a melt indexer made by Toyo Seiki Seisaku-sho Ltd. equipped with corrosion proof cylinder, die, and piston based upon ASTM D-1238-95 standard was used. 5g of sample powder was filled in a cylinder maintained at 372+1 0 C (for perfluoropolymers; for other fluoropolymers, the temperature is that specified in the table at section 8.2 of the ASTM standard), and after holding for 5 minutes, the polymer was extruded through a die orifice under a load (piston plus weight) of 5 kg. The extrusion rate in units of g/10 minutes is the MFR.
  • the collapse strength of the aggregated inorganic fine particles according to the present invention was measured by selecting aggregates with particle size of about 150 ⁇ m.
  • the average particle size of the commercial silica used as the comparative example is smaller than that of the samples of the present invention; hence the value of the experimental force P is low.
  • the collapse strength St which takes into account the effect of difference in the particle size, is greater.
  • Average particle size A sample of the fluoropolymer composition was placed in liquid nitrogen, three areas of the fabricated separated section were optionally selected with regards to each sample with an electron microscope, the size of the silica particles in the composition was observed, a distribution chart of the particle size and the number thereof was prepared (the particle size on the lateral axis having a logarithmic scale), and the size with the greatest number of inorganic fine particles was considered the average particle size.
  • Silica aggregate of 20 ⁇ m or greater From the result of observing at magnification of 200 (field of view: 450 ⁇ m x 450 ⁇ m), the number of silica particles of particle size 20 ⁇ m and greater and the particle size thereof were measured.
  • the first digit in the particle size was eliminated (e.g., 28 ⁇ m was reported as 20 ⁇ m)
  • Silica aggregate of 5 ⁇ m-20 ⁇ m As a result of observing at magnification of 500 (field of view: 180 ⁇ m x 180 ⁇ m), the number of silica particles with particle size of 5 ⁇ m-20 ⁇ m and the particle size thereof were measured. Also, the number of silica particles corresponding to each particle size counted was multiplied by 6.25 and convert the result to the area observed at magnification of 200.
  • Silica primary particles or silica aggregate of 500 nm-1 ⁇ m From the result of observing at magnification of 5000 (field of view: 18 ⁇ m x 18 ⁇ m), the number of silica primary particles or silica aggregates of particle size 500 nm-1 ⁇ m and the particle size thereof were measured. Also, the number of silica particles corresponding to the counted particle sizes was multiplied by 625 converted the result to the area observed at magnification of 200. The particle size was measured in nm units and the digits under 100 were eliminated (e.g. 650 nm was considered as 600 nm). However, the measured value of the particle size of the silica primary particle was retained as the particle size.
  • Silica primary particles or silica aggregate of 200 nm or less From the result of observing at magnification of 20000 (field of view: 4.5 ⁇ m x 4.5 ⁇ m), the number of silica primary particles or silica aggregates of particle size 200 nm or less and the particle size thereof were measured according to the same method as d) and converted into the result of the area
  • the dispersed state of the silica fine particles was evaluated according to the following standard using the aforementioned
  • Snowtex® MP2040 (average silica primary particle size: 190 nm). Designated herein as S1. ( K IL. !ly " IJ S QE ,/ ' O U.1 7 J 9
  • Snowtex® MP1040 (average silica primary particle size: 110 nm) .
  • Snowtex® ST-YL (average silica primary particle size: 57 nm) . Designated herein as S3.
  • Snowtex® 30 (average silica primary particle size: 12 nm) . Designated herein as S4.
  • silica sol 40 weight % silica in which the dispersed silica
  • 15 fine particles have the average particle sizes (primary particle size) shown in Table 1 was dispersed in 1 liter of deionized water in a beaker, and 292.3g of potassium bromide (KBr) as the hole forming agent was added, agitated until the KBr dissolved, and then 60 wt% nitric acid was added to adjust the pH to about 4.0 in order to promote the coagulation of the silica 0 fine particles. Next, the agitated mixed solution was transferred to a container made of fluoropolymer and dried at 80°C to constant weight.
  • KBr potassium bromide
  • the resulting cake was pulverized, classified with sieves (Japanese Standard) of 300 ⁇ m and 75 ⁇ m mesh, and powder obtained of average particle sizes 75 ⁇ m-300 ⁇ m. 100 g of the powder and 2.5L of 5 deionized water were added into a beaker and agitated for 30 minutes at 200 rpm while heating at 80°C. Thereafter, the beaker was left standing to allow the precipitation the solid material, and the clear fluid at the top containing the eluted KBr was removed.
  • sieves Japanese Standard
  • the sample was dried for about 10 hours at 120°C, vacuum dried 0 additionally for 3 hours at 12O 0 C, and samples obtained of aggregated silica fine particles S1 , S2, S3, and S4, with KBr removed and only the SiO 2 skeleton remaining.
  • the collapse strengths of the samples are shown in Table 1.
  • silica sol 40 weight % silica, average particle size (0.012 ⁇ m) shown in Table 1 was dispersed in 1 liter of water in a beaker, and 292.3g of KBr was added, and agitated until the KBr totally dissolved. 60 wt% nitric acid was added to adjust the pH about 4.0 in order to promote
  • the top containing the eluted KBr, was removed.
  • the sample was dried for about 10 hours at 12O 0 C, vacuum dried additionally for 3 hours at 120°C, and a sample obtained of aggregated silica fine particles S5, with KBr removed and only the Si ⁇ 2 skeleton remaining.
  • the electron micrograph of the sample obtained is
  • the commercial sintered aggregated silica fine particles R1 and R2 were analyzed for compressive load and collapse strength: (R2) 0.18 mN,
  • Example 1-4 Examples 1-4 and sintered aggregated silica fine particles S5 (Comparative Example 1) were melt mixed with PFA 350J for 1 minute 40 seconds at 340 0 C, 240 rpm using as the melt-mixing device that made by Toyo Seiki Seisaku-sho Ltd., KF-70V compact segment mixer, in combinations of high shear that displaced the phases of five kneading discs by a pitch of 0.5, and obtained the melt processible fluoropolymer compositions shown in Table 2.
  • the MFR and tensile properties of the melt processible fluoropolymer compositions were measured.
  • the pulverized and dispersed state of the silica was evaluated using electron microscopy. The results obtained are shown in Table 2.
  • Comparative Example 2 is an example of directly melt-mixing commercial silica nano particles of particle size 7 nm with melt processible fluoropolymer.
  • Example 1 the collapse strength of the aggregated silica fine particles used is weaker than that of Comparative Example 1 ; hence most of the aggregated silica fine particles were pulverized during the melt- mixing process.
  • a small amount of aggregated inorganic fine «" ⁇ " « « /U S Cl B /QNkI 79 particles of size about 1 ⁇ m-20 ⁇ m remained that were not completely pulverized.
  • Example 2 aggregated silica fine particles with weak collapse strength were used. As a consequence, aggregated silica fine particles of 5 size about 150 ⁇ m were pulverized and dispersed up to the level of the silica primary particles (particle size 190 nm) during the melt-mixing process (Figure 4).
  • the MFR and the elongation percent decreased with increase in the content of filler.
  • the MFR and elongation percent did not 15 decrease even when the aggregated silica fine particles were increased to 8 weight % and 15 weight % and remained at about the same level as without filler (Reference Example 1). This is considered to be the result of the nanolevel dispersion of the silica primary particles in the fluoropolymer.
  • the tensile modulus increased with increase in the content of the 20 aggregated silica fine particles.
  • MFR as can be seen in Table 2. At 3 wt% loading MFR is 1.58 compared to 2.01 for the fluoropolymer alone. In Example 4, with 15 wt% loading of aggregated fine silica, MFR drops only to 1.77, well above that 5 of Comparative Example 2 even though the loading is five times as high. In the present invention, it was possible to physically pulverize and disperse the aggregated inorganic fine particles of low strength that were mixed through the shear stress generated in the melt-mixing device to the nano inorganic fine particle level by melt-mixing a melt processible
  • melt processible fluoropolymer composition having excellent dynamic physical properties
  • a melt processible fluoropolymer composition having excellent dynamic physical properties and dimensional stability while maintaining to some extent the
  • a melt processible fluoropolymer can be made into a nanocomposite due to being able disperse the inorganic fine particles in the melt processible fluoropolymer to the nanolevel.
  • Molded melt processible fluoropolymer nanocomposite products capable of being provided according to the present invention have excellent dynamic physical properties, dimensional stability, fire resistance, melt moldability, abrasion/wear-proof characteristics, etc. and hence can be applied to various molded products. i / U S O B ./"Q Nk::!., 7 >9
  • the inorganic fine particles are dispersed in the polymer at the nanolevel; hence compared to the conventional fluoropolymer compound mixture wherein fillers are dispersed at the micron level, there is a merit of anticipated improvement in the physical properties even if a smaller amount of the aggregated inorganic fine particles is used than in the conventional fluoropolymer compound mixture.
  • melt processible fluoropolymer composition capable of being applied in various anticipated fields due to the particles being dispersed evenly at the nanolevel.
  • Applications for use in tubes, sheets, rods, fibers, packing, linings, wire insulation, including primary wire insulation, and cable covers are possible.

Abstract

La présente invention concerne une composition de fluoropolymère transformable à l'état fondu et de particules fines inorganiques de dimension moyenne de particules inférieure ou égale à 1 mm dispersées dans ledit fluoropolymère, ladite composition étant obtenue par un mélange-fusion du fluoropolymère transformable à l'état fondu et desdites particules fines inorganiques agrégées, lesdites particules fines inorganiques agrégées étant obtenues par le séchage d'une solution mélangée des particules fines inorganiques et d'un sel inorganique pour obtenir un matériau solide, l'élimination du sel inorganique de ce matériau solide en utilisant un solvant, et ensuite le séchage à une température où il n'y a pas de fusion en surface entre les particules fines inorganiques, moyennant quoi lesdits agrégats représentent le résultat de la force cohésive mutuelle des particules fines inorganiques, laquelle composition ayant de bonnes propriétés physiques et une bonne stabilité dimensionnelle par comparaison au seul fluoropolymère transformable à l'état fondu.
PCT/US2006/004179 2006-01-31 2006-02-07 Composition de fluoropolymere transformable a l'etat fondu contenant des nanoparticules WO2007120122A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP06850491A EP1979405A1 (fr) 2006-01-31 2006-02-07 Composition de fluoropolymere transformable a l'etat fondu contenant des nanoparticules
PCT/US2006/004179 WO2007120122A1 (fr) 2006-01-31 2006-02-07 Composition de fluoropolymere transformable a l'etat fondu contenant des nanoparticules
CN2006800520620A CN101336269B (zh) 2006-01-31 2006-02-07 包含纳米颗粒的可熔融加工氟聚合物

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US11/343,569 2006-01-31
US11/343,569 US7495049B2 (en) 2005-02-04 2006-01-31 Melt processible fluoropolymer composition containing nano particles
PCT/US2006/004179 WO2007120122A1 (fr) 2006-01-31 2006-02-07 Composition de fluoropolymere transformable a l'etat fondu contenant des nanoparticules

Publications (2)

Publication Number Publication Date
WO2007120122A1 true WO2007120122A1 (fr) 2007-10-25
WO2007120122A8 WO2007120122A8 (fr) 2007-12-21

Family

ID=38421742

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/004179 WO2007120122A1 (fr) 2006-01-31 2006-02-07 Composition de fluoropolymere transformable a l'etat fondu contenant des nanoparticules

Country Status (3)

Country Link
EP (1) EP1979405A1 (fr)
CN (1) CN101336269B (fr)
WO (1) WO2007120122A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9309370B2 (en) 2011-02-04 2016-04-12 3M Innovative Properties Company Amorphous perfluoropolymers comprising zirconium oxide nanoparticles
CN113307991A (zh) * 2021-06-08 2021-08-27 日氟荣高分子材料(上海)有限公司 一种具有高热氧稳定性的fep母粒及其加工方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6166577B2 (ja) * 2013-04-16 2017-07-19 三井・デュポンフロロケミカル株式会社 フッ素樹脂組成物、及びその成形物
US11339305B2 (en) * 2017-02-07 2022-05-24 The Chemours Company Fc, Llc Substrate coated with non-stick coating resistant to abrasion and scratching
CN109971066A (zh) * 2019-03-20 2019-07-05 苏州泰尚新材料有限公司 红外阻隔含氟组合物、制备方法及其应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001158859A (ja) * 1999-12-02 2001-06-12 Asahi Kasei Corp 複合重合体組成物
JP2001158828A (ja) * 1999-12-02 2001-06-12 Asahi Kasei Corp 重合体複合組成物

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5962553A (en) * 1996-09-03 1999-10-05 Raychem Corporation Organoclay-polymer composites
FR2822296A1 (fr) * 2001-03-19 2002-09-20 Atofina Elements de batteries lithium-ion fabriques a partir d'une poudre microcomposite a base d'une charge et d'un fluoropolymere

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001158859A (ja) * 1999-12-02 2001-06-12 Asahi Kasei Corp 複合重合体組成物
JP2001158828A (ja) * 1999-12-02 2001-06-12 Asahi Kasei Corp 重合体複合組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200155, Derwent World Patents Index; AN 2001-499476, XP002448540 *
DATABASE WPI Week 200201, Derwent World Patents Index; AN 2002-002027, XP002448539 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9309370B2 (en) 2011-02-04 2016-04-12 3M Innovative Properties Company Amorphous perfluoropolymers comprising zirconium oxide nanoparticles
CN113307991A (zh) * 2021-06-08 2021-08-27 日氟荣高分子材料(上海)有限公司 一种具有高热氧稳定性的fep母粒及其加工方法

Also Published As

Publication number Publication date
EP1979405A1 (fr) 2008-10-15
CN101336269A (zh) 2008-12-31
CN101336269B (zh) 2012-03-07
WO2007120122A8 (fr) 2007-12-21

Similar Documents

Publication Publication Date Title
US7495049B2 (en) Melt processible fluoropolymer composition containing nano particles
JP5252612B2 (ja) 樹脂複合体組成物およびその製造方法
EP1937762B1 (fr) Composition polymere avec particules inorganiques nanodimensionnees et a repartition uniforme
Baskaran et al. Mechanical and thermal properties of unsaturated polyester/calcium carbonate nanocomposites
EP1979405A1 (fr) Composition de fluoropolymere transformable a l'etat fondu contenant des nanoparticules
AU2017207521B9 (en) Process for preparation of polyethylene nanocomposite
JP2008115336A (ja) 接着性フッ素樹脂複合体組成物
EP1384750B1 (fr) Pprocédé de fabrication de compositions de fluoropolymères contenant des particules inorganiques nanométriques
Debnath et al. Preparation by suspension polymerization and characterization of polystyrene (PS)-poly (methyl methacrylate)(PMMA) core-shell nanocomposites
Gautam et al. Synthesis of montmorillonite clay/poly (vinyl alcohol) nanocomposites and their mechanical properties
TWI403551B (zh) 含奈米粒子之熱熔性氟聚合物組合物
WO2006082880A1 (fr) Composition composite de résine thermoplastique, procédé servant à produire celle-ci et utilisation de celle-ci
JP2008013610A (ja) フッ素樹脂複合体組成物からなる成形品
KR20190018148A (ko) 중합체 조성물, 이의 제조 방법, 이의 용도 및 이를 포함하는 조성물
JP2008239882A (ja) 抗菌性フッ素樹脂組成物
JP2006213577A (ja) 無機微粒子凝集体およびその製造方法
JP2008115335A (ja) フッ素樹脂複合体組成物からなる透明部材
JP2008088305A (ja) パーフルオロフッ素樹脂複合体組成物
KR101989163B1 (ko) 신택틱 폼 조성물 및 그의 제조방법
JP2008088306A (ja) パーフルオロフッ素樹脂複合体組成物
KR101658393B1 (ko) 자동차 라디에이터 호스 고무용 나노 콤포지트 조성물 및 이의 제조방법
Anandhan et al. 1Department of Metallurgical and Materials Engineering, National Institute of Technology Karnataka, Mangaluru, India, 2Department of Research & Development, India Innovation Center, Dover India Pvt Ltd., Bengaluru, India* Corresponding author. e-mail address: anandtmg@ gmail. com
WO2017211887A1 (fr) Composition polymère, son procédé de préparation et son utilisation
KR20110033334A (ko) 불소수지복합체 합성물로 이루어진 투명부재
Taha et al. A review on MWCNTS: the effect of its addition on the polymer matrix

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 06850491

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 200680052062.0

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2006850491

Country of ref document: EP