[go: up one dir, main page]

WO2015173194A1 - Fluoroélastomères - Google Patents

Fluoroélastomères Download PDF

Info

Publication number
WO2015173194A1
WO2015173194A1 PCT/EP2015/060376 EP2015060376W WO2015173194A1 WO 2015173194 A1 WO2015173194 A1 WO 2015173194A1 EP 2015060376 W EP2015060376 W EP 2015060376W WO 2015173194 A1 WO2015173194 A1 WO 2015173194A1
Authority
WO
WIPO (PCT)
Prior art keywords
optionally substituted
group
per
formula
fluoroelastomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2015/060376
Other languages
English (en)
Inventor
Stefano Bossolo
Marco DOSSI
Giovanni Comino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Specialty Polymers Italy SpA
Original Assignee
Solvay Specialty Polymers Italy SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvay Specialty Polymers Italy SpA filed Critical Solvay Specialty Polymers Italy SpA
Publication of WO2015173194A1 publication Critical patent/WO2015173194A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

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
    • C08F14/00—Homopolymers and 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
    • C08F14/18—Monomers containing fluorine
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the invention relates to crosslinkable fluoroelastomers comprising certain sulphur-containing groups, to a method for their manufacture, to a method for curing the same, and to cured articles derived there from.
  • Vulcanized (per)fluoroelastomers have been used in a variety of applications, in particular for manufacturing sealing articles such as oil seals, gaskets, shaft seals and O-rings, because of several desirable properties such as heat resistance, chemical resistance, weatherability, etc.
  • RAFT/MADIX agents have been found capable to act as a reversible chain transfer agent in free-radical polymerizations, thereby inducing reversible-addition fragmentation transfer reactions to create an equilibrium between propagating radicals (i.e. the growing polymer chain) and so-called dormant species (containing the chain transfer agent fragment) that can become active again, and hence providing polymer chains terminated with a possibly reactive end group.
  • RAFT reversible addition-fragmentation chain transfer
  • MADIX macromolecular design via inter-exchange of xanthate
  • RAFT/MADIX agents can be used successfully for providing (per)fluoroelastomers comprising certain functional end groups.
  • a (per)fluoroelastomer comprising at least one group of formula (I x ): wherein X, equal to or different from each other at each occurrence, is phosphorous or carbon, preferably carbon, and Z, equal to or different from each other at each occurrence, is a hydrocarbon group, possibly comprising one or more than one heteroatoms [fluoroelastomer (A)].
  • Figure 1 shows the generally accepted mechanism of RAFT/MADIX controlled radical polymerization.
  • RAFT/MADIX agents are capable to act as a reversible chain transfer agent in free-radical polymerizations, thereby inducing reversible-addition fragmentation transfer reactions to create an equilibrium between propagating radicals (i.e. the growing polymer chain) and so-called dormant species (containing the chain transfer agent fragment) that can become active again.
  • the generally accepted mechanism of RAFT/MADIX controlled radical polymerization is shown in Scheme I.
  • RAFT/MADIX agent Any RAFT/MADIX agent known in the art may be used in the inventive method.
  • suitable RAFT/MADIX agents are those disclosed in WO WO 98/058974 A RHODIA CHIMIE 19981230 and in WO WO 98/01478 A (E.I. DUPONT DE NEMOURS AND COMMONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH ORGANIZATION 19980115 and in FAVIER, A., et al, Experimental requirements for an efficient control of free-radical polymerizations via the Reversible-Addition Fragmentation chain Transfer (RAFT) process, Macromol. Rapid Commun., 2006, 27, 653-692
  • RAFT Reversible-Addition Fragmentation chain Transfer
  • the term “(per)fluoroelastomer” 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).
  • True elastomers are defined by the ASTM, Special Technical Bulletin, No. 184 standard as materials capable of being stretched, at room temperature, to twice their intrinsic length and which, once they have been released after holding them under tension for 5 minutes, return to within 10 % of their initial length in the same time.
  • -CF 3 -C 2 F 5 , -C 3 F 7 or a C 1 -C 6 (per)fluorooxyalkyl having one or more ether groups, like -C 2 F 5 -O-CF 3 ;
  • hydrogenated monomers are notably C 2 -C 8 non-fluorinated olefins (Ol), in particular C 2 -C 8 non-fluorinated alpha-olefins (Ol), including ethylene, propylene, 1-butene; diene monomers; styrene monomers; with alpha-olefins, as above detailed, being typically used.
  • Ol non-fluorinated olefins
  • alpha-olefins including ethylene, propylene, 1-butene; diene monomers; styrene monomers; with alpha-olefins, as above detailed, being typically used.
  • Fluoroelastomers (A) are in general amorphous products or products having a low degree of crystallinity (crystalline phase less than 20 % by volume) and a glass transition temperature (T g ) below room temperature. In most cases, the fluoroelastomer (A) has advantageously a T g below 10°C, preferably below 5°C, more preferably 0°C.
  • fluoroelastomer (A) of the present invention also comprises recurring units derived from at least one bis-olefin [bis-olefin (OF)] having general formula : wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 , equal or different from each other, are H, a halogen, or a C 1 -C 5 optionally halogenated group, possibly comprising one or more oxygen group; Z is a linear or branched C 1 -C 18 optionally halogenated alkylene or cycloalkylene radical, optionally containing oxygen atoms, or a (per)fluoropolyoxyalkylene radical, e.g. as described in EP 661304 A AUSIMONT SPA 19950705 .
  • the bis-olefin (OF) is preferably selected from the group consisting of those complying with formulae (OF-1), (OF-2) and (OF-3) : (OF-1) wherein j is an integer between 2 and 10, preferably between 4 and 8, and R1, R2, R3, R4, equal or different from each other, are H, F or C 1-5 alkyl or (per)fluoroalkyl group; (OF-2) wherein 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 OR B , wherein R B 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; preferably E is a –(CF 2 ) m -
  • fluoroelastomers having the following compositions (in mol %) : (i) vinylidene fluoride (VDF) 35-85 %, hexafluoropropene (HFP) 10-45 %, tetrafluoroethylene (TFE) 0-30 %, perfluoroalkyl vinyl ethers (PAVE) 0-15 %, bis-olefin (OF) 0-5 %; (ii) vinylidene fluoride (VDF) 50-80 %, perfluoroalkyl vinyl ethers (PAVE) 5 ⁇ 50 %, tetrafluoroethylene (TFE) 0-20 %, bis-olefin (OF) 0-5 %; (iii) vinylidene fluoride (VDF) 20-30 %, C 2 -C 8 non-fluorinated ole
  • the fluoroelastomer (A) may additionally comprise recurring units derived from one or more than one cure-site containing monomers.
  • cure-site containing monomers of type CSM2-A and CSM2-B suitable to the purposes of the present invention are notably those described in patents US 4281092 DU PONT 19810728 , US 4281092 DU PONT 19810728 , US 5447993 DU PONT 19950905 and US 5789489 DU PONT 19980804
  • the fluoroelastomer (A) possesses a number-averaged molecular weight (M n ) of at least 10 000, preferably of at least 12 000, more preferably at least 15 000, when determined according to GPC technique.
  • Polymers possessing a molecular weight of less than 10 000 are not such to deliver elastomeric properties when cured and cannot be qualified as fluoroelastomers.
  • M n number-averaged molecular weight
  • the fluoroelastomer (A) of the present invention advantageously possess at least one group of formula (I x ) at one of its chain ends.
  • the fluoroelastomer (A) has a linear structure
  • the fluoroelastomer (A) is made of a polymer chain possessing two chain ends, one of which is a group of formula (I x ) as above detailed.
  • the fluoroelastomer (A) comprises recurring units derived e.g. from the bis-olefin, as above detailed, the fluoroelastomer (A) advantageously possesses a branched structure, including more than two chain ends; in this case, it is possible for the fluoroelastomer (A) to include more than one chain end of formula (I x ), as above detailed.
  • the fluoroelastomer (A) may possess a chain end different from group of formula (I x ) which is substituted by a iodine and/or a bromine atom.
  • Optional substituents for R 4 and Z groups include epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and its salts), sulfonic acid (and its salts), alkoxy- or aryloxy- carbonyl, isocyanato, cyano, silyl, halo, and dialkylamino.
  • Z is selected, without limitation, from the group consisting of: -OR 5 , -SR 5 , where R 5 is an optionally substituted C 1 -C 20 alkyl, -NR 6 2 wherein each of R 6 , equal to or different from each other, is selected from optionally substituted C 1 -C 20 and alkyl optionally substituted aryl, and wherein e is an integer from 2 to 4.
  • Z is selected, without limitation, from the group consisting of -SCH 2 (C 6 H 5 ), -S(CH 2 ) u CO 2 H wherein u is an integer from 2 to 11, -SC z H 2z+1 , -OC z H 2z+1 , wherein z is an integer from 1 to 12, preferably from 2 to 12, such as 2, 3, 4, 6, 8, 10,12 , -SCH 2 CH 2 OH, -OCH 2 CF 3 , -OCH 2 CH 3 , -N(C 6 H 5 )(CH 3 ) .
  • aryl and heteroaryl refer to any substituent which includes or consists of one or more aromatic or heteroaromatic ring respectively, and which is attached via a ring atom.
  • the rings may be mono or polycyclic ring systems, although mono or bicyclic 5 or 6 membered rings are preferred.
  • alkyl used either alone or in combination, as in “alkenyloxyalkyl”, “alkylthio”, “alkylamino” and “dialkylamino” denotes straight chain, branched or cyclic alkyl, preferably C 1- C 20 alkyl or cycloalkyl.
  • alkoxy denotes straight chain or branched alkoxy, preferably C 1- C 20 alkoxy. Examples of alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy isomers.
  • alkenyl denotes groups formed from straight chain, branched or cyclic alkenes including ethylenically mono-, di- or poly-unsaturated alkyl or cycloalkyl groups as previously defined, preferably C 2- C 20 alkenyl.
  • acyl either alone or in combination, as in “acyloxy”, “acylthio", “acylamino” or “diacylamino”, denotes carbamoyl, aliphatic acyl group and acyl group containing an aromatic ring, which is referred to as aromatic acyl or a heterocyclic ring which is referred to as heterocyclic acyl, preferably C 1- C 20 acyl.
  • the invention further pertains to a method for manufacturing the fluoroelastomer (A), as above defined, said method including polymerizing a monomers mixture [mixture (M)] in the presence of a RAFT/MADIX agent of any general formulae (I) and (II): wherein X is carbon or phosphorous, preferably carbon; R a is a monovalent organic group optionally substituted with one or more hydrophilic groups, R b is a divalent organic group optionally substituted with one or more hydrophilic groups, and Z is any group that can promote sufficient reactivity of the thiocarbonyl group towards radical addition.
  • a RAFT/MADIX agent of any general formulae (I) and (II): wherein X is carbon or phosphorous, preferably carbon; R a is a monovalent organic group optionally substituted with one or more hydrophilic groups, R b is a divalent organic group optionally substituted with one or more hydrophilic groups, and Z is any group that can promote sufficient
  • the monomers of the mixture (M) are those as above detailed constituting the recurring units of the fluoroelastomer (A).
  • Z has preferably the meaning, as above defined for group of formula (I x ).
  • X is preferably a carbon atom, that is to say that the RAFT/MADIX agent complies with any general formulae (I’) and (II’) herein below: with R a , R b and Z being as above detailed.
  • R a may be selected from C 1 -C 12 alkyl, C 1 -C 12 alkoxy, aryl or heteroaryl, each of which may be substituted with one or more hydrophilic groups selected from -CO 2 H, -CO 2 R, -CN, -SO 3 H, -OSO 3 H, -SOR, -SO 2 R, -OP(OH) 2 , -P(OH) 2 , -PO(OH) 2 , -OH, -OR, -(OCH 2 -CHR 0 ) w -OH, -(OCH 2 -CHR 0 ) w -OR, -CONH 2 , -CONHR 1 , -CONR 1 R 2 , -NR 1 R 2 , -NR 1 R 2 R 3 , where R is selected from C 1 -C 12 alkyl; w is an integer from 1 to 10; R 0 is selected from hydrogen or R; R 1 , R 2 and
  • R a is selected, without limitation, from the group consisting of: -CH(CH 3 )CO 2 H, -CH(CH 3 )CO 2 CH 3 , -CH(CH 3 )CO 2 CH 2 CH 3 , -CH(CH 3 )CO 2 CH(CH 3 ) 2 , -CH(CO 2 H)CH 2 CO 2 H, -CH(CO 2 CH 3 )CH 2 CO 2 CH 3 , -CH(CO 2 CH 2 CH 3 )CH 2 CO 2 CH 2 CH 3 , -CH(CO 2 CH(CH 3 ) 2 )CH 2 CO 2 CH(CH 3 ) 2 , -C(CH 3 ) 2 CO 2 H, -C(CH 3 ) 2 CO 2 CH 3 , -C(CH 3 ) 2 CO 2 CH 2 CH 3 , -C(CH 3 ) 2 CO 2 CH(CH 3 ) 2 , -CH 2 (C 6 H 5 ), -C(CN)(CH 3 )CO 2 H, -CH(
  • R b may be selected from divalent C 1 -C 12 aliphatic, aryl or heteroaryl groups, each of which may be substituted with one or more hydrophilic groups selected from -CO 2 H, -CO 2 R, -CN, -SO 3 H, -OSO 3 H, -SOR, -SO 2 R, -OP(OH) 2 , -P(OH) 2 , -PO(OH) 2 , -OH, -OR, -(OCH 2 -CHR 0 ) w -OH, -(OCH 2 -CHR 0 ) w -OR, -CONH 2 , -CONHR 1 , -CONR 1 R 2 , -NR 1 R 2 , -NR 1 R 2 R 3 , where R is selected from C 1 -C 12 alkyl; w is an integer from 1 to 10; R 0 is selected from hydrogen or R; R 1 , R 2 and R 3 are independently selected
  • R b is selected, without limitation, from the group consisting of: -(CH 2 ) p -, with p being an integer of 1 to 12, preferably of 1 to 6, -CH(CH 3 )-CH 2 -CH 2 -, –CH(C 2 H 5 )-CH 2 -, -CHCO 2 H-CH 2 -, -CH(CO 2 CH 3 )-CH 2 -, -CH(CO 2 CH 2 CH 3 )-CH 2 -, -CH(CO 2 CH(CH 3 ) 2 )-CH 2 -, -CH(CO 2 H)CH(CO 2 H)-, -CH(CO 2 CH(CH 3 ) 2 )CH(CO 2 CH(CH 3 ) 2 )-, -CH(CO 2 CHCH 3 )CH(CO 2 CHCH 3 )-, -CH(CO 2 CHCH 3 )CH(CO 2 CHCH 3 )-, -(CH(CO 2 CHCH 3 )CH(CO 2 CH 2 CH
  • the polymerization can be carried out in any manner known to those skilled in the art, notably in solution or in aqueous emulsion.
  • Methods wherein the mixture (M) is polymerized in aqueous emulsions are generally preferred.
  • the method includes polymerizing the mixture (M) in aqueous emulsion in the presence of at least one surfactant.
  • the surfactant used in the method of the invention is generally a fluorinated surfactant. More specifically, fluorinated surfactant [surfactant (FS)] of formula : R f ⁇ (X - ) j (M + ) j wherein R f ⁇ is a C 3 –C 30 (per)fluoroalkyl chain, which can possibly be linear, cyclic of branched, a C 3 –C 30 (per)fluoro(poly)oxyalkylenic chain, which can possibly be linear, cyclic of branched, X - is -COO - , -PO 3 - or -SO 3 - , M + is selected from H + , NH 4 + , an alkaline metal ion and j can be 1 or 2 can be used.
  • fluorinated surfactant [surfactant (FS)] of formula : R f ⁇ (X - ) j (M + ) j
  • R f ⁇ is
  • surfactants As non limitative examples of surfactants (FS), mention may be made of ammonium and/or sodium perfluorocarboxylates, and/or (per)fluoropolyoxyalkylenes having one or more carboxylic end groups.
  • fluorinated surfactants are (per)fluorooxyalkylenic surfactants described in US 2007015864 3M INNOVATIVE PROPERTIES 20070108 , US 2007015865 3M INNOVATIVE PROPERTIES CO 20070118 , US 2007015866 3M INNOVATIVE PROPERTIES CO 20070118 , US 2007025902 3M INNOVATIVE PROPERTIES CO 20070201 .
  • the surfactant (FS) selected from the group consisting of: - CF 3 (CF 2 ) n1 COOM’, in which n 1 is an integer ranging from 4 to 10, preferably from 5 to 7, and more preferably being equal to 6 ; M’ represents H, NH 4 , Na, Li or K, preferably NH 4 ; - T(C 3 F 6 O) n0 (CFXO) m0 CF 2 COOM” [formula (FS 1 )], in which T represents Cl or a perfluoroalkoxyde group of formula C k F 2k+1 O with k is an integer from 1 to 3, one F atom being optionally substituted by a Cl atom ; n 0 is an integer ranging from 1 to 6 ; m 0 is an integer ranging from 0 to 6 ; M” represents H, NH 4 , Na, Li or K ; X represents F or CF 3 ; - F-(CF 2 —CF 2 ) n2
  • the method includes polymerizing the mixture (M) in aqueous emulsion further in the presence of at least one additional non-functional fluorinated fluid.
  • This technique is particularly advantageous as the addition of certain particular non-functional fluorinated fluid(s) [fluid (F)] can provide for an emulsion comprising dispersed droplets of said fluid having an average size of preferably less than 50 nm, more preferably of less than 40 nm, even more preferably of less than 30 nm.
  • Said nanometric size of droplets is particularly advantageous in that it ensure higher polymerization rates and small fluoropolymer particles.
  • Said non-functional fluorinated fluids which can be used according to this embodiment are preferably (per)fluoropolyethers comprising recurring units (R1), said recurring units comprising at least one ether linkage in the main chain and at least one fluorine atom (fluoropolyoxyalkene chain).
  • the recurring units R1 of the (per)fluoropolyether are selected from the group consisting of : (I) –CFX-O-, wherein X is –F or –CF 3 ; and (II) –CF 2 -CFX-O-, wherein X is –F or –CF 3 ; and (III) –CF 2 -CF 2 -CF 2 -O-; and (IV) –CF 2 -CF 2 -CF 2 -CF 2 -O-; and (V) –(CF 2 ) j -CFZ-O- wherein j is an integer chosen from 0 and 1 and Z is a fluoropolyoxyalkene chain comprising from 1 to 10 recurring units chosen among the classes (I) to (IV) here above; and mixtures thereof.
  • the (per)fluoropolyether is a compound complying with formula (I-p) here below : T 1 -(CFX) p -O-R f -(CFX) p’ -T 2 ( I-p) wherein : - each of X is independently F or CF 3 ; - p and p’, equal or different each other, are integers from 0 to 3; - R f is a fluoropolyoxyalkene chain comprising repeating units R°, said repeating units being chosen among the group consisting of : (i) -CFXO-, wherein X is F or CF 3 , (ii) -CF 2 CFXO-, wherein X is F or CF 3 , (iii) -CF 2 CF 2 O-, (iv) -CF 2 CF 2 CF 2 O-, (v) –(CF 2 ) j -CFZ-O- wherein
  • the aqueous emulsion comprises at least one surfactant (FS), as above detailed, and at least one fluid (F), as above detailed, and even more preferably those wherein the aqueous emulsion includes: - at least one surfactant (FS) of formula (FS 1 ): T(C 3 F 6 O) n0 (CFXO) m0 CF 2 COOM”, as above detailed; and - at least one fluid (F) of formula (I-p) T 1 -(CFX) p -O-R f -(CFX) p’ -T 2 ( I-p) as above detailed.
  • FS surfactant
  • F fluid
  • the aqueous emulsion polymerization may be carried out at a temperature between 10 to 150°C, preferably 20°C to 110°C and the pressure is typically between 2 and 35 bar, in particular 15 to 30 bar.
  • the reaction temperature may be varied during the polymerization e.g. for influencing the molecular weight distribution, i.e., to obtain a broad molecular weight distribution or to obtain a bimodal or multimodal molecular weight distribution.
  • the pH of the polymerization media may be in the range of pH 2-10, preferably 3-9, most preferably 4-8.
  • the aqueous emulsion polymerization is typically initiated by a radical initiator including any of the initiators known for initiating a free radical polymerization of fluorinated monomers.
  • Suitable initiators include peroxides and azo compounds and redox based initiators.
  • Specific examples of peroxide initiators include hydrogen peroxide, sodium or barium peroxide, diacylperoxides such as diacetylperoxide, disuccinyl peroxide, dipropionylperoxide, dibutyrylperoxide, dibenzoylperoxide, benzoylacetylperoxide, diglutaric acid peroxide and dilaurylperoxide, and further per-acids and salts thereof such as e.g.
  • ammonium, sodium or potassium salts examples include peracetic acid. Esters of the peracid can be used as well and examples thereof include tert.-butylperoxyacetate and tert.-butylperoxypivalate.
  • examples of inorganic include for example ammonium-alkali- or earth alkali salts of persulfates, permanganic or manganic acid or manganic acids.
  • a persulfate initiator e.g. ammonium persulfate (APS), can be used on its own or may be used in combination with a reducing agent.
  • Suitable reducing agents include bisulfites such as for example ammonium bisulfite or sodium metabisulfite, thiosulfates such as for example ammonium, potassium or sodium thiosulfate, hydrazines, azodicarboxylates and azodicarboxyldiamide (ADA).
  • Further reducing agents that may be used include sodium formaldehyde sulfoxylate (Rongalit ) or fluoroalkyl sulfinates, e.g. as disclosed in US 5285002 .
  • the reducing agent typically reduces the half-life time of the persulfate initiator.
  • a metal salt catalyst such as for example copper, iron or silver salts may be added.
  • the amount of radical initiator is not particularly limited; nevertheless in order to ensure adequate polymerization kinetics control, it is generally understood that the amount of initiator will be selected so as to achieve a molar ratio between the amount of RAFT/MADIX agent and of radical initiator of between 0.1 to 20, preferably of between 0.5 to 10, most preferably of 0.5 to 5 moles/moles.
  • composition (C) comprising: - at least one fluoroelastomer (A), as above defined; - from 0.1 to 15 weight parts, per 100 parts by weight of said fluoroelastomer (A), of at least one cross-linking co-agent; - from 0.1 to 10 weight parts, per 100 parts by weight of said fluoroelastomer (A), of at least one peroxide.
  • composition (C) of the invention comprises at least one peroxide, typically an organic peroxide.
  • dialkyl peroxides for instance di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, bis(1,1-diethylpropyl)peroxide, bis(1-ethyl-1-methylpropyl)peroxide, 1,1-diethylpropyl-1-ethyl-1-methylpropyl-peroxide, 2,5-dimethyl-2,5-bis(tert-amylperoxy)hexane; dicumyl peroxide; dibenzoyl peroxide; di-tert-butyl perbenzoate; bis[1,3-dimethyl-3-(tert-butylperoxy)butyl] carbonate.
  • dialkyl peroxides for instance di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, bis(1,1-diethylpropyl
  • the amount of peroxide ranges from 0.1 to 10 weight parts per 100 parts by weight of fluoroelastomer (A).
  • composition (C) amounts of peroxide of at least 0.5, preferably at least 1 weight parts per 100 parts by weight of fluoroelastomer (A).
  • composition (C) of the invention comprises at least one crosslinking co-agents.
  • the amount of peroxide ranges from 0.1 to 10 weight parts per 100 parts by weight of fluoroelastomer (A).
  • composition (C) amounts of crosslinking co-agent of at least 0.5, preferably at least 1 weight parts per 100 parts by weight of fluoroelastomer (A).
  • the crosslinking co-agent is generally selected from the group consisting of polyunsaturared compounds, i.e. from compounds comprising more than one ethylenic unsaturations.
  • crosslinking co-agents the following are commonly used : triallyl cyanurate; triallyl isocyanurate (TAIC); tris(diallylamine)-s-triazine; triallyl phosphite; N,N ⁇ diallylacrylamide; N,N,N',N'-tetraallylmalonamide; trivinyl isocyanurate; 2,4,6-trivinyl methyltrisiloxane; bis-olefins (OF), as above detailed; triazines substituted with ethylenically unsaturated groups, such as notably those described in EP 860436 A AUSIMONT SPA 19980826 and WO WO 97/05122 DU PONT (US) 19970213 ; among above mentioned crosslinking co-agents, TAIC and bis-olefins (OF), as above detailed, and more specifically those of formula (OF-1), as above detailed, have been found to provide particularly good results
  • composition (C) of the invention may additionally comprise other ingredients, such as notably: (a) a metal compound, generally in amounts of between 1 and 15, and preferably between 2 and 10 weight parts per 100 parts of fluoroelastomer (A), typically selected from the group consisting of (i) oxides and hydroxides of divalent metals, for instance Mg, Zn, Ca or Pb, (ii) salts of a weak acid, for instance Ba, Na, K, Pb, Ca stearates, benzoates, carbonates, oxalates or phosphites, and (iii) mixtures of (i) and (ii); (b) an acid acceptor of non-metal oxide/hydroxide type, selected from the group consisting of 1,8 ⁇ bis(dimethylamino)naphthalene, octadecylamine, oxiranes, glycidyl resins obtained by condensation of bisphenol A and epichlorhydrine, organosilances (such as 3-gly
  • composition (C) of the invention comprises no other ingredients beside those above listed; in other terms, the inventive composition (C) generally consists essentially of the fluoroelastomer (A), the peroxide, the crosslinking co-agent, and optionally metal compounds, acid acceptors and conventional additives, as above detailed.
  • the invention also pertains to a method of using the composition (C), as above described, for fabricating shaped articles.
  • composition (C) can be fabricated, e.g. by moulding (injection moulding, extrusion moulding), calendering, or extrusion, into the desired shaped article, which is advantageously subjected to vulcanization (curing) during the processing itself and/or in a subsequent step (post-treatment or post-cure), advantageously transforming the relatively soft, weak, fluoroelastomer (A) into a finished article made of non-tacky, strong, insoluble, chemically and thermally resistant cured fluoroelastomer.
  • composition (C) cured articles obtained from the composition (C), as above detailed.
  • the cured articles can be notably pipes, joints, O-ring, hose, and the like.
  • O-ethyl S-(1-methoxycarbonyl ethyl)dithiocarbonate (Rhodixan® A1) as chain transfer agent were introduced, and the reactor was heated and maintained at a set-point temperature of 80°C; a mixture of tetrafluoroethylene (TFE) (7.5% moles), vinylidene fluoride (VDF) (47.5% moles) and hexafluoropropene (HFP) (45%moles) was then added to reach a final pressure of 19 bar (1.9 MPa). 2.6 g of ammonium persulfate (APS) as initiator were then introduced.
  • TFE tetrafluoroethylene
  • VDF vinylidene fluoride
  • HFP hexafluoropropene
  • Pressure was maintained at set-point of 19 bar by continuous feeding of a gaseous mixture of TFE (11.0% moles), VDF (70.0% moles) and HFP (19.0% moles) up to a total of 500 g, for a total reaction time of 104 minutes, during which additional amounts of O-ethyl S-(1-methoxycarbonyl ethyl)dithiocarbonate in equal portions of 0.25 g, at 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% and 90% conversion of gaseous mixture, were fed to the reactor, hence totaling 2.5 g of MADIX agent. Then the reactor was cooled, vented and the latex recovered.
  • the latex was frozen at a temperature of -20°C for 24 hours, recovered at room temperature, separated from the aqueous phase, washed with demineralized water and dried in a convection oven at 90°C for 16 hours.
  • the composition of the obtained polymer by NMR was found to be the following: 11.5 % moles of recurring units derived from TFE; 69.9 % moles of recurring units derived from VDF, and 18.6 % moles of recurring units derived from HFP.
  • Molecular weight distribution data (Mn, PDI, Mw) as obtained by GPC are summarized in table 2.
  • Fluoroelastomers were characterized by GPC using instrumentation and conditions as detailed in the Table 1 below, and relevant parameter were determined based on polystyrene standards, taking into account polymer/solvent Mark-Houwink parameters for relevant standard and for fluoroelastomers.
  • Table 1 Mobile phase Tetrahydrofuran (THF) Flow rate 1.0 mL/min Temperature 35 °C Injection system Autosampler mod. Waters 717plus Injection volume 200 mL Pump Waters mod. 515 HPLC Column set Precolumn + 4 Waters Styragel HR: 10 6 , 10 5 , 10 4 and 10 3 ⁇ Detector Waters Refractive Index mod. 2414 Software for data acquisition and processing Waters Empower 3
  • THF Tetrahydrofuran
  • Example 1 In order to evaluate the reactivity of Example 1 in a standard peroxidic system a solubility test was performed on Example 1 (raw polymer) on compounded Example 1 and on the crosslinked specimen after molding in specified conditions (molding conditions 10 min 160°C, no postcure) :
  • Example 6 polymer 100 phr DRIMIX® TAIC 75(*) 4 phr Luperox® A70S(**) 2 phr Curing rate 120°C ML (lb x inch) 1.2 MH (lb x inch) 3.7 t02 (sec) 53 t50 (sec) 140 t90 (sec) 389
  • Example 6 In order to evaluate network formation of Example 6 in a standard peroxidic system a solubility/swelling test was performed on molded Example 6 compound (molding conditions 10 min 140°C, no postcure). Conditions - Solvent: MEK. Samples have been dissolved for 3 days under stirring at RT. Results are summarized in Table 6.

Landscapes

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

Abstract

L'invention se rapporte à un (per)fluoroélastomère comprenant au moins un groupe de formule (lx), dans laquelle X représente un atome de phosphore ou de carbone et, de préférence, de carbone, et Z représente un groupe hydrocarboné, comprenant éventuellement un ou plusieurs hétéroatomes [fluoroélastomère (A)], son procédé de fabrication, une composition durcissable en contenant et des articles durcis à base de celle-ci.
PCT/EP2015/060376 2014-05-12 2015-05-11 Fluoroélastomères Ceased WO2015173194A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14167932.4 2014-05-12
EP14167932 2014-05-12

Publications (1)

Publication Number Publication Date
WO2015173194A1 true WO2015173194A1 (fr) 2015-11-19

Family

ID=50685814

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2015/060376 Ceased WO2015173194A1 (fr) 2014-05-12 2015-05-11 Fluoroélastomères

Country Status (1)

Country Link
WO (1) WO2015173194A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107880196A (zh) * 2017-10-24 2018-04-06 复旦大学 一种（甲基）丙烯酸氟代烷基酯类聚合物的光控制聚合方法
WO2019123124A1 (fr) * 2017-12-19 2019-06-27 3M Innovative Properties Company Matériaux polymères formés à l'aide d'initiateurs ayant deux groupes contenant du thiocarbonylthio
CN110128766A (zh) * 2018-02-09 2019-08-16 大金工业株式会社 氟橡胶组合物及其成型品
CN111757895A (zh) * 2018-02-21 2020-10-09 3M创新有限公司 使用具有酮基团和两个含硫代羰基硫代基团的引发剂形成的聚合物材料
CN112839969A (zh) * 2018-10-18 2021-05-25 大金工业株式会社 含氟弹性体、交联性组合物和成型品
CN114174362A (zh) * 2019-09-04 2022-03-11 大金工业株式会社 含氟共聚物
EP4079770A4 (fr) * 2019-12-25 2024-01-24 Daikin Industries, Ltd. Procédé de production de fluoropolymère

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4035565A (en) 1975-03-27 1977-07-12 E. I. Du Pont De Nemours And Company Fluoropolymer containing a small amount of bromine-containing olefin units
US4281092A (en) 1978-11-30 1981-07-28 E. I. Du Pont De Nemours And Company Vulcanizable fluorinated copolymers
US4564662A (en) 1984-02-23 1986-01-14 Minnesota Mining And Manufacturing Company Fluorocarbon elastomer
EP0199138A2 (fr) 1985-03-28 1986-10-29 Daikin Industries, Limited Ethers fluorovinyliques et copolymères les comprenant
US4694045A (en) 1985-12-11 1987-09-15 E. I. Du Pont De Nemours And Company Base resistant fluoroelastomers
US4745165A (en) 1985-07-08 1988-05-17 Ausimont S.P.A. Process for the preparation of curable fluoroelastomers and products so obtained
US5285002A (en) 1993-03-23 1994-02-08 Minnesota Mining And Manufacturing Company Fluorine-containing polymers and preparation and use thereof
EP0661304A1 (fr) 1993-12-29 1995-07-05 AUSIMONT S.p.A. Elastomères fluorés comprenant des unités monomères dérivant d'une bis-oléfine
US5447993A (en) 1994-04-19 1995-09-05 E. I. Du Pont De Nemours And Company Perfluoroelastomer curing
WO1997005122A1 (fr) 1995-07-26 1997-02-13 E.I. Du Pont De Nemours And Company Triazines d'alcoylene fluorees et leur utilisation en tant qu'agents de reticulation
WO1998001478A1 (fr) 1996-07-10 1998-01-15 E.I. Du Pont De Nemours And Company Polymerisation presentant des caracteristiques vivantes
US5789489A (en) 1996-11-25 1998-08-04 E. I. Du Pont De Nemours And Company Fast-curing perfluoroelastomer composition
EP0860436A1 (fr) 1997-02-25 1998-08-26 Ausimont S.p.A. Composés contenant des cycles triazine
WO1998058974A1 (fr) 1997-06-23 1998-12-30 Rhodia Chimie Procede de synthese de polymeres a blocs par polymerisation radicalaire controlee
US20070015864A1 (en) 2005-07-15 2007-01-18 3M Innovative Properties Company Method of making fluoropolymer dispersion
US20070015866A1 (en) 2005-07-15 2007-01-18 3M Innovative Properties Company Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant
US20070015865A1 (en) 2005-07-15 2007-01-18 3M Innovative Properties Company Aqueous emulsion polymerization of fluorinated monomers using a perfluoropolyether surfactant
WO2010003929A1 (fr) 2008-07-08 2010-01-14 Solvay Solexis S.P.A. Méthode de fabrication de fluoropolymères
WO2013160621A1 (fr) * 2012-04-26 2013-10-31 Arkema France Copolymerisation radicalaire controlee a partir de trifluoroethylene

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4035565A (en) 1975-03-27 1977-07-12 E. I. Du Pont De Nemours And Company Fluoropolymer containing a small amount of bromine-containing olefin units
US4281092A (en) 1978-11-30 1981-07-28 E. I. Du Pont De Nemours And Company Vulcanizable fluorinated copolymers
US4564662A (en) 1984-02-23 1986-01-14 Minnesota Mining And Manufacturing Company Fluorocarbon elastomer
EP0199138A2 (fr) 1985-03-28 1986-10-29 Daikin Industries, Limited Ethers fluorovinyliques et copolymères les comprenant
US4745165A (en) 1985-07-08 1988-05-17 Ausimont S.P.A. Process for the preparation of curable fluoroelastomers and products so obtained
US4694045A (en) 1985-12-11 1987-09-15 E. I. Du Pont De Nemours And Company Base resistant fluoroelastomers
US5285002A (en) 1993-03-23 1994-02-08 Minnesota Mining And Manufacturing Company Fluorine-containing polymers and preparation and use thereof
EP0661304A1 (fr) 1993-12-29 1995-07-05 AUSIMONT S.p.A. Elastomères fluorés comprenant des unités monomères dérivant d'une bis-oléfine
US5447993A (en) 1994-04-19 1995-09-05 E. I. Du Pont De Nemours And Company Perfluoroelastomer curing
WO1997005122A1 (fr) 1995-07-26 1997-02-13 E.I. Du Pont De Nemours And Company Triazines d'alcoylene fluorees et leur utilisation en tant qu'agents de reticulation
WO1998001478A1 (fr) 1996-07-10 1998-01-15 E.I. Du Pont De Nemours And Company Polymerisation presentant des caracteristiques vivantes
US5789489A (en) 1996-11-25 1998-08-04 E. I. Du Pont De Nemours And Company Fast-curing perfluoroelastomer composition
EP0860436A1 (fr) 1997-02-25 1998-08-26 Ausimont S.p.A. Composés contenant des cycles triazine
WO1998058974A1 (fr) 1997-06-23 1998-12-30 Rhodia Chimie Procede de synthese de polymeres a blocs par polymerisation radicalaire controlee
US20070015864A1 (en) 2005-07-15 2007-01-18 3M Innovative Properties Company Method of making fluoropolymer dispersion
US20070015866A1 (en) 2005-07-15 2007-01-18 3M Innovative Properties Company Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant
US20070015865A1 (en) 2005-07-15 2007-01-18 3M Innovative Properties Company Aqueous emulsion polymerization of fluorinated monomers using a perfluoropolyether surfactant
US20070025902A1 (en) 2005-07-15 2007-02-01 3M Innovative Properties Company Recovery of fluorinated carboxylic acid from adsorbent particles
WO2010003929A1 (fr) 2008-07-08 2010-01-14 Solvay Solexis S.P.A. Méthode de fabrication de fluoropolymères
WO2013160621A1 (fr) * 2012-04-26 2013-10-31 Arkema France Copolymerisation radicalaire controlee a partir de trifluoroethylene

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
AMEDURI BRUNO: "Controlled Radical (Co)polymerization of Fluoromonomers", MACROMOLECULES, vol. 43, no. 24, 28 December 2010 (2010-12-28), pages 10163 - 10184, XP055145844, ISSN: 0024-9297, DOI: 10.1021/ma1019297 *
ETIENNE GIRARD ET AL: "Direct Synthesis of Vinylidene Fluoride-Based Amphiphilic Diblock Copolymers by RAFT/MADIX Polymerization", ACS MACRO LETTERS, vol. 1, no. 2, 21 February 2012 (2012-02-21), pages 270 - 274, XP055145840, ISSN: 2161-1653, DOI: 10.1021/mz2001143 *
FAVIER, A. ET AL.: "Experimental requirements for an efficient control of free-radical polymerizations via the Reversible-Addition Fragmentation chain Transfer (RAFT) process", MACROMOL. RAPID COMMUN., vol. 27, 2006, pages 653 - 692
LEI LIU ET AL: "Living/controlled free radical copolymerization of chlorotrifluoroethene and butyl vinyl ether under 60Co [gamma]-ray irradiation in the presence of S-benzyl O-ethyl dithiocarbonate", CHEMICAL COMMUNICATIONS, vol. 47, no. 27, 1 January 2011 (2011-01-01), pages 7839, XP055145848, ISSN: 1359-7345, DOI: 10.1039/c1cc11749a *
PERRIER, S. ET AL.: "Macromolecular design via Reversible Addition-Fragmentation Chain Transfer (RAFT)/Xanthates (MADIX) polymerization", J. PO/YM. SCI.: PARTA: POLYM. CHEM., vol. 43, 2005, pages 5347 - 5393

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107880196A (zh) * 2017-10-24 2018-04-06 复旦大学 一种（甲基）丙烯酸氟代烷基酯类聚合物的光控制聚合方法
CN107880196B (zh) * 2017-10-24 2019-12-03 复旦大学 一种（甲基）丙烯酸氟代烷基酯类聚合物的光控制聚合方法
WO2019123124A1 (fr) * 2017-12-19 2019-06-27 3M Innovative Properties Company Matériaux polymères formés à l'aide d'initiateurs ayant deux groupes contenant du thiocarbonylthio
US11492460B2 (en) 2017-12-19 2022-11-08 3M Innovative Properties Company Polymeric materials formed using initiators with two thiocarbonylthio-containing groups
CN111556877A (zh) * 2017-12-19 2020-08-18 3M创新有限公司 使用具有两个含硫代羰基硫基的基团的引发剂形成的聚合物材料
US11117992B2 (en) 2018-02-09 2021-09-14 Daikin Industries, Ltd. Fluoroelastomer composition and molded article thereof
CN110128766B (zh) * 2018-02-09 2021-07-09 大金工业株式会社 氟橡胶组合物及其成型品
CN110128766A (zh) * 2018-02-09 2019-08-16 大金工业株式会社 氟橡胶组合物及其成型品
CN111757895A (zh) * 2018-02-21 2020-10-09 3M创新有限公司 使用具有酮基团和两个含硫代羰基硫代基团的引发剂形成的聚合物材料
CN111757895B (zh) * 2018-02-21 2023-01-24 3M创新有限公司 使用具有酮基团和两个含硫代羰基硫代基团的引发剂形成的聚合物材料
CN112839969A (zh) * 2018-10-18 2021-05-25 大金工业株式会社 含氟弹性体、交联性组合物和成型品
CN115449008A (zh) * 2018-10-18 2022-12-09 大金工业株式会社 含氟弹性体、交联性组合物和成型品
CN115449008B (zh) * 2018-10-18 2023-10-24 大金工业株式会社 含氟弹性体、交联性组合物和成型品
CN114174362A (zh) * 2019-09-04 2022-03-11 大金工业株式会社 含氟共聚物
US20220195115A1 (en) * 2019-09-04 2022-06-23 Daikin Industries, Ltd. Fluorine-containing copolymer
EP4026694A4 (fr) * 2019-09-04 2023-08-30 Daikin Industries, Ltd. Copolymère contenant du fluor
US12428524B2 (en) * 2019-09-04 2025-09-30 Daikin Industries, Ltd. Fluorine-containing copolymer
EP4079770A4 (fr) * 2019-12-25 2024-01-24 Daikin Industries, Ltd. Procédé de production de fluoropolymère

Similar Documents

Publication Publication Date Title
US10377843B2 (en) Method for the controlled polymerization of fluoromonomers
WO2015173194A1 (fr) Fluoroélastomères
US10030087B2 (en) Method for manufacturing fluoroelastomers
US9688786B2 (en) Hyperbranched fluoroelastomer additive
JP5744902B2 (ja) フルオロエラストマーの製造方法
US11180592B2 (en) Method for manufacturing partially fluorinated polymers
IE921535A1 (en) Fluoroelastomers based on vinylidene fluoride exhibiting¹superior resistant to organic bases
WO2005073304A1 (fr) Fluoroelastomeres presentant une propriete amelioree a basse temperature, et procede de production des fluoroelastomeres
KR20110099254A (ko) (퍼)플루오로엘라스토머 조성물
US11015004B2 (en) Fluoroelastomer composition
KR102120657B1 (ko) 용매를 포함하는 퍼옥사이드-경화성 플루오로중합체 조성물 및 이의 사용 방법
US9631036B2 (en) Fluoroelastomers
EP3752562B1 (fr) Composition durcissable de fluoroélastomère
US8354472B2 (en) Fluoroelastomer composition
WO2017102820A1 (fr) Procédé de fabrication de fluoroélastomères

Legal Events

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

Ref document number: 15720744

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15720744

Country of ref document: EP

Kind code of ref document: A1