WO2024081314A1 - Compositions de fluoroélastomères durcissables et fluoroélastomères durcis à faible frottement (fkm) formés à partir de celles-ci - Google Patents

Compositions de fluoroélastomères durcissables et fluoroélastomères durcis à faible frottement (fkm) formés à partir de celles-ci Download PDF

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WO2024081314A1
WO2024081314A1 PCT/US2023/034944 US2023034944W WO2024081314A1 WO 2024081314 A1 WO2024081314 A1 WO 2024081314A1 US 2023034944 W US2023034944 W US 2023034944W WO 2024081314 A1 WO2024081314 A1 WO 2024081314A1
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fluoroelastomer
curable
curable fluoroelastomer
cured
composition
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PCT/US2023/034944
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English (en)
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Chorong JEONG
Ayako YOSHIURA
Kenji Terauchi
Takeshi Sato
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The Chemours Company Fc, Llc
Chemours-Mitsui Fluoroproducts Co., Ltd.
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Publication of WO2024081314A1 publication Critical patent/WO2024081314A1/fr

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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen

Definitions

  • compositions and methods for curing fluoroelastomers and cured fluoroelastomers More specifically, this disclosure relates to curable fluoroelastomer compositions including a curable fluoroelastomer, a dehydrohalogenating agent, an acid acceptor including bismuth oxide, and at least one silicon-containing chemical.
  • the high rotation speed of the motor shaft generates excessive frictional heat on the sealing material, and a decrease of the surface friction is considered important to minimize the heat generation and to enable the system design with high motor rotation speed.
  • Curable fluoroelastomer compositions disclosed herein provide low-friction cured fluoroelastomers. Friction reduction of fluoroelastomers can highly contribute to improved energy efficiency and cost reduction relative to conventional low-friction coating processes.
  • a curable fluoroelastomer composition comprises a curable fluoroelastomer, a dehydrohalogenating agent, an acid acceptor comprising bismuth oxide (Bi20s) present in the curable fluoroelastomer composition in an amount of at least 3 parts per hundred parts by weight of the curable fluoroelastomer (phr), and at least one silicon-containing chemical present in the curable fluoroelastomer composition in an amount of at least 0.05 parts per hundred parts by weight of the curable fluoroelastomer.
  • Bi20s bismuth oxide
  • the bismuth oxide is present in the curable fluoroelastomer composition in an amount of 5 to 15 parts per hundred parts by weight of the curable fluoroelastomer.
  • the at least one silicon- containing chemical is present in the curable fluoroelastomer composition in an amount of 0.05 to 5 parts per hundred parts by weight of the curable fluoroelastomer.
  • the at least one silicon- containing chemical is selected from the group consisting of silicon dioxide, calcium silicate (Ca2SiC>4), calcium metasilicate (CaSiOs), an organosilicone, y-aminopropyltriethoxylsilane, vinylethoxysilane, and combinations thereof.
  • the dehydrohalogenating agent is present in the curable fluoroelastomer composition in an amount of at least 1.0 parts per hundred parts by weight of the curable fluoroelastomer.
  • the dehydrohalogenating agent is selected from the group consisting of 2,2 bis(4 hydroxyphenyl)hexafluoropropane, methylhydroquinone, and 2-methylresorcinol.
  • the curable fluoroelastomer comprises a peroxide-curable fluoroelastomer curable by a peroxide cure system and the curable fluoroelastomer composition further comprises a peroxide curative.
  • the curable fluoroelastomer composition contains less than 0.1 parts per hundred parts by weight of the curable fluoroelastomer of magnesium oxide and calcium hydroxide, in combination.
  • the curable fluoroelastomer composition is free or substantially free of magnesium oxide and calcium hydroxide.
  • the curable fluoroelastomer is a dipolymer of hexafluoropropylene and vinylidene fluoride.
  • a cured fluoroelastomer cured from a curable fluoroelastomer composition comprises a curable fluoroelastomer, a dehydrohalogenating agent, an acid acceptor comprising bismuth oxide (Bi20s) present in the curable fluoroelastomer composition in an amount of at least 3 parts per hundred parts by weight of the curable fluoroelastomer, and at least one silicon- containing chemical present in the curable fluoroelastomer composition in an amount of at least 0.05 parts per hundred parts by weight of the curable fluoroelastomer.
  • Bi20s bismuth oxide
  • the bismuth oxide is present in the curable fluoroelastomer composition in an amount of 5 to 15 parts per hundred parts by weight of the curable fluoroelastomer.
  • the at least one silicon- containing chemical is present in the curable fluoroelastomer composition in an amount of 0.05 to 5 parts per hundred parts by weight of the curable fluoroelastomer.
  • the at least one silicon- containing chemical is selected from the group consisting of silicon dioxide, calcium metasilicate (CaSiOs), an organosilicone, y-aminopropyltriethoxylsilane, vinylethoxysilane, and combinations thereof.
  • the dehydrohalogenating agent is present in the curable fluoroelastomer composition in an amount of at least 1.0 parts per hundred parts by weight of the curable fluoroelastomer.
  • the dehydrohalogenating agent is selected from the group consisting of 2,2-bis(4-hydroxyphenyl)hexafluoropropane, methylhydroquinone, and 2- methylresorcinol.
  • the curable fluoroelastomer comprises a peroxide-curable fluoroelastomer curable by a peroxide cure system and the curable fluoroelastomer composition further comprises a peroxide curative.
  • the curable fluoroelastomer composition contains less than 0.1 parts per hundred parts by weight of the curable fluoroelastomer of magnesium oxide and calcium hydroxide, in combination.
  • the cured fluoroelastomer is free or substantially free of magnesium oxide and calcium hydroxide.
  • the cured fluoroelastomer has a static coefficient of friction of less than 0.5.
  • the cured fluoroelastomer has a static coefficient of friction of 0.2 to 0.4.
  • the cured fluoroelastomer has a dynamic coefficient of friction of less than 0.5.
  • the cured fluoroelastomer has a dynamic coefficient of friction of 0.15 to 0.4.
  • the cured fluoroelastomer has a tensile strength of 9.0 to 25 MPa.
  • a method of curing a curable fluoroelastomer comprises forming a curable fluoroelastomer composition and heating the curable fluoroelastomer composition to a cure temperature to cure the curable fluoroelastomer.
  • the curable fluoroelastomer composition comprises the curable fluoroelastomer, a dehydrohalogenating agent, an acid acceptor comprising bismuth oxide (Bi20s) present in the curable fluoroelastomer composition in an amount of at least 3 parts per hundred parts by weight of the curable fluoroelastomer, and at least one silicon-containing chemical present in the curable fluoroelastomer composition in an amount of at least 0.05 parts per hundred parts by weight of the curable fluoroelastomer.
  • Bi20s bismuth oxide
  • the heating comprises press curing the curable fluoroelastomer composition and wherein the cure temperature is in the range of about 160 to about 190 °C and the cure time is in the range of about 5 minutes to about 90 minutes.
  • the method further comprises post curing the cured fluoroelastomer at a post cure temperature for a post cure time.
  • the post cure temperature is in the range of in the range of about 200 to about 260 °C and the post cure time is about 15 minutes or greater.
  • the bismuth oxide is present in the curable fluoroelastomer composition in an amount of 5 to 15 parts per hundred parts by weight of the curable fluoroelastomer.
  • the at least one silicon-containing chemical is present in the curable fluoroelastomer composition in an amount of 0.05 to 5 parts per hundred parts by weight of the curable fluoroelastomer.
  • the at least one silicon-containing chemical is selected from the group consisting of silicon dioxide, calcium silicate (Ca2SiC>4), calcium metasilicate (CaSiOs), an organosilicone, y-aminopropyltriethoxylsilane, vinylethoxysilane, and combinations thereof.
  • the dehydrohalogenating agent is present in the curable fluoroelastomer composition in an amount of at least 1 .0 parts per hundred parts by weight of the curable fluoroelastomer.
  • the dehydrohalogenating agent is selected from the group consisting of 2,2-bis(4-hydroxyphenyl)hexafluoropropane, methylhydroquinone, and 2-methylresorcinol.
  • the curable fluoroelastomer comprises a peroxide-curable fluoroelastomer curable by a peroxide cure system and the curable fluoroelastomer composition further comprises a peroxide curative.
  • the curable fluoroelastomer composition contains less than 0.1 parts per hundred parts by weight of the curable fluoroelastomer of magnesium oxide and calcium hydroxide, in combination.
  • the cured fluoroelastomer is free or substantially free of magnesium oxide and calcium hydroxide.
  • the cured fluoroelastomer has a static coefficient of friction of less than 0.5.
  • the cured fluoroelastomer has a static coefficient of friction of 0.2 to 0.4.
  • the cured fluoroelastomer has a dynamic coefficient of friction of less than 0.5.
  • the cured fluoroelastomer has a dynamic coefficient of friction of 0.15 to 0.4.
  • curable fluoroelastomer compositions and cured fluoroelastomers including bismuth oxide and at least one silicon-containing chemical.
  • the compositions and methods provide low- friction cured fluoroelastomers.
  • the low-friction cured fluoroelastomers are free or substantially free of strong acid acceptors, which include, but are not limited to, magnesium oxide, calcium oxide, and calcium hydroxide.
  • silicon-containing chemical or “Si-containing chemical” refers to any chemical compound including silicon.
  • low-friction cured fluoroelastomer refers to a cured fluoroelastomer having a static coefficient of friction of less than 1 and a dynamic coefficient of friction of less than 1 .
  • the low-friction cured fluoroelastomer has a static coefficient of friction of about 0.5 or less and a dynamic coefficient of friction of about 0.5 or less.
  • substantially free of strong acid acceptors refers to a curable fluoroelastomer composition or a cured fluoroelastomer formed from a curable fluoroelastomer composition having less than 1 part per hundred parts by weight of the curable fluoroelastomer (phr) of strong acid acceptors.
  • Appropriate amounts of strong acid acceptors in the curable fluoroelastomer composition may include, but are not limited to, less than 1 phr, less than 0.5 phr, less than 0.4 phr, less than 0.3 phr, less than 0.2 phr, less than 0.1 phr, less than 0.05 phr, or any value, range, or subrange therebetween.
  • a curable fluoroelastomer composition includes a curable fluoroelastomer, a dehydrohalogenating agent, an acid acceptor including bismuth oxide (E ⁇ Os) present in the curable fluoroelastomer composition in an amount of at least 3 phr, and at least one silicon-containing chemical present in the curable fluoroelastomer composition in an amount of at least 0.05 phr.
  • E ⁇ Os bismuth oxide
  • Appropriate amounts of bismuth oxide in the curable fluoroelastomer composition may include, but are not limited to, 1.5 phr or greater, 2 phr or greater, 3 ph r or greater, 1 .5 to 25 phr, 2 to 20 phr, 3 to 18 phr, 5 to 15 phr, or any value, range, or subrange therebetween.
  • Appropriate amounts of the silicon-containing chemical may include, but are not limited to, at least 0.05 phr, at least 0.1 phr, at least 0.2 phr, 0.05 to 15 phr, 0.1 to 15 phr, 0.2 to 5 phr, or any value, range, or subrange therebetween.
  • Appropriate silicon-containing chemicals may include, but are not limited to, silicon dioxide; calcium silicate (Ca2SiC>4); calcium metasilicate (CaSiOs); an organosilicone; y-aminopropyltriethoxylsilane; vinylethoxysilane; talc; diatomaceous earth; wollastonite; metal silicates, including, but not limited to, calcium silicate, sodium silicate, borosilicate, lithium disilicate, and/or potassium silicate; water glass; soda-lime glass; borosilicate glass; Z-glass; E-glass; frit glass; silica, including, but not limited to, fumed silica, pyrogenic silica, precipitated silica, and/or silica fume; and/or metallic silicon.
  • Appropriate amounts of the dehydrohalogenating agent may include, but are not limited to, at least 1 .0 phr, 1 .0 to 5 phr, at least 1 .2 phr, 1 .2 to 5 phr, 1 .0 to 4 phr, or any value, range, or subrange therebetween.
  • Appropriate dehydrohalogenating agent may include, but are not limited to, 2,2 bis(4 hydroxyphenyl)hexafluoropropane (BpAF), methylhydroquinone, 2-methylresorcinol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) perfluoropropane, resorcin, 1 ,3-dihydroxybenzene, 1 ,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1 ,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) ) butane, 4,4-bis (4-hydroxyphenyl) valeric acid, 2,2-bis (4-hydroxyphenyl) tetrafluorodichloropropane, 4,4'
  • the curable fluoroelastomer includes a polyhydroxy- curable fluoroelastomer curable by a polyhydroxy curing agent.
  • polyhydroxy-curable refers to fluoroelastomers that are known to crosslink with polyhydroxy curing agents such as BpAF.
  • fluoroelastomers include, but are not limited to, those having a plurality of carbon-carbon double bonds along the main elastomer polymer chain and also fluoroelastomers that contain sites that may be readily dehydrofluorinated.
  • fluoroelastomers include, but are not limited to, those that contain adjacent copolymerized units of vinylidene fluoride (VF2) and hexafluoropropylene (HFP) as well as fluoroelastomers that contain adjacent copolymerized units of VF2 (or tetrafluoroethylene) and a fluorinated comonomer having an acidic hydrogen atom, such as, for example, 2-hydropentafluoropropylene; 1 -hydropentafluoropropylene; trifluoroethylene; 2,3,3,3-tetrafluoropropene; or 3,3,3- trifluoropropene.
  • VF2 vinylidene fluoride
  • HFP hexafluoropropylene
  • fluoroelastomers that contain adjacent copolymerized units of VF2 (or tetrafluoroethylene) and a fluorinated comonomer having an acidic hydrogen atom, such as, for
  • Preferred fluoroelastomers include the copolymers of i) vinylidene fluoride with hexafluoropropylene and, optionally, tetrafluoroethylene (TFE); ii) vinylidene fluoride with a perfluoro(alkyl vinyl ether) such as perfluoro(methyl vinyl ether), 2-hydropentafluoropropylene and optionally, tetrafluoroethylene; iii) tetrafluoroethylene with propylene and 3,3,3-trifluoropropene; iv) tetrafluoroethylene, perfluoro(methyl vinyl ether) and hexafluoro-2-(pentafluorophenoxy)-1- (trifluorovinyloxy)propane, and v) ethylene with tetrafluoroethylene, perfluoro(methyl vinyl ether) and 3,3,3-trifluoropropylene.
  • TFE tetrafluor
  • the polyhydroxy- curable fluoroelastomer is a dipolymer of hexafluoropropylene and vinylidene fluoride.
  • Polyhydroxy-curable fluoroelastomers may also include iodine-, bromine-, or chlorine-containing elastomers.
  • the curable fluoroelastomer is a dipolymer of hexafluoropropylene and vinylidene fluoride.
  • the curable fluoroelastomer includes a peroxide- curable fluoroelastomer curable by a peroxide cure system and the curable fluoroelastomer composition further includes a peroxide curative.
  • the curable composition includes one or more additives.
  • Appropriate additives may include, but are not limited to, fillers, processing aids, accelerators, weak acid acceptors, peroxides, and/or colorants.
  • the filler may one or more inorganic fillers, one or more polymeric fillers, or combinations thereof.
  • Appropriate inorganic fillers may include, but are not limited to, a medium thermal carbon black, silica, talc, titanium dioxide (TiCk), barium sulfate (BaSC>4), and/or calcium carbonate (CaCO 3 ).
  • Appropriate polymeric fillers may include, but are not limited to, polytetrafluoroethylene (PTFE).
  • Appropriate amounts of filler may include, but are not limited to, about 10 to about 40 phr, about 20 to about 40 phr, about 25 to about 35 phr, about 30 phr, or any value, range, or sub-range therebetween.
  • Appropriate amounts of processing aid may include, but are not limited to, about 0.1 to about 2 phr, about 0.2 to about 2 phr, about 0.5 to about 1 .5 phr, about 1 phr, or any value, range, or sub-range therebetween.
  • Appropriate accelerators may include, but are not limited to, tertiary sulfonium salts such as [(C6H 5 )2S + (C6HI 3 )][CI]', and [(C6HI 3 )2S(C5H 5 )] + [CH 3 CO2]' and quaternary ammonium, phosphonium, arsonium, and stibonium salts of the formula RsRsRzRsY+X where Y is phosphorous, nitrogen, arsenic, or antimony; Rs, Re, R?, and Rs are individually C1-C20 alkyl, aryl, aralkyl, alkenyl, and the chlorine, fluorine, bromine, cyano, -OR, and -COOR substituted analogs thereof, with R being C1-C20 alkyl, aryl, aralkyl, alkenyl, and where X is halide, hydroxide, sulfate, s
  • benzyltriphenylphosphonium chloride benzyltriphenylphosphonium bromide, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tributylallylphosphonium chloride, tributyl-2-methoxypropylphosphonium chloride, 1 ,8-diazabicyclo[5.4.0]undec-7-ene, and benzyldiphenyl(dimethylamino)phosphonium chloride.
  • curing accelerators include methyltrioctylammonium chloride, methyltributylammonium chloride, tetrapropylammonium chloride, benzyltrioctylphosphonium bromide, benzyltrioctylphosphonium chloride, methyltrioctylphosphonium acetate, tetraoctylphosphonium bromide, methyltriphenylarsonium tetrafluoroborate, tetraphenylstibonium bromide, 4-chlorobenzyltriphenyl phosphonium chloride, 8- benzyl-1 ,8-diazabicyclo(5.4.0)-7-undecenonium chloride, diphenylmethyltriphenylphosphonium chloride, allyltriphenyl-phosphonium chloride, tetrabutylphosphonium bromide, m-trifluoromethyl-benzyltrioctylphosphon
  • the curable fluoroelastomer is a peroxide curable fluoroelastomer and the curable fluoroelastomer composition is a peroxide curable fluoroelastomer composition further includes a peroxide curative.
  • Appropriate peroxide curatives may include, but are not limited to, triallyl isocyanurate (TAIC), 1 ,1 -bis (t-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5- dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, a,a-bis (t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy)-hexyne-3, benzoyl peroxide, t-butyl peroxybenzene, t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, and/or t
  • Appropriate amounts of peroxide curative in a peroxide curable fluoroelastomer composition may include, but are not limited to, about 3.0 to about 5.0 phr, about 3.2 to about 4.8 phr, about 3.4 to about 4.6 phr, about 3.6 to about 4.4 phr, about 3.8 to about 4.2 phr, about 4 phr, or any value, range, or sub-range therebetween.
  • Appropriate weak acid acceptors may include, but are not limited to, zinc oxide, lead oxide, and/or hydrotalcite.
  • Appropriate amounts of weak acid acceptor may include, but are not limited to, about 1 phr or less, about 0.1 to about 1 phr, about 0.2 to about 0.8 phr, about 0.5 phr or less, about 0.2 to about 0.5 phr, or any value, range, or sub-range therebetween.
  • the curable fluoroelastomer composition contains less than 1 .0 phr, such as, for example, less than 0.1 phr, of magnesium oxide and calcium hydroxide, in combination. In some embodiments, the curable fluoroelastomer composition is free or substantially free of magnesium oxide and calcium hydroxide.
  • a cured fluoroelastomer cured from a curable fluoroelastomer composition comprises a curable fluoroelastomer, a dehydrohalogenating agent, an acid acceptor comprising bismuth oxide (E ⁇ C ) present in the curable fluoroelastomer composition in an amount of at least 3 parts per hundred parts by weight of the curable fluoroelastomer, and at least one silicon- containing chemical present in the curable fluoroelastomer composition in an amount of at least 0.05 parts per hundred parts by weight of the curable fluoroelastomer.
  • E ⁇ C bismuth oxide
  • the cured fluoroelastomer has a static coefficient of friction of less than 0.5, such as, for example, 0.2 to 0.4.
  • the cured fluoroelastomer has a dynamic coefficient of friction of less than 0.5, such as, for example, 0.15 to 0.4.
  • the cured fluoroelastomer has a tensile strength of 9.0 to 25 MPa.
  • the cured fluoroelastomer has an elongation at break of 150 to 200 %.
  • a method of curing a curable fluoroelastomer comprises forming a curable fluoroelastomer composition and heating the curable fluoroelastomer composition to a cure temperature to cure the curable fluoroelastomer.
  • the curable fluoroelastomer composition comprises the curable fluoroelastomer, a dehydrohalogenating agent, an acid acceptor comprising bismuth oxide (Bi20s) present in the curable fluoroelastomer composition in an amount of at least 3 parts per hundred parts by weight of the curable fluoroelastomer, and at least one silicon-containing chemical present in the curable fluoroelastomer composition in an amount of at least 0.05 parts per hundred parts by weight of the curable fluoroelastomer.
  • Bi20s bismuth oxide
  • the curable fluoroelastomer composition is cured under conventional curing conditions.
  • the heating includes press curing.
  • Appropriate cure temperatures for the heating may include, but are not limited to, about 160 to about 190 °C, about 165 to about 185 °C, about 170 to about 180 °C, about 170 °C, about 180 °C, or any value, range, or subrange therebetween.
  • Appropriate cure times for the heating may depend on the cure temperature and may include, but are not limited to, about 5 minutes to about 90 minutes, about 5 minutes to about 60 minutes, about 5 minutes to about 40 minutes, about 10 minutes to about 30 minutes, about 5 minutes to about 20 minutes, or any value, range, or subrange therebetween.
  • the method further includes post curing the cured fluoroelastomer at a post cure temperature for a post cure period of time.
  • Appropriate post cure temperatures may include, but are not limited to, about 200 to about 260 °C, about 210 to about 250 °C, about 220 to about 240 °C, about 225 to about 235 °C, about 230 °C, or any value, range, or subrange therebetween.
  • Appropriate post cure times may depend on the post cure temperature and may include, but are not limited to, about 15 minutes or greater, about 15 minutes to about 24 hours, about 15 minutes to about 16 hours, about 15 minutes to about 8 hours, about 15 minutes to about 4 hours, about 15 minutes to about 2 hours, about 15 minutes to about 1 hour, or any value, range, or subrange therebetween.
  • Comparative fluoroelastomer curing compositions included curable fluoroelastomer, 30 parts by weight per 100 parts curable fluoroelastomer (phr) carbon black filler, and dehydrohalogenating agent and acid acceptor in the amounts shown in Tables 1-4. Certain comparative fluoroelastomer curing compositions further included accelerator, Si-containing chemical, and/or processing aid, as indicated in Tables 1-4 in phr.
  • Inventive fluoroelastomer curing compositions included curable fluoroelastomer, 30 phr carbon black filler, and dehydrohalogenating agent, Bi20s acid acceptor, and Si-containing chemical in the amounts shown in Tables 1-4, with the exception that Inventive Example 10 included only 5 phr carbon black filler, with some of the listed Si-containing chemical also acting as filler. Certain inventive fluoroelastomer curing compositions further included accelerator, processing aid, and/or additional acid acceptor, as indicated in Tables 1-4 in phr. FLUOROELASTOMER CURING RESULTS AND CURED PROPERTIES
  • Fluoroelastomer curing compositions were press cured at a press cure temperature in the range of 170 to 180 °C for a press cure time in the range of 7 to 60 minutes. Cured fluoroelastomers were then post cured at a post cure temperature of 230 °C for a post cure time in the range of 30 minutes to 24 hours, with the exception of Comparative Example 7, which did not cure, and Comparative Example 8, which was not post-cured.
  • Table 1 shows that the presence of bismuth oxide and silicon-containing chemical, in combination, in a curable fluoroelastomer composition produces a low- friction cured fluoroelastomer.
  • the Si-containing chemicals in Inventive Examples 1-8 were: a silicon dioxide (1.1 ), a sodium salt of silicic acid (1), a silicon dioxide (2), a silicon dioxide (3), a silicon dioxide (4), a silicon dioxide (5), a y-aminopropyltriethoxysilane (6), a vinyltriethoxysilane (7), a combination of an organosilicone and a silicon dioxide (8), and a wollastonite (9), respectively.
  • Inventive Example 9 shows that the further inclusion of a small amount of a weak acid acceptor (zinc oxide) does not negatively affect the friction properties of the resulting cured fluoroelastomer.
  • Comparative Example 1 shows that bismuth oxide as an acid acceptor does not provide a low-friction cured fluoroelastomer in the absence of an Si-containing chemical.
  • Comparative Examples 2 and 3 show that a standard acid acceptor combination of 3 phr magnesium oxide and 6 phr calcium hydroxide, both strong acid acceptors, in place of bismuth oxide do not provide a low-friction cured fluoroelastomer either in the absence or in the presence of an Si-containing chemical.
  • Comparative Examples 4 and 5 show that the presence of just 1 phr of magnesium oxide or calcium hydroxide disrupts the ability of the combination of bismuth oxide and Si-containing chemical to provide a low-friction cured fluoroelastomer.
  • Comparative example 1.1 shows that a relatively lower amount (0.01 phr) of Si-containing chemical results in relatively poor friction properties of the resulting cured fluoroelastomer.
  • Inventive Example 10 in Table 2 shows that an amount of BpAF dehydrohalogenating agent as low as 1.28 phr was sufficient to produce a low- friction cured fluoroelastomer, whereas the 0.96 phr of BpAF of Comparative Example 6 was insufficient.
  • Compositions including the alternative dehydrohalogenating agents methyl-hydroquinone and 2-methylresorcinol of Inventive Examples 1 1 and 12, respectively, at 1.12 phr, in place of BpAF were also able to provide low-friction cured fluoroelastomers.
  • Inventive Example 13 shows that an amount of Bi20s as low as 5 phr was sufficient to produce a low-friction cured fluoroelastomer, whereas the 1 phr of bismuth oxide of Comparative Example 7 failed to cure.
  • Table 3 shows that the composition of Comparative Example 8 without a post cure did not achieve a low-friction cured fluoroelastomer.
  • Inventive Examples 14-16 had the same composition as Comparative Example 8 but were post cured at 230 °C for the amount of time indicated in Table 3. Just 30 minutes of post cure time at 230 °C was sufficient to produce a low-friction cured fluoroelastomer and increasing the post cure time up to 24 hours did not further reduce the coefficients of friction.
  • Table 4 shows that compositions of peroxide (PO) curable fluoroelastomer can also be cured to low-friction cured fluoroelastomer by including bismuth oxide and an Si-containing chemical in appropriate amounts in the composition.
  • Inventive Examples 17, 18, and 19 each included a different PO curable fluoroelastomer having 66% F, 68% F, and 64% F, respectively.
  • the compositions of Table 4 also included 1.5 phr of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2.5 phr of triallyl isocyanurate (TAIC) as peroxide curatives.
  • TAIC triallyl isocyanurate
  • Comparative Example 9 lacked bismuth oxide and Comparative Example 10 lacked an Si-containing chemical, and both compositions did not produce a low-friction cured fluoroelastomer.
  • compositions including Bi20s and Si-containing chemical and containing different BpAF curable fluoroelastomers of varying F content over the range of 66% to 70% were tested and produced low-friction cured fluoroelastomers (data not shown).

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Abstract

L'invention concerne une composition de fluoroélastomère durcissable comprenant un fluoroélastomère durcissable, un agent de déshydrohalogénation, un accepteur d'acide comprenant de l'oxyde de bismuth présent dans la composition de fluoroélastomère durcissable en une quantité d'au moins 3 parties pour cent parties en poids du fluoroélastomère durcissable, et au moins un produit chimique contenant du silicium présent dans la composition de fluoroélastomère durcissable en une quantité d'au moins 0,2 partie pour cent parties en poids du fluoroélastomère durcissable. Un fluoroélastomère durci durci à partir de la composition de fluoroélastomère durcissable a un coefficient de frottement statique et un coefficient de frottement dynamique inférieur à 1.
PCT/US2023/034944 2022-10-12 2023-10-11 Compositions de fluoroélastomères durcissables et fluoroélastomères durcis à faible frottement (fkm) formés à partir de celles-ci WO2024081314A1 (fr)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3876654A (en) 1970-12-23 1975-04-08 Du Pont Fluoroelastomer composition
US4250278A (en) 1978-05-01 1981-02-10 Daikin Kogyo Co., Ltd. Fluorinated rubber composition
US4259463A (en) 1977-12-14 1981-03-31 Montedison S.P.A. Vulcanizable compositions based on copolymers of vinylidene fluoride and containing vulcanization accelerators which are aminophosphinic compounds
US4882390A (en) 1988-04-01 1989-11-21 Minnesota Mining And Manufacturing Company Fluoroelastomer composition with organo-onium compounds
US4912171A (en) 1988-04-01 1990-03-27 Minnesota Mining And Manufacturing Company Fluoroelastomer curing process with phosphonium compound
US5591804A (en) 1995-12-21 1997-01-07 Minnesota Mining And Manufacturing Company Fluorinated onium salts, curable compositions containing same, and method of curing using same
US20120190798A1 (en) * 2010-08-13 2012-07-26 E.I. Du Pont De Nemours And Company Curable fluoroelastomer compositions
EP2676998A1 (fr) * 2011-02-17 2013-12-25 NOK Corporation Composition de caoutchouc fluoré et procédé de fabrication d'un caoutchouc fluoré réticulé
CN107501817A (zh) * 2017-07-06 2017-12-22 无为华兴高分子材料有限公司 一种耐热耐老化氟塑料
US20190330444A1 (en) * 2016-12-28 2019-10-31 3M Innovative Properties Company Silicon-containing halogenated elastomers
CN112592550A (zh) * 2020-12-15 2021-04-02 西北橡胶塑料研究设计院有限公司 一种油封用氟橡胶材料及其制备方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3876654A (en) 1970-12-23 1975-04-08 Du Pont Fluoroelastomer composition
US4259463A (en) 1977-12-14 1981-03-31 Montedison S.P.A. Vulcanizable compositions based on copolymers of vinylidene fluoride and containing vulcanization accelerators which are aminophosphinic compounds
US4250278A (en) 1978-05-01 1981-02-10 Daikin Kogyo Co., Ltd. Fluorinated rubber composition
US4882390A (en) 1988-04-01 1989-11-21 Minnesota Mining And Manufacturing Company Fluoroelastomer composition with organo-onium compounds
US4912171A (en) 1988-04-01 1990-03-27 Minnesota Mining And Manufacturing Company Fluoroelastomer curing process with phosphonium compound
US5591804A (en) 1995-12-21 1997-01-07 Minnesota Mining And Manufacturing Company Fluorinated onium salts, curable compositions containing same, and method of curing using same
US20120190798A1 (en) * 2010-08-13 2012-07-26 E.I. Du Pont De Nemours And Company Curable fluoroelastomer compositions
EP2676998A1 (fr) * 2011-02-17 2013-12-25 NOK Corporation Composition de caoutchouc fluoré et procédé de fabrication d'un caoutchouc fluoré réticulé
US20190330444A1 (en) * 2016-12-28 2019-10-31 3M Innovative Properties Company Silicon-containing halogenated elastomers
CN107501817A (zh) * 2017-07-06 2017-12-22 无为华兴高分子材料有限公司 一种耐热耐老化氟塑料
CN112592550A (zh) * 2020-12-15 2021-04-02 西北橡胶塑料研究设计院有限公司 一种油封用氟橡胶材料及其制备方法

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