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
  • C08F214/28—Hexyfluoropropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D127/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/20—Homopolymers or copolymers of hexafluoropropene

Definitions

• Fluoroelastomers including copolymers of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) and copolymers of tetrafluoroethylene (TFE), vinylidene fluoride (VDF), and hexafluoropropylene (HFP) are known to have excellent mechanical properties, heat resistance, weather resistance, and chemical resistance, for example. Such beneficial properties render fluoroelastomers useful for example, as O-rings, seals, hoses, skid materials, and coatings (e.g., metal gasket coating for automobiles).
• VDF vinylidene fluoride
• HFP hexafluoropropylene
• TFE tetrafluoroethylene
• VDF vinylidene fluoride
• HFP hexafluoropropylene
• Peroxides have been used to crosslink polymers to make cured fluoroelastomers.
• Peroxide-curable fluoropolymers typically have bromine or iodine cure sites or end groups. Certain peroxides have recently been shown to increase the cure speed of amorphous fluoropolymers in U.S. Pat. Appl. Pub. No. 2012/0088884 (Fukushi et al.).
• the present disclosure provides a curable composition of an amorphous, peroxide-curable fluoropolymer and a solvent, useful, for example, for making cured fluoroelastomers.
• the curable compositions have at least one of the following unexpected properties: (1) an unexpectedly low viscosity in view of the high weight percentage of amorphous peroxide-curable fluoropolymer in the composition or (2) an unexpected ability to cure in view of the solvent present in the composition.
• the present disclosure provides a curable composition that includes an amorphous, peroxide-curable fluoropolymer having a first solubility parameter, a solvent having a second solubility parameter, and a peroxide.
• the amorphous, peroxide-curable fluoropolymer is present from 60 percent to 97.5 percent by weight versus the weight of the curable composition, and the solvent is present from 1 percent to 39 percent by weight versus the weight of the curable composition.
• the absolute value of the first solubility parameter minus the second solubility parameter is less than or equal to 8.2 (MPa) 1/2 .
• the present disclosure provides a curable composition that includes an amorphous, peroxide-curable fluoropolymer, a solvent, and a peroxide.
• the amorphous, peroxide-curable fluoropolymer is present from 60 percent to 97.5 percent by weight versus the weight of the curable composition.
• the solvent has a solubility parameter in a range from 9.6 (MPa) 1/2 to 26 (MPa) 1/2 and is present from 1 percent to 39 percent by weight versus the weight of the curable composition.
• the present disclosure provides a method of making a cured fluoroelastomer.
• the method includes providing the curable composition disclosed herein and heating the curable composition at a cure temperature to make the cured fluoroelastomer.
• the solvent is removed by drying before attempting to cure the polymer because typical hydrocarbon solvents can react with radicals, for example, by hydrogen abstraction. Even residual solvent can interfere with crosslinking.
• the curable composition disclosed herein can be cured without removing the solvent.
• the present disclosure provides a method of making a cured fluoroelastomer.
• the method includes providing the curable composition disclosed herein and heating the curable composition at a cure temperature to make the cured fluoroelastomer without first removing the solvent.
• phrases “comprises at least one of” followed by a list refers to comprising any one of the items in the list and any combination of two or more items in the list.
• the phrase “at least one of” followed by a list refers to any one of the items in the list or any combination of two or more items in the list.
• solvent refers to a homogeneous liquid material (inclusive of combinations of two or more materials) that has a boiling point and that is capable of at least partially dissolving the amorphous peroxide-curable fluoropolymer at 25° C.
• curable joining polymer chains together by covalent chemical bonds, usually via crosslinking molecules or groups, to form a network polymer. Therefore, in this disclosure the terms “cured” and “crosslinked” may be used interchangeably.
• a cured or crosslinked polymer is generally characterized by insolubility, but may be swellable in the presence of an appropriate solvent.
• amorphous fluoropolymers can be dissolved in solvent and coated on a substrate.
• the typical amorphous polymer content of these solutions can be from 20% to 50% by weight versus the weight of the solution.
• Higher fluoropolymer content in these solutions may be desirable to increase coating thickness and to reduce volatile organic compounds (VOCs).
• VOC volatile organic compound
• the viscosity of a solution of amorphous fluoropolymer generally increases as the molecular weight of the amorphous fluoropolymer increases. Accordingly, amorphous fluoropolymers having relatively low molecular weights can be useful for making solvents with higher fluoropolymer content and/or lower solution viscosity. If the molecular weight of the amorphous fluoropolymer is too low, however, it will be difficult to cure. Finding the balance between molecular weight and curing can be challenging.
• the solvent is typically removed by drying before attempting to cure the polymer because typical hydrocarbon solvents can react with radicals, for example, by hydrogen abstraction. Even residual solvent can interfere with the curing or crosslinking reaction.
• the curable compositions according to the present disclosure include a relatively high weight percent of amorphous fluoropolymer in certain solvents.
• the amorphous fluoropolymer is in a range from 60% to 97.5% by weight of the amorphous fluoropolymer versus the weight of the curable composition.
• the amorphous fluoropolymer is not present at 80% by weight versus the weight of the curable compositions.
• the amorphous fluoropolymer is present in a range from 60% to less than 80% by weight versus the weight of the curable composition.
• the solvent may be present in a range from 19% to 39% by weight versus the weight of the curable composition.
• the amorphous fluoropolymer may be present in a range from 60% up to 79%, 78%, 77%, 76%, 75%, or less than 75% by weight, versus the weight of the curable composition. In other embodiments, the amorphous peroxide-curable fluoropolymer is present in a range from greater than 80 percent by weight to 97.5 percent by weight versus the weight of the curable composition. In these embodiments, the solvent may be present in a range from 1% to 19% versus the weight of the curable composition.
• the amorphous fluoropolymer may be present in a range from 81% to 97.5%, 81% to 95%, greater than 80% to 90%, or greater than 90% to 97.5% by weight, versus the weight of the curable composition.
• the absolute value of the solubility parameter difference between the amorphous fluoropolymer ( ⁇ a ) and solvent ( ⁇ b ) may be less than or equal to 8.2 (MPa) 1/2 (4 (cal/cc) 1/2 ). In other words,
• the absolute value of the solubility parameter difference between fluoropolymer ( ⁇ a ) and solvent ( ⁇ b ) is less than or equal to 6.1 (MPa) 1/2 (3 (cal/cc) 1/2 ), or less than or equal to 4.1 (MPa) 1/2 (2 (cal/cc) 1/2 ).
• solubility parameter, ⁇ , of a fluoroelastomer including VDF and HFP in a 78/22 molar ratio is reported to be 8.7 (cal/cc) 1/2 (17.8 (MPa) 1/2 ) in Myers and Abu-Isa, Journal of Applied Polymer Science , Vol. 32, 3515-3539 (1986).
• the solubility parameter of an amorphous fluoropolymer is considered to be 17.8 (MPa) 1/2
• the solvent has a solubility parameter in a range from 9.6 (MPa) 1/2 to 26 (MPa) 1/2 , in some embodiments, 11.7 (MPa) 1/2 to 23.9 (MPa) 1/2 , and in some embodiments, 13.7 (MPa) 1/2 to 21.9 (MPa) 1/2 .
• Solvents useful for practicing the present disclosure have a boiling point and can be removed from the cured fluoroelastomers made from curable compositions disclosed herein, if desired, using normal drying procedures with heat or reduced pressure. These features distinguish the solvents from ionic liquids (e.g., those disclosed in International Application Publication No. WO 2012/006487 (Fukushi et al.), and solvents useful for practicing the present disclosure do not include ionic liquids.
• the solvent has a boiling point in a range from 30° C. to 200° C.
• solvents useful for practicing the present disclosure include ketones, esters, carbonates, and formates such as tert-butyl acetate, 4-methyl-2-pentanone, n-butyl acetate, ethyl acetate, 2-butanone, ethyl formate, methyl acetate, cyclohexanone, dimethyl carbonate, acetone, and methyl formate.
• the solvent comprises at least one of acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-butyl acetate, tert-butyl acetate, or dimethyl carbonate.
• the solvent comprises at least one of ethyl acetate or methyl acetate.
• the solvent is not an alcohol. Alcohols tend to be particularly detrimental to a peroxide-cure.
• Solvents useful for practicing the present disclosure can be selected based on their ozone impact.
• the ozone impact of VOCs was calculated and reported as maximum incremental reactivity (MIR) values in units of grams of ozone per gram or VOC.
• MIR maximum incremental reactivity
• Certain solvents have been found to have negligible photochemical reactivity and are listed as VOC exempt in 40 CFR Part 51.100(s) (as amended through Jan. 21, 2009).
• the solvent useful for practicing the present disclosure has a calculated ozone impact of up to 0.35 on the maximum incremental reactivity (MIR) scale measured in units of grams of ozone per grams of solvent.
• MIR maximum incremental reactivity
• curable compositions according to the present disclosure with their high polymer content and low ozone impact can provide low ground-level ozone.
• Solubility MIR parameter Boiling Point O 3 g/ Solvent (cal/cc) 1/2 MPa 1/2 (° C.) solvent g) tert-butyl acetate (TBA) 7.7 15.8 98 0.18 4-methyl-2-pentanone 8.4 17.2 117 3.88 (MIBK) n-butyl acetate (BA) 8.5 17.4 126 0.83 amorphous 8.7 17.8 Not available Not fluoropolymer available ethyl acetate (EA) 9.1 18.6 77 0.63 2-butanone (MEK) 9.3 19.0 80 1.48 ethyl formate (EF) 9.4 19.2 54 0.48 methyl acetate (MA) 9.6 19.6 57 0.072 cyclohexanone 9.9 20.3 156 1.35 dimethyl carbonate 9.9 20.3 90 0.059 (DMC) acetone 10.0 20.5 56 0.36 methyl formate 10.2 20.9 32 0.057 IPA 11.5 23.5 82.5 0.61 ethanol 12.8 2
• Curable compositions according to the present disclosure also include a peroxide.
• peroxides useful for practicing the present disclosure are acyl peroxides.
• Acyl peroxides tend to decompose at lower temperatures than alkyl peroxides and allow for lower temperature curing.
• the peroxide is di(4-t-butylcyclohexyl)peroxydicarbonate, di(2-phenoxyethyl)peroxydicarbonate, di(2,4-dichlorobenzoyl) peroxide, dilauroyl peroxide, decanoyl peroxide, 1,1,3,3-tetramethylethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, disuccinic acid peroxide, t-hexyl peroxy-2-ethylhexanoate, di(4-methylbenzoyl) peroxide, t-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxy 2-ethylhexyl carbonate, or t-butylperoxy isoprop
• the peroxide is a diacyl peroxide.
• the peroxide is benzoyl peroxide or a substituted benzoyl peroxide (e.g., di(4-methylbenzoyl) peroxide or di(2,4-dichlorobenzoyl) peroxide).
• the peroxide is present in the curable composition in an amount effective to cure the composition.
• the peroxide is present in the composition in a range from 0.5% by weight to 10% by weight versus the weight of the curable composition.
• the peroxide is present in the composition in a range from 1% by weight to 5% by weight versus the weight of the curable composition.
• the curable composition according to the present disclosure further comprises a crosslinker.
• Those skilled in the art are capable of selecting conventional crosslinkers based on desired physical properties.
• crosslinkers examples include tri(methyl)allyl isocyanurate (TMAIC), triallyl isocyanurate (TAIC), tri(methyl)allyl cyanurate, poly-triallyl isocyanurate (poly-TAIC), xylylene-bis(diallyl isocyanurate) (XBD), N,N′-m-phenylene bismaleimide, diallyl phthalate, tris(diallylamine)-s-triazine, triallyl phosphite, 1,2-polybutadiene, ethyleneglycol diacrylate, diethyleneglycol diacrylate, and CH 2 ⁇ CH—R f1 —CH ⁇ CH 2 , wherein R f1 is a perfluoroalkylene having from 1 to 8 carbon atoms.
• TMAIC tri(methyl)allyl isocyanurate
• TAIC triallyl isocyanurate
• XBD xylylene-bis(diallyl isocyanurate)
• the crosslinker is typically present in an amount of 1% by weight to 10% by weight versus the weight of the curable composition. In some embodiments, the crosslinker is present in a range from 2% by weight to 5% by weight versus the weight of the curable composition.
• Amorphous fluoropolymers useful for practicing the present disclosure may include one or more interpolymerized units derived from at least two principal monomers.
• suitable candidates for the principal monomer(s) include perfluoroolefins (e.g., tetrafluoroethylene (TFE) and hexafluoropropylene (HFP), or any perfluoroolefin of the formula CF 2 ⁇ CF—Rf, where Rf is fluorine or a perfluoroalkyl of 1 to 8, in some embodiments 1 to 3, carbon atoms), perfluorovinyl ethers (e.g., perfluoroalkyl vinyl ethers (PAVE) and perfluoroalkoxyalkyl vinyl ethers (PAOVE)), halogenated fluoroolefins (e.g., trifluorochloroethylene (CTFE)), hydrogen-containing monomers such as olefins (e.g., ethylene and propylene)
• polymerized units derived from non-fluorinated olefin monomers are present in the amorphous fluoropolymer at up to 25 mole percent of the fluoropolymer, in some embodiments up to 10 mole percent or up to 3 mole percent.
• polymerized units derived from at least one of PAVE or PAOVE monomers are present in the amorphous fluoropolymer at up to 50 mole percent of the fluoropolymer, in some embodiments up to 30 mole percent or up to 10 mole percent.
• amorphous fluoropolymer when perhalogenated, in some embodiments perfluorinated, typically at least 50 mole percent (mol %) of its interpolymerized units are derived from TFE and/or CTFE, optionally including HFP.
• the balance of the interpolymerized units of the amorphous fluoropolymer (10 to 50 mol %) is made up of one or more perfluoroalkyl vinyl ethers and/or perfluoroalkoxyalkyl vinyl ethers, and a suitable cure site monomer.
• the fluoropolymer When the fluoropolymer is not perfluorinated, it typically contains from about 5 mol % to about 95 mol % of its interpolymerized units derived from TFE, CTFE, and/or HFP, from about 5 mol % to about 90 mol % of its interpolymerized units derived from VDF, ethylene, and/or propylene, up to about 40 mol % of its interpolymerized units derived from a vinyl ether, and from about 0.1 mol % to about 5 mol %, in some embodiments from about 0.3 mol % to about 2 mol %, of a suitable cure site monomer.
• Suitable perfluorinated ethers include those of the formula CF 2 ⁇ CFO—(CF 2 ) m —(O(CF 2 ) p ) n —ORf, wherein Rf is a perfluorinated (C 1 -C 4 ) alkyl group, m is 1 to 4, n is 0 to 6, and p is 1 to 2, or CF 2 ⁇ CF(CF 2 ) m —O—Rf, wherein m is 1 to 4 and Rf is a perfluorinated aliphatic group optionally containing O atoms.
• perfluoroalkoxyalkyl vinyl ethers include CF 2 ⁇ CFOCF 2 OCF 3 , CF 2 ⁇ CFOCF 2 OCF 2 CF 3 , CF 2 ⁇ CFOCF 2 CF 2 OCF 3 , CF 2 ⁇ CFOCF 2 CF 2 CF 2 OCF 3 , CF 2 ⁇ CFOCF 2 OCF 2 CF 3 , CF 2 ⁇ CFOCF 2 OCF 2 CF 3 , CF 2 ⁇ CFOCF 2 CF 2 OCF 2 CF 3 , CF 2 ⁇ CFOCF 2 CF 2 OCF 2 CF 3 , CF 2 ⁇ CFOCF 2 CF 2 CF 2 OCF 2 CF 3 , CF 2 ⁇ CFOCF 2 CF 2 CF 2 OCF 2 CF 3 , CF 2 ⁇ CFOCF 2 CF 2 OCF 2 OCF 3 , CF 2 ⁇ CFOCF 2 CF 2 OCF 2 OCF 3 , CF 2 ⁇ CFOCF 2 CF
• perfluoroalkoxyalkyl allyl ethers that may be included in the amorphous fluoropolymer include CF 2 ⁇ CFCF 2 OCF 2 CF 2 OCF 3 , CF 2 ⁇ CFCF 2 OCF 2 CF 2 CF 2 OCF 3 and CF 2 ⁇ CFCF 2 OCF 2 OCF 3 .
• These perfluorinated ethers are typically liquids and may be pre-emulsified with an emulsifier before its copolymerization with the other comonomers, for example, addition of a gaseous fluoroolefin.
• amorphous fluoropolymers useful or practicing the present disclosure include a TFE/propylene copolymer, a TFE/propylene/VDF copolymer, a VDF/HFP copolymer, a TFE/VDF/HFP copolymer, a TFE/perfluoromethyl vinyl ether (PMVE) copolymer, a TFE/CF 2 ⁇ CFOC 3 F 7 copolymer, a TFE/CF 2 ⁇ CFOCF 3 /CF 2 ⁇ CFOC 3 F 7 copolymer, a TFE/CF 2 ⁇ C(OC 2 F 5 ) 2 copolymer, a TFE/ethyl vinyl ether (EVE) copolymer, a TFE/butyl vinyl ether (BVE) copolymer, a TFE/EVE/BVE copolymer, a VDF/CF 2 ⁇ CFOC 3 F 7 copolymer, an ethylene/HFP copolymer, ethylene
• the amorphous fluoropolymer presently disclosed is typically prepared by a sequence of steps, which can include polymerization, coagulation, washing, and drying.
• an aqueous emulsion polymerization can be carried out continuously under steady-state conditions.
• an aqueous emulsion of monomers e.g., including any of those described above
• water, emulsifiers, buffers and catalysts are fed continuously to a stirred reactor under optimum pressure and temperature conditions while the resulting emulsion or suspension is continuously removed.
• batch or semibatch polymerization is conducted by feeding the aforementioned 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 monomers into the reactor to maintain a constant pressure until a desired amount of polymer is formed.
• unreacted monomers are removed from the reactor effluent latex by vaporization at reduced pressure.
• the amorphous fluoropolymer can be recovered from the latex by coagulation.
• the polymerization is generally conducted in the presence of a free radical initiator system, such as ammonium persulfate.
• the polymerization reaction may further include other components such as chain transfer agents and complexing agents.
• the polymerization is generally carried out at a temperature in a range from 10° C. and 100° C., or in a range from 30° C. and 80° C.
• the polymerization pressure is usually in the range of 0.3 MPa to 30 MPa, and in some embodiments in the range of 2 MPa and 20 MPa.
• perfluorinated or partially fluorinated emulsifiers may be useful. Generally these fluorinated emulsifiers are present in a range from about 0.02% to about 3% by weight with respect to the polymer. Polymer particles produced with a fluorinated emulsifier typically have an average diameter, as determined by dynamic light scattering techniques, in range of about 10 nanometers (nm) to about 300 nm, and in some embodiments in range of about 50 nm to about 200 nm.
• emulsifiers perfluorinated and partially fluorinated emulsifier having the formula [R f —O-L-COO ⁇ ] i X i+ wherein L represents a linear partially or fully fluorinated alkylene group or an aliphatic hydrocarbon group, R f represents a linear partially or fully fluorinated aliphatic group or a linear partially or fully fluorinated aliphatic group interrupted with one or more oxygen atoms, X i+ represents a cation having the valence i and i is 1, 2 or 3. (See, e.g. U.S. Pat. No. 2007/0015864 to Hinzter et al.).
• Suitable emulsifiers also include perfluorinated polyether emulsifiers having the formula CF 3 —(OCF 2 ) m —O—CF 2 —X, wherein m has a value of 1 to 6 and X represents a carboxylic acid group or salt thereof, and the formula CF 3 —O—(CF 2 ) 3 —(OCF(CF 3 )—CF 2 ) z —O-L-Y wherein z has a value of 0, 1, 2 or 3, L represents a divalent linking group selected from —CF(CF 3 )—, —CF 2 —, and —CF 2 CF 2 — and Y represents a carboxylic acid group or salt thereof.
• Suitable emulsifiers include perfluorinated polyether emulsifiers having the formula R f —O(CF 2 CF 2 O) m CF 2 COOA wherein R f is C n F (2n+1) ; where n is 1 to 4, A is a hydrogen atom, an alkali metal or NH 4 , and m is an integer of from 1 to 3. (See, e.g., U.S. Pat. No. 2006/0199898 to Funaki; Hiroshi et al.).
• Suitable emulsifiers also include perfluorinated emulsifiers having the formula F(CF 2 ) n O(CF 2 CF 2 O) m CF 2 COOA wherein A is a hydrogen atom, an alkali metal or NH 4 , n is an integer of from 3 to 10, and m is 0 or an integer of from 1 to 3.
• perfluorinated emulsifiers having the formula F(CF 2 ) n O(CF 2 CF 2 O) m CF 2 COOA wherein A is a hydrogen atom, an alkali metal or NH 4 , n is an integer of from 3 to 10, and m is 0 or an integer of from 1 to 3.
• Further suitable emulsifiers include fluorinated polyether emulsifiers as described in U.S. Pat. No. 6,429,258 to Morgan et al.
• perfluoroalkyl component of the perfluoroalkoxy has 4 to 12 carbon atoms, or 7 to 12 carbon atoms.
• Suitable emulsifiers also include partially fluorinated polyether emulsifiers having the formula [R f —(O) t —CHF—(CF 2 ) n —COO-] j X i+ wherein R f represents a partially or fully fluorinated aliphatic group optionally interrupted with one or more oxygen atoms, t is 0 or 1 and n is 0 or 1, X i+ represents a cation having a valence i and i is 1, 2 or 3. (See, e.g. U.S. Pat. Publ. No. 2007/0142541 to Hintzer et al.).
• emulsifiers include perfluorinated or partially fluorinated ether containing emulsifiers as described in U.S. Pat. Publ. Nos. 2006/0223924 to Tsuda; Nobuhiko et al., 2007/0060699 to Tsuda; Nobuhiko et al, 2007/0142513 to Tsuda; Nobuhiko et al and 2006/0281946 to Morita; Shigeru et al.
• Fluoroalkyl for example, perfluoroalkyl, carboxylic acids and salts thereof having 6-20 carbon atoms, such as ammonium perfluorooctanoate (APFO) and ammonium perfluorononanoate.
• APFO ammonium perfluorooctanoate
• U.S. Pat. No. 2,559,752 to Berry may also be useful.
• the emulsifiers can be removed or recycled from the fluoropolymer latex as described in U.S. Pat. No. 5,442,097 to Obermeier et al.; U.S. Pat. No. 6,613,941 to Felix et al.; U.S. Pat. No. 6,794,550 to Hintzer et al.; U.S. Pat. No. 6,706,193 to Burkard et al.; and U.S. Pat. No. 7,018,541 Hintzer et al.
• the polymerization process may be conducted with no emulsifier (e.g., no fluorinated emulsifier).
• Polymer particles produced without an emulsifier typically have an average diameter, as determined by dynamic light scattering techniques, in a range of about 40 nm to about 500 nm, typically in range of about 100 nm and about 400 nm, and suspension polymerization will typically produce particles sizes up to several millimeters.
• a water soluble initiator can be useful to start the polymerization process.
• Salts of peroxy sulfuric acid such as ammonium persulfate, are typically applied either alone or sometimes in the presence of a reducing agent, such as bisulfites or sulfinates (disclosed in U.S. Pat. No. 5,285,002 Grootaert and U.S. Pat. No. 5,378,782 to Grootaert) or the sodium salt of hydroxy methane sulfinic acid (sold under the trade designation “RONGALIT”, BASF Chemical Company, New Jersey, USA). Most of these initiators and the emulsifiers have an optimum pH-range where they show most efficiency. For this reason, buffers are sometimes useful.
• Buffers include phosphate, acetate or carbonate buffers or any other acid or base, such as ammonia or alkali metal hydroxides.
• concentration range for the initiators and buffers can vary from 0.01% to 5% by weight based on the aqueous polymerization medium.
• Peroxide-curable amorphous fluoropolymers typically include a chloro, bromo-, or iodo-cure site.
• the amorphous fluoropolymer comprises a bromo- or iodo-cure site.
• the amorphous fluoropolymer comprises an iodo-cure site.
• the cure site can be an iodo-, bromo-, or chloro-group chemically bonded at the end of a fluoropolymer chain.
• the weight percent of elemental iodine, bromine, or chlorine in the amorphous fluoropolymer may range from about 0.2 wt.
• any one of an iodo-chain transfer agent, a bromo-chain transfer agent, or a chloro-chain transfer agent can be used in the polymerization process.
• suitable iodo-chain transfer agents include perfluoroalkyl or chloroperfluoroalkyl groups having 3 to 12 carbon atoms and one or two iodo-groups.
• iodo-perfluoro-compounds include 1,3-diiodoperfluoropropane, 1,4-diiodoperfluorobutane, 1 6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,10-diiodoperfluorodecane, 1,12-diiodoperfluorododecane, 2-iodo-1,2-dichloro-1,1,2-trifluoroethane, 4-iodo-1,2,4-trichloroperfluorobutane and mixtures thereof.
• Suitable bromo-chain transfer agents include perfluoroalkyl or chloroperfluoroalkyl groups having 3 to 12 carbon atoms and one or two iodo-groups.
• Chloro-, bromo-, and iodo-cure site monomers may also be incorporated into the amorphous fluoropolymer by including cure site monomers in the polymerization reaction.
• cure site monomers include those of the formula CX 2 ⁇ CX(Z), wherein each X is independently H or F, and Z is I, Br, or R f —Z, wherein Z is I or Br and R f is a perfluorinated or partially perfluorinated alkylene group optionally containing O atoms.
• the cure site monomers is CH 2 ⁇ CHI, CF 2 ⁇ CHI, CF 2 ⁇ CFI, CH 2 ⁇ CHCH 2 I, CF 2 ⁇ CFCF 2 I, CH 2 ⁇ CHCF 2 CF 2 I, CF 2 ⁇ CFCH 2 CH 2 I, CF 2 ⁇ CFCF 2 CF 2 I, CH 2 ⁇ CH(CF 2 ) 6 CH 2 CH 2 I, CF 2 ⁇ CFOCF 2 CF 2 I, CF 2 ⁇ CFOCF 2 CF 2 CF 2 I, CF 2 ⁇ CFOCF 2 CF 2 CH 2 I, CF 2 ⁇ CFCF 2 OCH 2 CH 2 I, CF 2 ⁇ CFO(CF 2 ) 3 OCF 2 CF 2 I, CH 2 ⁇ CHBr,
• the chain transfer agents having the cure site and/or the cure site monomers can be fed into the reactor by batch charge or continuously feeding. Because feed amount of chain transfer agent and/or cure site monomer is relatively small compared to the monomer feeds, continuous feeding of small amounts of chain transfer agent and/or cure site monomer into the reactor is difficult to control. Continuous feeding can be achieved by a blend of the iodo-chain transfer agent in one or more monomers. Examples of monomers useful for such a blend include hexafluoropropylene (HFP) and perfluoromethyl vinyl ether (PMVE).
• HFP hexafluoropropylene
• PMVE perfluoromethyl vinyl ether
• amphorphous fluoropolymers useful for practicing the present disclosure have weight average molecular weights in a range from 10,000 grams per mole to 200,000 grams per mole. In some embodiments, the weight average molecular weight is at least 15,000, 20,000, 25,000, 30,000, 40,000, or 50,000 grams per mole up to 100,000, 150,000, 160,000, 170,000, 180,000, or up to 190,000 grams per mole.
• Amorphous fluoropolymers disclosed herein typically have a distribution of molecular weights and compositions. Weight average molecular weights can be measured, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using techniques known to one of skill in the art.
• Amorphous fluoropolymers useful for practicing the present disclosure may have a Mooney viscosity in a range from 0.1 to 100 (ML 1+10) at 100° C. according to ASTM D1646-06 TYPE A. In some embodiments, amorphous fluoropolymers useful for practicing the present disclosure have a Mooney viscosity in a range from 0.1 to 20, 0.1 to 10, or 0.1 to 5 (ML 1+10) at 100° C. according to ASTM D1646-06 TYPE A.
• any coagulant which is commonly used for coagulation of a fluoropolymer latex may be used, and it may, for example, be a water soluble salt (e.g., calcium chloride, magnesium chloride, aluminum chloride or aluminum nitrate), an acid (e.g., nitric acid, hydrochloric acid or sulfuric acid), or a water-soluble organic liquid (e.g., alcohol or acetone).
• the amount of the coagulant to be added may be in range of 0.001 to 20 parts by mass, for example, in a range of 0.01 to 10 parts by mass per 100 parts by mass of the fluorinated elastomer latex.
• the fluorinated elastomer latex may be frozen for coagulation.
• the coagulated amorphous fluoropolymer can be collected by filtration and washed with water.
• the washing water may, for example, be ion exchanged water, pure water, or ultrapure water.
• the amount of the washing water may be from 1 to 5 times by mass to the amorphous fluoropolymer, whereby the amount of the emulsifier attached to the amorphous fluoropolymer can be sufficiently reduced by one washing.
• Curable compositions according to the present disclosure can be prepared by compounding the solvent, amorphous fluoropolymer, peroxide, and optionally the crosslinker described above.
• Compounding can be carried out, for example, on a roll mill (e.g., two-roll mill), internal mixer (e.g., Banbury mixers), or other rubber-mixing device. Thorough mixing is typically desirable to distribute the components and additives uniformly throughout the curable composition so that it can cure effectively.
• the compounding can be carried out in one or several steps. For example, certain components such as the crosslinker may be compounded into a mixture of the amorphous fluoropolymer, solvent, and peroxide just before use.
• the solvent may be compounded into a mixture of the amorphous fluoropolymer, peroxide, and optionally crosslinker in a second step. It is typically desirable that the temperature of the composition during mixing should not rise high enough to initiate curing. For example, the temperature of the composition may be kept at or below about 50° C.
• Curable compositions according to the present disclosure can also be made by combining the solvent, amorphous fluoropolymer, peroxide, and optionally the crosslinker described above and shaking or stirring the mixture, if necessary, until a solution is formed.
• the amount of solvent may be in excess of 39% by weight versus the weight of the composition. In such instances, the solvent may be removed by heat and/or reduced pressure until the curable composition disclosed herein is achieved.
• curable compositions according to the present disclosure have an unexpectedly low viscosity in view of the high weight percentage of amorphous peroxide-curable fluoropolymer in the composition.
• the curable composition has a viscosity at 25° C. in a range from 100 poise to 24,000 poise.
• the curable composition has a viscosity at 25° C. in a range from 1,000 poise to 10,000 poise. Viscosities in these ranges allow the curable composition to be used easily, for example, as a caulk.
• Unexpectedly low viscosities for the curable compositions according to the present disclosure are shown in the Examples, below.
• curable compositions of Examples 1 and 2 which included 75% by weight amorphous fluoropolymer and 21% by weight butyl acetate, had viscosities 1,800 and 2,217 poise, respectively.
• Curable compositions of Examples 3 to 10 which included 80% by weight amorphous fluoropolymer and 16% by weight of solvents including DMC, methyl acetate, tert-butyl acetate, acetone, ethyl acetate, butyl acetate, MEK, and MIBK ranged in viscosities from 1,109 poise to 5,682 poise.
• curable compositions having the amorphous fluoropolymer in a range from greater than 80 percent by weight to 97.5 percent by weight versus the weight of the curable composition have viscosities at 25° C. in a range from 4500 poise to 24,000 poise, depending on the solvent.
• curable compositions having at least 90% amorphous fluoropolymer by weight, versus the weight of the curable compositions can have viscosities of less than 15,000 poise.
• curable compositions according to the present disclosure have an unexpected ability to cure in view of the solvent present in the curable composition.
• the curing of an amorphous fluoropolymer can be evaluated on a sealed torsion shear rotorless curemeter in accordance with ASTM D 5289-07 by measuring delta torque or tan delta.
• Delta torque is the difference between maximum torque and minimum torque, and it is related to crosslink density of cured fluoroelastomer. A higher delta torque indicates the fluoroelastomer has more crosslinking or a higher crosslink density.
• curable compositions disclosed herein have a delta torque at 130° C. for 12 minutes of at least 0.4 dNm or 0.5 dNm as measured by a sealed torsion shear rotorless curemeter in accordance with ASTM D 5289-07.
• the delta torque at 130° C. for 12 minutes is at least 1.0 dNm or at least 2.0 dNm.
• curable compositions disclosed herein have a tan delta after 12 minutes at 130° C.
• curable compositions according to the present disclosure exhibit cure at 130° C. as measured by a sealed torsion shear rotorless curemeter in view of Illustrative Examples 5 and 10, which include 50% by weight fluoropolymer and greater than 40% by weight solvent versus the weight of the composition.
• curable compositions according to the present disclosure also have good shelf stability. For example, as shown in Example 11, below, a curable composition was still fluid after 314 days at room temperature and was still readily cured at 130° C. as measured by a sealed torsion shear rotorless curemeter in accordance with ASTM D 5289-07. Thus, in many embodiments, the curable compositions according to the present disclosure are shelf stable and yet unexpectedly curable at or above peroxide-decomposition temperatures.
• the curable composition according to the present disclosure can be used to make cured fluoroelastomers in the form of a variety of articles, including final articles, such as O-rings, and/or preforms from which a final shape is made, (e.g. a tube from which a ring is cut).
• final articles such as O-rings, and/or preforms from which a final shape is made, (e.g. a tube from which a ring is cut).
• the curable composition can be extruded using a screw type extruder or a piston extruder.
• the extruded or pre-formed curable compositions can be cured in an oven at ambient pressure.
• the curable composition can be shaped into an article using injection molding, transfer molding, or compression molding.
• Injection molding of the curable composition for example, can be carried out by masticating the curable composition in an extruder screw and collecting it in a heated chamber from which it is injected into a hollow mold cavity by means of a hydraulic piston. After vulcanization the article can then be demolded.
• Advantages of injection molding process include short molding cycles, little or no preform preparation, little or no flash to remove, and low scrap rate. Since the viscosity of the curable composition is relatively low, the cylinder, barrel and screw temperature can be low, and the fill or injection time can be minimized.
• the curable composition according to the present disclosure can also be used to prepare cure-in-place gaskets (CIPG) or form-in-place gaskets (FIPG).
• CIPG cure-in-place gaskets
• FIPG form-in-place gaskets
• a bead or thread of the curable composition can be deposited from a nozzle onto a substrate's surface. After forming to a desired gasket pattern, the curable composition may be cured in place with heat, for example, in an oven at ambient pressure.
• the curable composition according to the present disclosure can also be useful as a fluoroelastomer caulk, which can be useful, for example, to fill voids in, coat, adhere to, seal, and protect various substrates from chemical permeation, corrosion, and abrasion, for example.
• Fluoroelastomer caulk can be useful as a joint sealant for steel or concrete containers, seals for flue duct expansion joints, door gaskets sealants for industrial ovens, fuel cell sealants or gaskets, and adhesives for bonding fluoroelastomer gaskets (e.g., to metal).
• the curable composition can be dispensed by hand and cured with heat at ambient pressure.
• the curable composition is positioned on a substrate before heating the curable composition at a cure temperature.
• the cure temperature can be selected based on the decomposition temperature of the peroxide.
• a temperature can be selected that is above (in some embodiments, at least 10° C., 20° C., 30° C., 40° C., or at least 50° C. above) the ten-hour half-life temperature of the peroxide.
• the cure temperature is above 100° C.
• the cure temperature is in a range from 120° C. to 180° C.
• the cure time can be at least 5, 10, 15, 20, or 30 minutes up to 24 hours, depending on the composition of the peroxide-curable, amorphous fluoropolymer and the cross-sectional thickness of the cured fluoroelastomer.
• a solvent removal step is not necessary before curing the curable composition to make a cured fluoroelastomer. Accordingly, in some embodiments of the method of making a cured fluoroelastomer according to the present disclosure, heating the curable composition at a cure temperature is carried out without first removing the solvent. In many solvent-cast fluoroelastomer coatings, a drying step precedes the curing step. This step can add time and cost to a process. Such a drying step is typically carried out at a temperature below the ten-hour half-life temperature of the peroxide.
• the drying can carried out at a temperature of at least 20° C., 25° C., or 30° C. below the ten-hour half-life temperature of the peroxide. Therefore, in some embodiments of the method of making a cured fluoroelastomer according to the present disclosure, heating the curable compositions at two distinct temperatures and/or heating the curable composition at a temperature below the ten-hour half-life temperature of the peroxide is avoided.
• the cured fluoroelastomer prepared by the method disclosed herein contains solvent. Because of the compatibility of the solvent with the cured fluoroelastomer and because of the low ozone impact of the solvent in some embodiments of the curable composition and cured fluoroelastomer made from the curable composition, residual solvent in the cured fluoroelastomer need not be removed before use.
• the cured fluoroelastomer is post-cured at a temperature sufficient to remove the solvent.
• the cured fluoroelastomer can be post-cured, for example, in an oven at a temperature of about 120° C.
• Additives such as carbon black, stabilizers, plasticizers, lubricants, fillers, and processing aids typically utilized in fluoropolymer compounding can be incorporated into the curing compositions, provided they have adequate stability for the intended service conditions. In particular, low temperature performance can be enhanced by incorporation of perfluoropolyethers. See, for example, U.S. Pat. No. 5,268,405 to Ojakaar et al.
• Carbon black fillers can be employed in fluoropolymers 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) and large particle size furnace blacks. When used, 1 to 100 parts filler per hundred parts fluoropolymer (phr) of large size particle black is generally sufficient.
• Fluoropolymer fillers may also be present in the curable compositions. Generally, from 1 to 100 phr of fluoropolymer filler is used.
• the fluoropolymer filler can be finely divided and easily dispersed as a solid at the highest temperature used in fabrication and curing of the curable composition. By solid, it is meant that the filler material, if partially crystalline, will have a crystalline melting temperature above the processing temperature(s) of the curable composition(s).
• One way to incorporate fluoropolymer filler is by blending latices. This procedure, using various kinds of fluoropolymer filler, is described in U.S. Pat. No. 6,720,360 to Grootaert et al.
• the curable composition according to the present disclosure is free of fillers or contains less than 5%, 2%, or 1% by weight fillers versus the weight of the curable composition.
• the curable composition according to the present disclosure can be free of inorganic fillers.
• One advantage to avoiding fillers in the curable compositions disclosed herein is that visible light transmissive cured fluoroelastomers may be obtained. In part because of the compatibility of the solvent with the cured fluoroelastomer, the cured fluoroelastomer prepared from the curable composition disclosed herein can have relatively high visible and infrared light transmission.
• the cured fluoroelastomer prepared by the method disclosed herein has an average visible light transmission of at least about 70 percent (in some embodiments, at least about 75 or 80 percent). In some embodiments, the cured fluoroelastomer prepared by the method disclosed herein has an average transmission over a range of 360 nm to 1100 nm of at least about 70 percent (in some embodiments, at least about 75 or 80 percent). Even in embodiments in which the cured fluoroelastomer does not incorporate a filler, useful mechanical properties are obtained. See, for example, Example 34, below.
• acid acceptors may be employed to facilitate the cure and thermal stability of the compound.
• Suitable acid acceptors may include magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphite, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, hydrotalcite, alkali stearates, magnesium oxalate, or combinations thereof.
• the acid acceptors can be used in amounts ranging from about 1 to about 20 parts per 100 parts by weight of the amorphous fluoropolymer.
• the curable composition is free of such adjuvants or includes less than 0.5% by weight of such adjuvants versus the weight of the curable composition.
• the curable composition is free of silanes or includes less than 1% or less than 0.5% of a silane.
• silanes include aminosilanes or Schiff bases derived from aminosilanes.
• the present disclosure provides a curable composition
• a curable composition comprising: an amorphous, peroxide-curable fluoropolymer having a first solubility parameter, wherein the amorphous, peroxide-curable fluoropolymer is present from 60 percent to 97.5 percent by weight versus the weight of the curable composition,
• a solvent having a second solubility parameter wherein the solvent is present from 1 percent to 39 percent by weight versus the weight of the curable composition, and a peroxide, wherein the absolute value of the first solubility parameter minus the second solubility parameter is less than or equal to 8.2 (MPa) 1/2 .
• the present disclosure provides the curable composition of the first embodiment, wherein the absolute value of the first solubility parameter minus the second solubility parameter is less than or equal to 4.1 (MPa) 1/2 .
• the present disclosure provides a curable composition comprising:
• an amorphous, peroxide-curable fluoropolymer wherein the amorphous, peroxide-curable fluoropolymer is present from 60 percent to 97.5 percent by weight versus the weight of the curable composition, a solvent having a solubility parameter in a range from 9.6 (MPa) 1/2 to 26 (MPa) 1/2 , wherein the solvent is present from 1 percent to 39 percent by weight versus the weight of the curable composition, and a peroxide.
• the present disclosure provides the curable composition of the third embodiment, wherein the solubility parameter of the solvent is in a range from 13.7 (MPa) 1/2 to 21.9 (MPa) 1/2 .
• the present disclosure provides the curing composition of any one of the first to fourth embodiments, wherein the amorphous peroxide-curable fluoropolymer is not present at 80 percent by weight versus the weight of the curable composition.
• the present disclosure provides the curable composition of any one of the first to fifth embodiments, wherein the amorphous peroxide-curable fluoropolymer is present in a range from 60 percent by weight to less than 80 percent by weight versus the weight of the curable composition.
• the present disclosure provides the curable composition any one of the first to fifth embodiments, wherein the amorphous peroxide-curable fluoropolymer is present in a range from greater than 80 percent by weight to 97.5 percent by weight versus the weight of the curable composition.
• the present disclosure provides the curable composition of any one of the first to seventh embodiments, further comprising a crosslinker.
• the present disclosure provides the curable composition of the first to eighth embodiment, wherein the crosslinker is tri(methyl)allyl isocyanurate, triallyl isocyanurate, tri(methyl)allyl cyanurate, poly-triallyl isocyanurate, xylylene-bis(diallyl isocyanurate), N,N′-m-phenylene bismaleimide, diallyl phthalate, tris(diallylamine)-s-triazine, triallyl phosphite, 1,2-polybutadiene, ethyleneglycol diacrylate, diethyleneglycol diacrylate, or CH 2 ⁇ CH—R f1 —CH ⁇ CH 2 wherein R f1 is a perfluoroalkylene having from 1 to 8 carbon atoms.
• the crosslinker is tri(methyl)allyl isocyanurate, triallyl isocyanurate, tri(methyl)allyl cyanurate, poly-triallyl isocyanurate, xyly
• the present disclosure provides the curable composition of the eighth or ninth embodiment, wherein the crosslinker is present in the curable composition in a range from 1 percent to 10 percent by weight.
• the present disclosure provides the curable composition of any one of the first to tenth embodiments, wherein the amorphous, peroxide-curable fluoropolymer comprises a bromo- or iodo-cure site.
• the present disclosure provides the curable composition of the eleventh embodiment, wherein the amorphous, peroxide-curable fluoropolymer comprises an iodo-cure site.
• the present disclosure provides the curable composition of any one of the first to the twelfth embodiments, wherein the curable composition has a viscosity at 25° C. in a range from 100 poise to 24,000 poise.
• the present disclosure provides the curable composition of any one of the first to thirteenth embodiments, wherein the curable composition has a viscosity at 25° C. in a range from 1,000 poise to 10,000 poise.
• the present disclosure provides the curable composition of any one of the first to fourteenth embodiments, wherein the peroxide is an acyl peroxide.
• the present disclosure provides the curable composition of any one of the first to fifteenth embodiments, wherein the peroxide is a diacyl peroxide.
• the present disclosure provides the curable composition of any one of the first to sixteenth embodiments, wherein the peroxide is present in the curable composition in a range from 0.5 percent to 10 percent by weight.
• the present disclosure provides the curable composition of any one of the first to seventeenth embodiments, wherein the solvent has a boiling point in a range from 30° C. to 200° C.
• the present disclosure provides the curable composition of any one of the first to eighteenth embodiments, having a delta torque at 130° C. for 12 minutes greater than 0.5 dNm as measured by a sealed torsion shear rotorless curemeter in accordance with ASTM D 5289-07.
• the present disclosure provides the curable composition of any one of the first to nineteenth embodiments, having a tan delta after 12 minutes at 130° C. of less than 0.3 as measured by a sealed torsion shear rotorless curemeter in accordance with ASTM D 5289-07.
• the present disclosure provides the curable composition of any one of the first to twentieth embodiments, wherein the solvent comprises at least one of acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-butyl acetate, tert-butyl acetate, or dimethyl carbonate.
• the solvent comprises at least one of acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-butyl acetate, tert-butyl acetate, or dimethyl carbonate.
• the present disclosure provides the curable composition of the twenty-first embodiment, wherein the solvent is ethyl acetate or methyl acetate.
• the present disclosure provides the curable composition of any one of the first to twenty-first embodiments, wherein the solvent has a calculated ozone impact of up to 0.35 on the maximum incremental reactivity scale measured in units of grams of ozone per grams of solvent.
• the present disclosure provides a method of making a cured fluoroelastomer, the method comprising:
• the present disclosure provides the method of the twenty-fourth embodiment, wherein the method does not include first removing the solvent before heating the curable composition.
• the present disclosure provides the method of the twenty-fourth or twenty-fifth embodiment, wherein the cure temperature is above 100° C.
• the present disclosure provides the method of any one of the twenty-fourth to twenty-sixth embodiments, wherein the cure temperature is at least the ten-hour half-life temperature of the peroxide.
• the present disclosure provides the method of any one of the twenty-fourth to twenty-seventh embodiments, wherein the curable composition is positioned on a substrate before heating the curable composition.
• the present disclosure provides the method of any one of the twenty-fourth to twenty-eighth embodiments, wherein the cured fluoroelastomer has an average light transmission in a range from 360 nanometers to 1100 nanometers of at least 70 percent.
• the present disclosure provides the method of any one of the twenty-fourth to twenty-ninth embodiments, wherein the cured fluoroelastomer includes solvent.
• the present disclosure provides a cured fluoroelastomer made by the method of any one of the twenty-fourth to thirtieth embodiments.
• Polymer Mooney viscosity was determined in accordance with ASTM D1646-06 TYPE A by a MV 2000 instrument (available from Alpha Technologies, Akron, Ohio, USA) using large rotor with one minute preheat and 10 minutes measurement (ML 1+10) at 100° C. Results are reported in Mooney units.
• the polymer solvent solution viscosity was measured using a dynamic mechanical analyzer (DMA), RPA 2000 instrument (available from Alpha Technologies, Akron, Ohio, USA) in accordance with ASTM D 6204-07.
• the apparent viscosity was measured at 1.0% strain and the frequency ( ⁇ ) of 0.2-200 rad/sec.
• the temperature for these measurements was 25° C. 5 g to 7 g of the solution was placed on a polyester terephthalte (PET) film and the solution was cooled in a freezer box at ⁇ 40° C. for 10 min to increase the initial viscosity for preventing overflow the sample when the sample was pressed between the dies.
• DMA dynamic mechanical analyzer
• RPA 2000 instrument available from Alpha Technologies, Akron, Ohio, USA
• the polymer solvent solution viscosity was measured with a Brookfield viscometer DV-II (available from Brookfield Engineering Laboratories, Inc., Middleboro, Mass., USA) in accordance with ASTM D 2196-05.
• the LV4 spindle was used at 0.3 rpm.
• the cure characteristics were measured using a RPA 2000 instrument (available from Alpha Technologies, Akron, Ohio, USA) with Moving Die Rheometer (MDR, a sealed torsion shear rotorless curemeter) mode under conditions corresponding to ASTM D5289-07.
• the frequency was 100 cpm (10.47 rad/s) and the strain was 0.5 degree (6.98%).
• the following parameters were recorded:
• Tensile strength at break and elongation at break were measured using a T2000 tensometer (available from Alpha Technologies, Akron, Ohio, USA) in accordance with ASTM D 412-06a.
• the dumbbells for mechanical properties were cut with ASTM Die D.
• Amorphous Fluoropolymer A was prepared as follows. An 80 liter reactor was charged with 52 kg water, 40 g ammonium persulfate (APS, (NH 4 ) 2 S 2 O 8 ) and 160 g of a 50% aqueous solution of potassium phosphate dibasic (K 2 HPO 4 ). The reactor was evacuated, the vacuum was broken and it was pressurized with nitrogen to 25 psi (0.17 MPa). This vacuum and pressurization was repeated three times. After removing oxygen, the reactor was heated to 80° C.
• APS ammonium persulfate
• K 2 HPO 4 potassium phosphate dibasic
• HFP hexafluoropropylene
• NOVEC HFE-7500 2-trifluoromethyl-3-ethoxydodecafluorohexane
• HFP was added based on the amount of 1,4-diiodooctafluorobutane added.
• the blend was then attached to the reactor and was fed using a blanket of N 2 .
• the blend contained 89.9 wt % of HFP and variable wt % amounts of 1,4-diiodooctafluorobutane and “NOVEC HFE 7500” according to Table 1 for Amorphous Fluoropolymers A-D.
• VDF vinylidene fluoride
• HFP hexafluoropropylene
• NOVEC HFE 7500 hexafluoropropylene
• Total precharge of VDF and the blend of HFP, 1,4-diiodooctafluorobutane and “NOVEC HFE 7500” was 800 g, and 1536 g, respectively.
• the reactor was agitated at 450 rpm.
• the blend of hexafluoropropylene (HFP), 1,4-diiodooctafluorobutane and “NOVEC HFE 7500” and VDF was continuously fed to the reactor to maintain the pressure at 220 psi (1.52 MPa).
• the ratio of the blend and VDF was 0.651 by weight and no emulsifier was used for the polymerization.
• the monomer and blend feeds were discontinued and the reactor was cooled.
• the resulting dispersion had a solid content of 29.7 wt. % and a pH of 3.6.
• the dispersion particle size was 323 nm and the total amount of dispersion was about 76.5 kg.
• Amorphous Fluoropolymer E is commercially available as “E-18894” from 3M Company.
• the fluoropolymer has a 36 Mooney viscosity measured at 100° C., is a terpolymer of tetrafluoroethylene (TFE), hexafluoropropylene (HFP) and vinylidene fluoride (VDF), and is 65.7% of fluorine by weight.
• a curable composition was prepared using a 15 cm (6 inch) two roll mill by compounding Amorphous Fluoropolymer A prepared as described under “Amorphous Fluoropolymer A-D preparation” with 2 phr of benzoyl peroxide (BPO, available under the trade designation “LUPEROX A98” from Aldrich, Milwaukee, Wis.). Then a 75% solution by weight was made by dissolving 20.4 g of the compounded Amorphous Fluoropolymer A and BPO in 5.68 g of butyl acetate with 0.6 g of triallylisocyanurate (TAIC) co-agent (98%, obtained under the trade designation “TAIC” from Nippon Kasei, Japan) in a glass jar.
• TAIC triallylisocyanurate
• the glass jar was shaken on a shaker for 16 hrs and the polymer was dissolved.
• the solution formulation is summarized in Table 2 based on parts per hundred rubber (phr).
• the solution viscosity was measured as described under “Solution DMA Viscosity” and the viscosity of the solution at 25° C. and 200 rad/s was 1,800 poise.
• the sample was cured as described under “Cure Rheology”. Results are shown in Table 3.
• Example 2 and Illustrative Example 1 were prepared and tested according to the methods of Example 1 except the peroxides in Table 2 were used instead of benzoyl peroxide (BPO).
• BPO benzoyl peroxide
• the 2,4-dichlorobenzoyl peroxide (CBPO) is available from 3B Scientific Corp., Libertyville, Ill., and 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane (DBPH) is available under the trade designation “LUPEROX 101” from Aldrich, Milwaukee, Wis.
• the solution viscosities were measured as described under “Solution DMA Viscosity”, and the samples were cured as described under “Cure Rheology”.
• Results are shown in Table 3 and indicate significantly improved cure when using benzoyl peroxide (BPO).
• BPO benzoyl peroxide
• Example 2 Ex 1 Formulation (phr) Amorphous Fluoropolymer A 100 100 100 100 TAIC 3 3 3 3 Butyl acetate 28.4 28.4 28.4 Benzoyl peroxide (BPO) 2 0 0 2,4-diclhlorbenzoyl peroxide (CBPO) 0 2 0 2,5-diemthyl-2,5-di(t-butylperoxy)- 0 0 2 hexane (DBPH) Polymer wt % 75 75 75 75 75 75 75 75 75 75 75 75 75 75
• the amorphous fluoropolymer was completely dissolved in the solvents, and the results are summarized in Table 4.
• the “Solution DMA Viscosity” and the “Solution Brookfield Viscosity” of Example 8 was measured at various temperatures from 25° C. to 40° C. and the results are summarized in Table 5.
• DMA viscosity ( ⁇ ′) was measured at 200 rad/s with 1% strain and Brookfield viscosity was measured at 0.3 rpm using LV4 spindle.
• Example 11 The curable composition of Example 11 was prepared and tested according to the methods of Example 1 except the fluoropolymer content (%) was 60. The sample was cured as described under “Cure Rheology”. Also “Cure Rheology” was measured again after 314 days for the same curable composition stored at room temperature in a jar. The results are shown in Table 6.
• Example 29 the curable composition was prepared and tested according to the methods of Example 1 except Amorphous Fluoropolymer B was used instead of Amorphous Fluoropolymer A.
• Example 30 the solution was prepared and tested according to the methods of Example 16 except Amorphous Fluoropolymer B was used instead of Amorphous Fluoropolymer A.
• Example 31 the solution was prepared and tested according to the methods of Example 1 except Amorphous Fluoropolymer C was used instead of Amorphous Fluoropolymer A. The results are summarized in Table 9.
• a 50% by weight amorphous fluoropolymer solution was prepared by dissolving 100 g of Amorphous Fluoropolymer D with 2 g of benzoyl peroxide (BPO) and 3 g of triallylisocyanurate (TAIC) in 95 g of ethyl acetate as the solvent (boiling point: 77° C.) in a glass jar. The glass jar was shaken on a shaker for 16 hours and the polymer, BPO, and TAIC were dissolved. “Solution Brookfield Viscosity” was 7.8 poise with LV4 spindle at 100 rpm.
• a sample of 43.7 g of the solution of Illustrative Example 10 was coated onto a poly(ethylene terephthalate) (PET) film, and the coated solution on the PET sheet was dried in an oven at 50° C. for 10 minutes to evaporate the solvent. After drying, the weight of the coated solution was 30.9 g, and the calculated amorphous fluoropolymer content of the coated solution was 70.7%.
• the coated solution was removed from the PET film to measure solution viscosity and cure. The viscosity was measured as described under “Solution DMA Viscosity”, and the sample was cured as described under “Cure Rheology”. The results are shown in Table 10.
• a sample of 16.7 g of the solution of Illustrative Example 10 was coated onto a PET film, and the coated solution on the PET sheet was dried in an oven at 50° C. for 10 minutes and at 23° C. for 16 hours to evaporate the solvent. After drying, the weight of the coated solution was 8.6 g, and the calculated amorphous fluoropolymer content of the coated solution was 97.3%.
• the coated solution was removed from the PET film to measure solution viscosity and cure. The viscosity was measured as described under “Solution DMA Viscosity”, and the sample was cured as described under “Cure Rheology”. The results are shown in Table 10.
• Example 34 a 30% by weight amorphous fluoropolymer solution was prepared by dissolving 50 g of Amorphous Fluoropolymer E with 1 g of benzoyl peroxide (BPO) and 1.5 g of triallylisocyanurate (TAIC) in 114 g of MEK in a glass jar. The glass jar was shaken on a shaker for 16 hours, and the polymer, BPO and TAIC were dissolved. The “Solution Brookfield Viscosity” was 3.4 poise with LV4 spindle at 100 rpm. The solution (60.7 g) was coated onto a PET film, and the coated solution on the PET sheet was dried in an oven at 50° C. for 30 minutes.
• BPO benzoyl peroxide
• TAIC triallylisocyanurate
• the weight of the coated solution was 22 g, and the calculated amorphous fluoropolymer content of the coated solution was 82.5%.
• the dried solution was removed from the PET film to measure solution viscosity and cure. The viscosity was measured as described under “Solution DMA Viscosity” and the sample was cured as described under “Cure Rheology”.
• the dried solution was further cured at 130° C. for 10 minutes.
• the cured “dried solution” was removed as a film from the PET film and the thickness of the cured film was 0.34 mm.
• the cured film was clear.
• Three dumbbells for mechanical property testing were cut from the cured film with ASTM Die D. Tensile strength at break and elongation at break were measured as described under “Mechanical Properties”. The tensile strength at break was 7.6 MPa (1,096 psi) and elongation at break was 623%.
• Example 10 The solution of Illustrative Example 10 was coated onto a PET film, and the coated solution on the PET sheet was dried in an oven at 50° C. for 10 minutes to evaporate the solvent. After drying for this time and temperature, the calculated amorphous fluoropolymer content of Example 32 was 70.7% (see Example 32 above).
• the dried solution of Example 35 was further cured at 130° C. for 10 minutes.
• the cured “dried solution” was removed as a film from the PET film and the thickness of the cured film was 0.3 mm.
• the cured film was clear and showed a good mechanical property. Transmission was tested using E20 UV-VIS spectroscopy (available from Parkin Elmer Waltham, Mass.). The average transmission of the film from 360 nm to 1100 nm was 81%.

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