WO2019137920A1 - Composition durcissable de fluoroélastomère - Google Patents

Composition durcissable de fluoroélastomère Download PDF

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WO2019137920A1
WO2019137920A1 PCT/EP2019/050351 EP2019050351W WO2019137920A1 WO 2019137920 A1 WO2019137920 A1 WO 2019137920A1 EP 2019050351 W EP2019050351 W EP 2019050351W WO 2019137920 A1 WO2019137920 A1 WO 2019137920A1
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per
group
azobis
composition
peroxide
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PCT/EP2019/050351
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Dipankar BASAK
Trupti NALAWADE
Ritu Ahuja
Valeriy KAPELYUSHKO
Nicola Ranieri
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Solvay Specialty Polymers Italy S.P.A.
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Publication of WO2019137920A1 publication Critical patent/WO2019137920A1/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
    • 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
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/20—Carboxylic acid amides
    • 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
    • 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
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators

Definitions

  • the invention pertains to certain fluoroelastomer compositions having
  • Vulcanized (per)fluoroelastomers are materials with excellent heat- resistance and chemical-resistance characteristics, which are generally used in the manufacture of sealing articles such as oil seals, gaskets, shaft seals and O-rings in which the leaktightness, the mechanical properties and the resistance to substances such as mineral oils, hydraulic fluids, solvents or chemical agents of diverse nature must be ensured over a wide range of working temperatures, from low to high temperatures, and wherein materials might be called to comply with severe requirements in terms of purity, plasma resistance and particles release.
  • curing temperatures for (per)fluoroelastomers are generally higher than curing temperatures for non-fluorocarbon elastomers, and generally range from about 160°C to about 180°C or even beyond.
  • FIPG formed-in-place gasket
  • INNOVATIVE PROPERTIES CO 09/07/2009 provides a composition having an amorphous peroxide curable fluoropolymer with an iodine, bromine or chlorine containing cure site; an organic peroxide; and a coagent, where the fluoropolymer 90% cure time as measured by sealed torsion shear rotorless cure-meter in ASTM D5289-07 is less than 30 minutes at 130°C. This lower curing temperature is achieved through the choice of organic peroxide having fast decomposition rates at said lower temperature.
  • WO 2010/147815 (3M INNOVATIVE
  • PROPERTIES CO) 23/12/2010 provides a comprising an amorphous peroxide curable fluoropolymer having ability to cure at 110°C, including a low molecular weight fluororubber comprising an iodine, bromine or chlorine containing cure site, and an organic peroxide with a 10-hour half- life temperature below 90°C, i.e. having ability to decompose effectively at low temperature.
  • the present invention provides compositions of (per)fluoroelastomers that can be quickly cured at temperatures as low as e.g. 50°C, or even lower, without compromising physical properties of articles derived from these compositions. These (per)fluoroelastomers may also exhibit low
  • compositions which can be useful in milling and molding applications and cure in place applications.
  • the presently disclosed compositions may also include one or more conventional adjuvants, such as, for example, fillers, acid acceptors, process aids, or colorants.
  • compositions comprising a
  • peroxide curable (per)fluoroelastomer an organic peroxide, and a reducing agent can solve above mentioned problems and are particularly effective in enabling curing to occur at lower temperatures than traditional curing, and in particular at temperatures as low as 50°C, while maintaining mechanical and sealing properties of (per)fluoroelastomers.
  • composition (C) [composition (C)]
  • fluoroelastomer (A) is intended to designate a fluoropolymer resin serving as a base constituent for obtaining a true elastomer, said fluoropolymer resin comprising more than 10 % wt, preferably more than 30 % wt, of recurring units derived from at least one ethylenically unsaturated monomer comprising at least one fluorine atom (hereafter, (per)fluorinated monomer) and, optionally, recurring units derived from at least one ethylenically unsaturated monomer free from fluorine atom (hereafter, hydrogenated monomer) .
  • fluoroelastomer (A) comprises recurring units derived from at least one (per)fluorinated monomer, wherein said (per)fluorinated monomer is generally selected from the group consisting of:
  • TFE tetrafluoroethylene
  • FIFP hexafluoropropene
  • pentafluoropropylene pentafluoropropylene
  • hexafluoroisobutylene tetrafluoroethylene
  • FIFP hexafluoropropene
  • pentafluoropropylene pentafluoropropylene
  • hexafluoroisobutylene hexafluoroisobutylene
  • VDF vinylidene fluoride
  • TrFE trifluoroethylene
  • - chloro- and/or bromo- and/or iodo-C2-C6 fluoroolefins like chlorotrifluoroethylene (CTFE);
  • R fi is a C1-C6 fluoro- or perfluoroalkyl, e.g. -CF3, -C2F 5 , -C3F 7 ;
  • each of Rf3 , Rf4 , Rts , Rf6, equal to or different from each other, is independently a fluorine atom, a C1-C6 fluoro- or per(halo)fluoroalkyl, optionally comprising one or more oxygen atom, e.g. -CF3, -C2F 5 , - C3F7, -OCFs, -OCF2CF2OCF3.
  • Examples of hydrogenated monomers are notably hydrogenated alpha- olefins, including ethylene, propylene, 1 -butene, diene monomers, styrene monomers, alpha-olefins being typically used.
  • Fluoroelastomers (A) are in general amorphous products or products
  • T g glass transition temperature
  • the fluoroelastomer (A) has advantageously a T g below 10° C, preferably below 5°C, more preferably 0°C.
  • the fluoroelastomer (A) is preferably selected among:
  • VDF-based copolymers in which VDF is copolymerized with at least one additional comonomer selected from the group consisting of :
  • HFP hexafluoropropylene
  • C 2 -C8 fluoroolefins comprising at least one of iodine, chlorine and bromine, such as chlorotrifluoroethylene (CTFE);
  • (d) (per)fluoroalkylvinylethers (PAVE) of formula CF 2 CFOR f , wherein R f is a C 1 -C6 (per)fluoroalkyl group, preferably CF 3 , C 2 F 5 , C3F 7 ;
  • (e) (per)fluoro-oxy-alkylvinylethers of formula CF 2 CFOX, wherein X is a C 1 -C 12 ((per)fluoro)-oxyalkyl comprising catenary oxygen atoms, e.g. the perfluoro-2-propoxypropyl group;
  • R f3 , R M , R f 5, R f 6, equal to or different from each other, is independently selected from the group consisting of fluorine atom and C 1 -C6
  • (per)fluoroalkyl groups optionally comprising one or more than one oxygen atom, such as notably -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3; preferably, perfluorodioxoles;
  • R f2 is selected from the group consisting of C 1 -C6 (per)fluoroalkyls; C 5 -C6 cyclic (per)fluoroalkyls; and C 2 -C6 (per)fluorooxyalkyls, comprising at least one catenary oxygen atom;
  • R f2 is preferably -CF 2 CF3 (MOVE1 ); - CF2CF2OCF3 (MOVE2); or -CF 3 (MOVE3);
  • TFE-based copolymers in which TFE is copolymerized with at least one additional comonomer selected from the group consisting of (c), (d), (e), (g), (h) and (i) as above detailed .
  • Fluoroelastomer (A) is generally selected among TFE-based copolymers, as above detailed.
  • fluoroelastomer (A) of the present invention may also be used as fluoroelastomer (A) of the present invention.
  • bis-olefin [bis-olefin (OF)] having
  • R 4 , Rs and R6, equal or different from each other, are H or C1 -C5 alkyl;
  • Z is a linear or branched C1 -C18 (hydro)carbon radical (including alkylene or cycloalkylene radical), optionally containing oxygen atoms, preferably at least partially fluorinated, or a (per)fluoro(poly)oxyalkylene radical comprising one or more catenary ethereal bonds.
  • the bis-olefin (OF) is preferably selected from the group consisting of those complying with formulae (OF-1), (OF-2) and (OF-3) :
  • R1 , R2, R3, R4, equal or different from each other are H, F or Ci-s alkyl or (per)fluoroalkyl group;
  • each of A, equal or different from each other and at each occurrence, is independently selected from F, Cl, and H; each of B, equal or different from each other and at each occurrence, is independently selected from F, Cl, H and ORB, wherein RB is a branched or straight chain alkyl radical which can be partially, substantially or completely fluorinated or chlorinated; E is a divalent group having 2 to 10 carbon atom, optionally fluorinated, which may be inserted with ether linkages;
  • R5, R6, R7, equal or different from each other are H, F or Ci-5 alkyl or
  • the fluoroelastomer (A) has a number-averaged molecular weight of advantageously at least 3 000 and/or of advantageously at most 45 000.
  • M n The number average molecular weight (M n ) is defined mathematically as:
  • N is the number of moles of chains
  • M possessing length M
  • number average molecular weight is generally determined by GPC, using tetrahydrofuran (THF) as eluent against monodisperse polystyrene standards.
  • THF tetrahydrofuran
  • Other molecular parameters which can be notably determined by GPC are the weight average molecular weight (M w ) :
  • PDI polydispersity index
  • the fluoroelastomer (A) of the invention has a number-averaged molecular weight of preferably at least 5 000, more preferably at least 6 000, even more preferably at least 10 000.
  • the fluoroelastomer (A) of the invention has a number-averaged molecular weight of preferably at most 40 000, more preferably at most 35 000, even more preferably at most 30 000.
  • fluoroelastomer (A) comprises iodine and/or bromine cure sites.
  • the amount of iodine and/or bromine cure site is such that the I and/or Br content is of from 0.04 to 10.0 % wt, with respect to the total weight of fluoroelastomer (A).
  • iodine and/or bromine cure sites might be comprised as pending groups bound to the backbone of the fluoroelastomer (A) polymer chain or might be comprised as terminal groups of said polymer chain.
  • the iodine and/or bromine cure sites are comprised as pending groups bound to the backbone of the iodine and/or bromine cure sites.
  • brominated and/or iodinated cure-site comonomers selected from:
  • the iodine and/or bromine cure sites are comprised as terminal groups of the fluoroelastomer (A) polymer chain; the fluoroelastomer according to this embodiment is generally obtained by addition to the polymerization medium during fluoroelastomer (A) manufacture of at least one of:
  • suitable chain- transfer agents are typically those of formula R f (l) x (Br) y , in which R f is a (per)fluoroalkyl or a (per)fluorochloroalkyl containing from 1 to 8 carbon atoms, while x and y are integers between 0 and 2, with 1 ⁇ x+y ⁇ 2 (see, for example, patents US 4243770 (DAI KIN IND LTD ) 06/01/1981 and US 4943622 (NIPPON MEKTRON KK ) 24/07/1990 ); and
  • fluoroelastomer (A) should be of at least 0.05 % wt, preferably of at least 0.06 % weight, with respect to the total weight of fluoroelastomer (A).
  • fluoroelastomer (A) preferably 7 % wt, more specifically not exceeding 5 % wt, or even not exceeding 4 % wt, with respect to the total weight of fluoroelastomer (A), are those generally selected for avoiding side reactions and/or detrimental effects on thermal stability.
  • Exemplary fluoroelastomers (A) which can be used in the composition of the present invention are those having iodine cure sites comprised as terminal groups and having following monomers composition (in mol %, with respect to the total moles of recurring units) :
  • TFE tetrafluoroethylene
  • PAVE perfluoroalkylvinylethers
  • OF bis-olefin
  • TFE tetrafluoroethylene
  • MOVE perfluoro-methoxy-vinylethers
  • PAVE perfluoroalkylvinylethers
  • OF bis-olefin
  • composition (C) further comprises at least an organic peroxide
  • peroxide (O) peroxide (O)
  • the choice of the said peroxide (O) is not particularly critical provided that the same is capable of generating radicals with the assistance of a transition metal catalyst.
  • peroxides mention can be made of:
  • di(alkyl/alryl) peroxides including for instance di-tert-butyl peroxide, 2,5- dimethyl-2,5-bis(tert-butylperoxy)hexane, di(t- butylperoxyisopropyl)benzene, dicumyl peroxide;
  • diacyl peroxides including dibenzoyl peroxide, disuccinic acid peroxide, di(4-methylbenzoyl)peroxide, di(2,4-dichlorobenzoyl)peroxide, dilauroyl peroxide, decanoyl peroxide;
  • - percarboxylic acids and esters including di-tert-butyl perbenzoate, t- butylperoxy-2-ethylhexanoate, 1 ,1 ,3,3-tetramethylethylbutyl peroxy-2- ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane;
  • - peroxycarbonates including notably di(4-t- butylcyclohexyl)peroxydicarbonate, di(2-phenoxyethyl)peroxydicarbonate, bis[1 ,3-dimethyl-3-(tert-butylperoxy)butyl] carbonate, t- hexylperoxyisoproprylcarbonate, t-butylperoxyisopropylcarbonate,
  • - ketone peroxides such as cyclohexanone peroxide and acetyl acetone peroxide
  • - oil-soluble azo initiators such as 2, 2'-azobis (4-methoxy-2. 4-dimethyl valeronitrile), 2, 2'-azobis (2.4-dimethyl valeronitrile), 2,2'- azobis(isobutyronitrile), 2, 2'-azobis(2-cyano-2-butane), dimethyl-2, 2'- azobisdimethyli sobutyrate, dimethyl-2, 2'-azobis(2-methylpropionate), 2,2'- azobis(2-methylbutyronitrile), 1 ,1'-azobis(cyclohexane-l-carbonitrile), 2, 2'- azobis[N-(2-propenyl)-2-methylpropionamide], 1 -[(1 -cyano-1 -methyl ethyl)azo]formamide, 2, 2'-azobis(N-cyclohexy1 -2-methylpropionamide), 2,2'-azobis(i sobutyronitrile), 2,2'-azobis(2-cyano
  • the amount of peroxide (O) in the composition (C) is generally of 0.1 to 15 phr, preferably of 0.2 to 12 phr, more preferably of 1.0 to 7.0 phr, relative to 100 weight parts of fluoroelastomer (A).
  • the catalyst (M) will be selected in a manner such to catalyse the formation of radicals by decomposition of peroxide (O).
  • the catalyst (M) may comprise the said transition metal under any form, e.g. as a salt, as an oxide, or as an organometallic complex; further, the catalyst (M) may consists in a transition metal compound or may be comprise an inert support on which a transition metal compound is deposed or anchored.
  • Any organometallic complex or salt of one or more than one of Ce, Co, Cr, Cu, Fe, Mn, Ni, Rh, Sn, Zn and Ru can be used as catalyst (M).
  • organic carboxylates are generally preferred.
  • transition metal carboxylates useful as catalysts include Iron (II) acetate, Iron (III) acetate, Iron (II) octoate, Iron (III) octoate, Cobalt (II) acetate, Cobalt (III) acetate, Cobalt (II) octoate, Cobalt (III) octoate, Tin (II) octoate, Copper (I) acetate, Copper (II) acetate.
  • organometallic complexes of one or more than one of Ce, Co, Cr, Cu, Fe, Mn, Ni, Rh, Sn, and Ru are those which have provided good performances as catalyst (M).
  • Organometallic complex which are particularly preferred are those
  • transition metal atom comprising at least one transition metal atom and at least one chelating organometallic ligand, i.e. a ligand forming two or more coordinate bonds with the transition metal atom.
  • organometallic complexes including these ligands those possessing alpha, beta-diketonates and alpha-nitro- ketonates are particularly preferred as catalysts (M).
  • catalysts M
  • metallocene-type organometallic complexes comprising chelating carbons have also found applicabililty as catalysts (M); when catalyst (M)is a metallocene, ligands in metallocene-type organometallic complexes are those comprising one or more than one ligand selected from those possessing a cyclopendadienyl-type anion moiety; among these ligands, mention can be made of cyclopentadienyl, pentamethylcyclopentadienyl, indenyl, ferrocenyl, 2-phenylindenyl, and corresponding bridged structures.
  • ferrocene (II) of structure:
  • bis(pentametylciclopentadienyl)cobalt (III) salts having cation of formula: and including hexafluorophosphate and tetrafluoroborates.
  • composition (C) may comprise one catalyst (M) as above detailed, or a plurality of catalysts (M), differing notably for the nature of the transition metal, for the oxidation state of the transition metal and/or for the ligand/counterion or other structural features.
  • composition (C) is a composition (C)
  • Catalyst (MFe), catalyst (Mco) and catalyst (Msn) are selected from
  • catalyst (M Fe ) is preferably selected from the group consisting of Fe(lll) acetylacetonate (referred to as M Fei , herein after), Fe(ll) acetate (referred to as M Fe 2, herein after), ferrocene (referred to as MFe3, herein after);
  • catalyst (Mco) is preferably selected from the group consisting of Co (III) acetylacetonate (referred to as Mcoi , herein after), Co(ll) octoate (referred to as Mco2, herein after), Co(ll)
  • catalyst (Msn) is preferably selected from Tin(ll) octoate (referred to as Msni , herein after).
  • Mcoi alone, or in combination with at least one of Mcoi , Mco2 and Msni .
  • the amount of catalyst (M) in the composition (C) is selected in a manner for ensuring effectiveness in generating radicals from organic peroxide; generally catalyst (M) is used in an amount such that the weight ratio between peroxide (O) and catalyst (M) is of at most 20:1 , preferably at most 10: 1 and of at least 0.5: 1 , preferably of at least 1 :1.
  • the amount of catalyst (M) in the composition (C) will generally be of 0.005 to 15 phr, preferably of 0.001 to 12 phr, more preferably of 0.05 to 7.0 phr, and most preferably of 0.1 to 5.0 phr, relative to 100 weight parts of fluoroelastomer (A).
  • composition (C) comprises at least one polyunsaturated
  • composition (C) may comprise one or more than one compound (U), as above detailed.
  • Compounds (U) may be selected from compounds comprising two carbon- carbon unsaturations, compounds comprising three carbon-carbon unsaturations and compounds comprising four or more than four carbon- carbon unsaturations.
  • bis-olefins [bis-olefin (OF)], as above detailed, preferably selected from those complying with any of formulae (OF-1), (OF-2) and (OF-3), as above detailed.
  • each of R cy is independently selected from H or a group -R rcy or-OR rCy , with R rcy being C1-C5 alkyl, possibly comprising halogen(s), and each of J cy , equal to or different from each other and at each occurrence, is independently selected from a bond or a divalent hydrocarbon group, optionally comprising heteroatoms;
  • tri-substuituted cyanurate compounds include notably preferred triallyl cyanurate, trivinyl cyanurate;
  • each of Ri SO c y is independently selected from H or a grou p -Rrisocy or -ORrisoc y , with Rrisocy being C1-C5 alkyl, possibly comprising halogen(s), and each of Ji SO c y , equal to or different from each other and at each occurrence, is independently selected from a bond or a divalent hydrocarbon group, optionally comprising heteroatoms;
  • tri-substuituted isocyanurate compounds include notably preferred triallyl isocyanurate (otherwise referred to as“TAIC”), trivinyl isocyanurate, with TAIC being the most preferred;
  • TAIC triallyl isocyanurate
  • TAIC trivinyl isocyanurate
  • each of R az is independently selected from H or a group -Rraz Or-OR ra z , with R raz being C1 -C5 alkyl, possibly comprising halogen(s), and each of J az , equal to or different from each other and at each occurrence, is independently selected from a bond or a divalent hydrocarbon group, optionally comprising heteroatoms; tri-substituted triazine compounds
  • EP 0860436 A AUSIMONT SPA
  • WO 97/05122 DU PONT 13/02/1997 ;
  • each of R Ph is independently selected from H or a group -R rph or-OR rph , with R rph being C1 -C5 alkyl, possibly comprising halogen(s), and each of J Ph , equal to or different from each other and at each occurrence, is independently selected from a bond or a divalent hydrocarbon group, optionally comprising heteroatoms; tri- substituted phosphite compounds
  • each of R s is independently selected from H or a group -Rrsi or -ORrsi, with R rSi being C1-C5 alkyl, possibly comprising halogen(s), each of R’ S i, equal to or different from each other and at each occurrence, is independently selected from C1-C5 alkyl groups, possibly comprising halogen(s), and each of J S i, equal to or different from each other and at each occurrence, is independently selected from a bond or a divalent hydrocarbon group, optionally comprising heteroatoms;
  • tri- substituted alkyltrisiloxanes compounds include notably preferred 2,4,6- trivinyl methyltrisiloxane and 2,4,6-trivinyl ethyltrisiloxane;
  • each of Ra n is independently selected from H or a group— Rran or— ORran, with R ran being C1-C5 alkyl, possibly comprising halogen(s), and each of J an , equal to or different from each other and at each occurrence, is independently selected from a bond or a divalent hydrocarbon group, optionally comprising heteroatoms;
  • N,N-disubstituted acrylamide compounds include notably preferred N,N-diallylacrylamide.
  • olefins OF
  • OF-1 olefins of (OF-1) type
  • TAIC tri-substuituted isocyanurate compounds
  • the amount of the compound (U) ranges normally from 0.1 to 20 weight parts per 100 parts by weight (phr) of fluoroelastomer (A), preferably from 1 to 15 weight parts per 100 parts by weight of fluoroelastomer (A), more preferably from 1 to 10 weight parts per 100 parts by weight of
  • composition (C) may further additionally comprise ingredients which maybe commonly used for the peroxide curing of fluoroelastomers; more specifically, composition (C) may generally further comprise
  • metallic basic compounds are generally selected from the group consisting of (j) oxides or hydroxides of divalent metals, for instance oxides or hydroxides of Mg, Zn, Ca or Pb, and (jj) metal salts of a weak acid, for instance Ba,
  • one or more than one acid acceptor which is not a metallic basic compound in amounts generally of from 0.5 to 15.0 phr, and preferably of from 1 to 10.0 phr, more preferably 1 to 5 phr, relative to 100 weight parts of fluoroelastomer (A); these acid acceptors are generally selected from nitrogen-containing organic compounds, such as
  • the composition (C) may additionally comprise at least one organic solvent; suitable organic solvents are but not limiting to ketonic solvents such as acetone, methylethylketone; polar solvents such as acetonitrile, dimethylfrmamide (DMF), dimethylsulfoxide (DMSO), N-Methyl-2-pyrrolidone (NMP); esters such as ethyl acetate; ethers such as tetrahydrofuran, 1 ,4-dioxane etc. More preferable solvents are acetone, and methylethylketone.
  • suitable organic solvents are but not limiting to ketonic solvents such as acetone, methylethylketone; polar solvents such as acetonitrile, dimethylfrmamide (DMF), dimethylsulfoxide (DMSO), N-Methyl-2-pyrrolidone (NMP); esters such as ethyl acetate; ethers such as t
  • the composition (C) may include at least one plasticizer (P), generally selected from those known for fluororubbers.
  • Plasticizers (P) will be generally selected among ester- based plasticizers, such as glutarates (e.g. Diisodecyl glutarate), adipates (e.g. Bis(2-ethylhexyl)adipate, dimethyl adipate, monomethyl adipate, dioctyl adipate, Dibutoxyethoxyethyl adipate, Dibutoxyethyl adipate, Diisodecyl adipate), maleates (e.g.
  • glutarates e.g. Diisodecyl glutarate
  • adipates e.g. Bis(2-ethylhexyl)adipate, dimethyl adipate, monomethyl adipate, dioctyl adipate, Dibutoxyethoxyethyl adipate
  • citrates e.g. triethyl citrate, tributyl citrate, acetyltriethylcitrate, acetyl tributy
  • the invention also pertains to a method for fabricating shaped articles comprising curing the composition (C), as above described.
  • composition (C) can be fabricated, e.g. by moulding (injection
  • composition into a finished article made of non-tacky, strong, insoluble, chemically and thermally resistant cured fluoroelastomer material.
  • the method of the invention comprises curing at a temperature which
  • composition (C) of delivering cured shaped articles while avoiding the need of exposing the part to be cured at high temperatures is a particular beneficial effect of the present invention.
  • the invention pertains to cured articles obtained from the composition (C), as above detailed.
  • Said cured articles are generally obtained by moulding and curing the fluoroelastomer composition, as above detailed.
  • These cured articles may be sealing articles, including 0(square)-rings, packings, gaskets, diaphragms, shaft seals, valve stem seals, piston rings, crankshaft seals, cam shaft seals, and oil seals or maybe piping and tubings, in particular flexible hoses or other items, including conduits for delivery of hydrocarbon fluids and fuels.
  • M Fei Iron (III) acetylacetonate
  • MC O 2 is Cobalt (II) octoate
  • Ms ni Tin (II) octoate.
  • (Per)fluoroelastomers were obtained from Solvay Specialty Polymers Italy S.P.A.:
  • A-1 was TECNOFLON ® P LQM008A;
  • A-2 was a peroxide curable TFEA/DF/HFP fluoroelastomer comprising about 2.3 % wt of iodine and possessing a Mn of about 15 000;
  • TECNOFLON ® P457 a peroxide curable TFEA/DF/HFP fluoroelastomer comprising iodine and having Mooney viscosity measured at 121 °C (ML 1 + 10) according to ASTM D1646 of 21 MU.
  • M100 is the tensile strength in MPa at an elongation of 100 %
  • M50 is the tensile strength in MPa at an elongation of 50 %
  • TS is the tensile strength in MPa
  • EB is the elongation at break in %.
  • the Shore A hardness (3") has been determined on 3 pieces of plaque piled according to the ASTM D 2240 method.
  • Compression set (vide infra c-set) values have been determined on 6 mm buttons (type 2), according to the ASTM D 395, method B, punched off from a cured cylinder specimen, at a temperature of 23°C or 70°C.
  • the specimen is immersed into MEK in a closed glass vessel (ratio 1 g of polymer in 50 mL of MEK), at room temperature for 16 hours (overnight) without stirring.
  • Suitable polymer amount for test is 2 g.
  • ATF Dexron VI transmission fluid resistance test has been performed according to ASTM D471 , e.g. by exposing cured specimens ATF Dexron VI at 150 °C for 72 or 168 hours and evaluating variation in weight (D wt) (swelling-related properties) and mechanical properties (DM50, ATS, DEB) for samples before and after said exposure to ATF Dexron VI for the given time period. Results are summarized in Table 2.
  • a curable elastomeric composition was prepared by mixing the following components in acetone: fluoroelastomer (A-1) (100 phr), methyl ethyl ketone peroxide (4.0 phr), triallylisocyanurate (4.0 phr), and M Fei (1.81 phr) at 25 °C and thin-film was casted by slow evaporation of the volatiles. The resulting compound was post-cured at 50 °C for 16 h. The cured sample exhibited the properties shown in Table 1.
  • a curable elastomeric composition was prepared by mixing the following components in acetone: fluoroelastomer (A-1) (100 phr), methyl ethyl ketone peroxide (3.0 phr), triallylisocyanurate (5.0 phr), and M Fei (1.81 phr) at 25°C and thin-film was casted by slow evaporation of the volatiles. The resulting compound was post-cured at 50 °C for 16 h. The cured sample exhibited the properties shown in Table 1.
  • a curable elastomeric composition was prepared by mixing the following components in acetone: fluoroelastomer (A-1) (100 phr), methyl ethyl ketone peroxide (7.0 phr), triallylisocyanurate compound (5.0 phr), and M Fei (1.81 phr) at 25 °C and thin-film was casted by slow evaporation of the volatiles. The resulting compound was post-cured at 50 °C for 16 h. The cured sample exhibited the properties shown in Table 1.
  • a curable elastomeric composition was prepared by mixing the following components in acetone: fluoroelastomer (A-1) (100 phr), Benzoyl Peroxide (Luperox ® A75, ti / 2, 10 h ⁇ 90 °C(benzene)) (4.0 phr), triallylisocyanurate (4.0 phr), and M Fei (1.81 phr) at 25 °C and thin-film was casted by slow evaporation of the volatiles. The resulting compound, which upon post- curing at 50 °C for 16 h produced“well-crosslinked” material.
  • a curable elastomeric composition was prepared by mixing the following components in acetone: fluoroelastomer (A-1) (100 phr), tert- butyl peroxy- 2-ethylhexyl carbonate (Luperox ® TBEC, ti / 2, 10 h - 100 °C (hydrocarbon solvent)) (4.0 phr), triallylisocyanurate (4.0 phr), and M Fei (1.81 phr) at 25 ° C and thin-film was casted by slow evaporation of the volatiles. The resulting compound, which upon post-curing at 50 °C for 16 h produced“ well-crosslinked” material.
  • a curable elastomeric composition was prepared by mixing the following components in acetone: fluoroelastomer (A-1) (100 phr), methyl ethyl ketone peroxide (4.0 phr), triallylisocyanurate compound (4.0 phr), and MC O 2 (1.81 phr) at 25 °C and thin-film was casted by slow evaporation of the volatiles. The resulting compound was post-cured at 50 °C for 16 h and found to be“well-crosslinked” and insoluble in MEK.
  • a curable elastomeric composition was prepared by mixing the following components in acetone: fluoroelastomer (A-1) (100 phr), methyl ethyl ketone peroxide (4.0 phr), triallylisocyanurate compound (4.0 phr), and M Fei (1.81 phr) in combination with Ms ni (0.9 phr) at 25 °C and thin-film was casted by slow evaporation of the volatiles. The resulting compound, which upon post-curing at 50 °C for 16 h produced“well-crosslinked” material.
  • a curable elastomeric composition was prepared by mixing the following components in acetone: fluoroelastomer (A-1) (100 phr), methyl ethyl ketone peroxide (7.0 phr), triallylisocyanurate (15.0 phr), and M Fei (1.81 phr) in combination with Mcoi (0.9 phr) at 25 °C and thin-film was casted by slow evaporation of the volatiles. The resulting compound, which upon post-curing at 50 °C for 16 h produced“well-crosslinked” material. [0096]
  • A-1 100 phr
  • methyl ethyl ketone peroxide 7.0 phr
  • triallylisocyanurate (15.0 phr)
  • M Fei (1.81 phr
  • a curable elastomeric composition was prepared by mixing the following components in acetone: fluoroelastomer (A-1) (100 phr), methyl ethyl ketone peroxide (7.0 phr), triallylisocyanurate (15.0 phr), and M Fei (1.81 phr) in combination with Mco2 (0.9 phr) at 25 °C and thin-film was casted by slow evaporation of the volatiles. The resulting compound, which upon post-curing at 50 °C for 16 h produced“well-crosslinked” material.
  • a curable elastomeric composition was prepared by mixing the following components: fluoroelastomer (A-1) (100 phr), triallylisocyanurate (4.0 phr) at room temperature. This was followed by addition of M Fei (1.81 phr, dispersed in methylethylketone; 10 wt%) and tributyl-O-acetylcitrate (4.0 phr) as plasticizer and left for overnight. Then methyl ethyl ketone peroxide (4.0 phr, 10 wt% in methylethylketone) was added in portions over a period of 15 min. The viscous solution was poured to form a thin-film. The resulting compound was post-cured at 50 °C for 16 h to produce“well- crosslinked” film.
  • Example 1 The above reference Example 1 was repeated, without any metal catalyst (M).
  • the resulting compound was post-cured as described in example 1 and crosslinking feasibility of the cured sample was tested.
  • the non- crosslinked material was readily soluble in MEK.
  • Example 1 The above reference Example 1 was repeated, without any metal catalyst (M).
  • the resulting compound was post-cured at 90 °C for 16 h and crosslinking feasibility of the cured sample was tested.
  • the non- crosslinked material was readily soluble in MEK.
  • a curable elastomeric composition was prepared by mixing the following components in acetone: fluoroelastomer (A-2) (100 phr), methyl ethyl ketone peroxide (4.0 phr), triallylisocyanurate (4.0 phr), and M Fei (1.81 phr) at 25 °C and thin-film was casted by slow evaporation of the volatiles. The resulting compound was post-cured at 50 °C for 16 h to produce“well- crosslinked” film.
  • fluoroelastomer A-2 (100 phr)
  • methyl ethyl ketone peroxide 4.0 phr
  • triallylisocyanurate 4.0 phr
  • M Fei (1.81 phr
  • Typical thickness of the cured films was around 0.5 mm.
  • Table 2 herein below is a recollection of data regarding chemical resistance test carried out on cured specimens as obtained from Ex. 1 , after a preliminary additional post-cure step.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de fluoroélastomère durcissable comprenant notamment un peroxyde et un catalyseur à métal de transition apte à catalyser la décomposition dudit peroxyde, de manière à permettre une réticulation à des températures plus basses que les formulations durcissables de caoutchouc fluoré classiques.
PCT/EP2019/050351 2018-01-10 2019-01-08 Composition durcissable de fluoroélastomère WO2019137920A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2021137084A1 (fr) * 2019-12-30 2021-07-08 3M Innovative Properties Company Composition comprenant un polymère fluoré, du peroxyde de benzoyle et un agent de réticulation et articles et procédés associés
WO2022065055A1 (fr) * 2020-09-28 2022-03-31 株式会社バルカー Matériau d'étanchéité et procédé de production d'un matériau d'étanchéité

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Publication number Priority date Publication date Assignee Title
WO2021137084A1 (fr) * 2019-12-30 2021-07-08 3M Innovative Properties Company Composition comprenant un polymère fluoré, du peroxyde de benzoyle et un agent de réticulation et articles et procédés associés
WO2022065055A1 (fr) * 2020-09-28 2022-03-31 株式会社バルカー Matériau d'étanchéité et procédé de production d'un matériau d'étanchéité

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