WO2012084587A1 - Low viscosity fluoroelastomers - Google Patents
Low viscosity fluoroelastomers Download PDFInfo
- Publication number
- WO2012084587A1 WO2012084587A1 PCT/EP2011/072520 EP2011072520W WO2012084587A1 WO 2012084587 A1 WO2012084587 A1 WO 2012084587A1 EP 2011072520 W EP2011072520 W EP 2011072520W WO 2012084587 A1 WO2012084587 A1 WO 2012084587A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluoroelastomer
- moles
- per
- recurring units
- formula
- Prior art date
Links
- 0 *C1(N)OC(N)=C(*)O1 Chemical compound *C1(N)OC(N)=C(*)O1 0.000 description 3
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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1408—Monomers containing halogen
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/10—Homopolymers or copolymers of unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/184—Monomers containing fluorine with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
- C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers
Definitions
- the present invention relates to novel fluoroelastomers, to a process for their production and their use, as well as a process for producing fluororubber mouldings and/or coatings.
- the liquid injection moulding technique has found wide use in the elastomer domain, in particular for the processing of silicon rubbers, typically provided as two-components liquid mixtures, comprising a crosslinkable resin and a catalyst.
- So-called 'liquid' or low viscosity fluoroelastomers have been proposed in the art as materials intended for processing notably via liquid injection moulding machines, i.e. processing tools wherein much lower temperatures and pressures are used with respect to traditional injection moulding devices which are intended to process molten materials.
- Traditional injection moulding machines generally consist of a material hopper, an injection ram or screw-type plunger, and a heating unit or press, which holds the mould in which the components are shaped; in the liquid injection moulding devices, the ram or plunger is merely replaced by a metering injectors.
- a standard injection moulding device working typically with molten polymers at pressures of 100 ⁇ 200 bar, while in a so called 'liquid' injection moulding machines, pressures of 15 ⁇ 20 bar being largely sufficient to promote flow of material into the mould.
- liquid status or low viscosity are required for processing according to screen printing or form-in-place techniques.
- a woven mesh is generally used for supporting a stencil.
- Said stencil thus provides open areas enabling transferring a liquid precursor of the elastomer ink (either neat or as a solution) as a sharp-edged image onto a substrate.
- a roller or squeegee is generally moved across the screen stencil, forcing or pumping the liquid ink past the threads of the woven mesh in the open areas. Subsequent curing and optionally evaporating/drying the solvent carrier enables fixing the elastomer into target shape.
- the use of liquid or low viscosity elastomers could enable avoiding the use of liquid carriers, with substantial advantages in equipment simplicity, environmental friendliness and processing speed.
- the rubber precursor is dispensed onto the parts in a viscous uncured form using dispense nozzles especially designed, e.g. to attain specific gasket sizes & shapes.
- Viscosity of the elastomer should be such to be efficiently ejected from nozzles, while still retaining the shape of ejected form onto the part until curing occurs.
- the dispensed parts can either be cured using an inline heating oven or placed in a stand alone oven for batch curing.
- the challenge of the use of these techniques for processing fluororubbers is to simultaneously achieve a suitable low liquid viscosity of the fluoroelastomer, to advantageously ensure appropriate flow of the material in the mould, during the roll coating and/or in the dispenser noozle, while still ensuring outstanding curing capabilities, so as to provide for finished article having required mechanical and sealing properties at reasonable throughput rate.
- Liquid fluoroelastomers endowed with reduced viscosities have been disclosed in the art.
- liquid fluoroelastomers that can at least be pumped at limited temperatures and that can be processed not only in conventional processing machinery but also in liquid injection moulding, screen printing and form-in-place devices maintaining outstanding cross-linking behaviour, and yielding resulting final parts exhibiting good mechanical as well as ageing properties, substantially similar to those of conventional solid fluororubbers.
- the object of the present invention is therefore to provide fluoroelastomers that advantageously exhibit this property profile.
- (per)fluoroelastomer [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) .
- 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.
- Fluoroelastomer (A) typically comprises recurring units derived from monomer (M) and from at least one (per)fluorinated monomer different from monomer (M).
- -CF 3 -CF 3 , -C 2 F 5 , -C 3 F 7 ;
- - fluoro-oxyalkylvinylethers different from formula (I) and complying with formula CF 2 CFOX 0 , in which X 0 is a C 1 -C 12 oxyalkyl, or a C 1 -C 12 (per)fluorooxyalkyl having one or more ether groups, like perfluoro-2-propoxy-propyl;
- hydrogenated monomers are notably non fluorinated 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 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.
- the fluoroelastomer (A) is preferably selected among: (1) VDF-based copolymers, comprising recurring units derived from VDF, from the monomer (M) and optionally from at least one additional (per)fluorinated monomer different from monomer (M) and VDF [comonomer (C)]; (2) TFE-based copolymers, comprising recurring units derived from TFE, from the monomer (M) and optionally from at least one additional (per)fluorinated monomer different from monomer (M) and TFE [comonomer (C)].
- Comonomer (C) will be generally selected from (per)fluorinated monomers, as above detailed, with the provision that: - if the fluoroelastomer (A) is a VDF-based copolymer, comonomer (C) is not VDF; and - if the fluoroelastomer (A) is aTFE-based copolymer, comonomer (C) is not TFE.
- the sum of recurring units derived from monomer (M) and comonomer (C) in fluoroelastomer (A) of the invention generally represents at least 10 % moles, preferably at least 15 % moles, more preferably at least 17 % moles, with respect to the total amount of recurring units of fluoroelastomer (A).
- the fluoroelastomer (A) comprises at least 1 % moles, with respect to the total moles of recurring units, of recurring units derived from monomer (M); typically, fluoroelastomer (A) will comprise at least 3 %, more preferably at least 5 %, more preferably at least 10 % moles, with respect to the total moles of recurring units, of recurring units derived from monomer (M).
- R f3 , R f4 , R f5 , R f6 are independently selected among fluorine atoms and C 1 -C 6 (per)fluoroalkyl groups, optionally comprising one or more than one oxygen atom, such as notably -CF 3 , -C 2 F 5 , -C 3 F 7 , -OCF 3 , -OCF 2 CF 2 OCF 3 ; preferably, perfluorodioxoles; (g) C 2 -C 8 non-fluorinated olefins (Ol), for example ethylene and propylene; and (2) TFE-based copolymers, comprising recurring units derived from TFE, recurring units derived from monomer (M) and, optionally, from at least one comonomer selected from the group consisting of classes (
- VDF-based copolymers are preferred and provide for increased crosslinking density, thus improved mechanical properties, while reducing the cost.
- VDF-based copolymers polymers comprising (with respect to total moles of recurring units of fluoroelastomer (A)): - from 5 to 35 % moles, preferably from 7 to 30 % moles, more preferably from 15 to 25 % moles of recurring units derived from monomer (M); - from 0.5 to 35 % moles, preferably from 1 to 30 % moles, more preferably from 2 to 25 % moles of recurring units derived from at least one C 2 -C 8 perfluoroolefin, typically selected from tetrafluoroethylene (TFE), hexafluoropropylene (HFP), hexafluoroisobutylene, preferably from TFE; with the provisio that the sum of recurring units derived from monomer (M) and from the perfluoroolefin is of at least 10 % moles, preferably at least 15 % moles, more preferably at least 17% moles; and -
- fluoroelastomer (A) of the present invention also comprises recurring units derived from a 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 or C 1 -C 5 alkyl; Z is a linear or branched C 1 -C 18 alkylene or cycloalkylene radical, optionally containing oxygen atoms, preferably at least partially fluorinated, 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 -
- the fluoroelastomer of the invention has a number-averaged molecular weight of 3 000 to 45 000.
- the number average molecular weight (M n ) is: , which can be notably determined by GPC.
- M w weight average molecular weight
- PDI polydispersity index
- the fluoroelastomer (A) of the invention has a number-averaged molecular weight of preferably at least 7 000, more preferably at least 10 000, even more preferably at least 12 000.
- 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.
- the fluoroelastomer (A) preferably possesses a dynamic viscosity, measured according to ASTM D4440 of less than 4 000 Pa x sec, preferably of less than 3 000 Pa x sec, more preferably of less than 2 000 Pa x sec, even more preferably of less than 1 500 Pa x sec, when determined at 40°C at a shear rate of 0.5 rad/sec.
- fluoroelastomer (A) preferably possesses a dynamic viscosity, measured according to ASTM D4440 of less than 150 Pa x sec, preferably of less than 140 Pa x sec, more preferably of less than 120 Pa x sec, when determined at 80°C at a shear rate of 0.5 rad/sec.
- fluoroelastomers (A) wherein the dynamic viscosity, measured according to ASTM D4440 at 40°C and at a shear rate of 0.5 rad/sec, is of at least 10 Pa x sec, preferably at least 50 Pa x sec, more preferably at least 100 Pa x sec, are those which exhibit best crosslinking behaviour.
- the fluoroelastomer (A) comprises cure sites; the selection of cure sites is not particularly critical, provided that they ensure adequate reactive in curing.
- the fluoroelastomer (A) can comprise said cure sites either as pendant groups bonded to certain recurring units or as end groups of the polymer chain.
- 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 .
- fluoroelastomer (A) of the invention comprises iodine or bromine cure sites in an amount of 0.001 to 10% wt.
- Iodine cure sites are those selected for maximizing curing rate.
- the content of iodine and/or bromine in the fluoroelastomer (A) should be of at least 0.05 % wt, preferably of at least 0.1 % weight, more preferably of at least 0.15 % weight, with respect to the total weight of fluoroelastomer (A).
- amounts of iodine and/or bromine not exceeding 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.
- iodine or bromine cure sites of these preferred embodiments of the invention 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 fluoroelastomer polymer chain;
- the fluoroelastomer (A) typically comprises recurring units derived from brominated and/or iodinated cure-site comonomers selected from: - bromo and/or iodo alpha-olefins containing from 2 to 10 carbon atoms such as bromotrifluoroethylene or bromotetrafluorobutene described, for example, in US 4035565 DU PONT 19770712 or other compounds bromo and/or iodo alpha-olefins disclosed in US 4694045 DU PONT 19870915 ; - iodo and/or bromo fluoroalkyl vinyl ethers (as notably described in patents US 4745165 AUSIMONT SPA 19880517 , US 4564662 MINNESOTA
- the fluoroelastomer according to this embodiment generally comprises recurring units derived from brominated and/or iodinated cure-site monomers in amounts of 0.05 to 5 mol per 100 mol of all other recurring units of the fluoroelastomer, so as to advantageously ensure above mentioned iodine and/or bromine weight content.
- the iodine and/or bromine cure sites are comprised as terminal groups of the fluoroelastomer polymer chain;
- the fluoroelastomer according to this embodiment is generally obtained by addition to the polymerization medium during fluoroelastomer manufacture of anyone of: - iodinated and/or brominated chain-transfer agent(s);
- suitable chain-chain transfer agents are typically those of formula R f (I) 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 DAIKIN IND LTD 19810106 and US 4943622 NIPPON MEKTRON KK 19900724 ); and - alkali metal or alkaline-earth metal iodides and/
- the invention also pertains to the use of the fluoroelastomer (A) as above described for fabricating shaped articles.
- the fluoroelastomer (A) can then 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 into a finished article made of non-tacky, strong, insoluble, chemically and thermally resistant cured fluoroelastomer.
- moulding injection moulding, extrusion moulding
- calendering or extrusion
- the fluoroelastomer of the invention is advantageously cured by peroxide curing technique, by ionic technique, by tin-catalyzed curing or by a mixed peroxidic/ionic technique.
- the peroxide curing is typically performed according to known techniques via addition of suitable peroxide that is capable of generating radicals by thermal decomposition.
- Organic peroxides are generally employed.
- an object of the invention is thus a peroxide curable composition
- a peroxide curable composition comprising fluoroelastomer (A) as above detailed and at least one peroxide, typically an organic peroxide.
- dialkyl peroxides for instance di-tert-butyl peroxide and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; dicumyl peroxide; dibenzoyl peroxide; di-tert-butyl perbenzoate; bis[1,3-dimethyl-3-(tert-butylperoxy)butyl] carbonate.
- suitable peroxide systems are those described, notably, in patent applications EP 136596 A MONTEDISON SPA 19850410 and EP 410351 A AUSIMONT SRL 19910130 , whose content is hereby incorporated by reference.
- ingredients generally comprised in the peroxide curable composition are : (a) curing coagents, in amounts generally of between 0.5 % and 10 % and preferably between 1 % and 7 % by weight relative to the polymer; among these 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 97/05122 (DU PONT [US]) 13/02/1997 ;
- Ionic curing can be achieved by mixing to the fluoroelastomer (A) one or more curing agent and one or more accelerator suitable for ionic curing, as well known in the art.
- an object of the invention is thus an ionically curable composition
- fluoroelastomer (A) as above detailed and at least one curing agent and at least one accelerator.
- the amounts of accelerator(s) are generally comprised between 0.05 and 5 phr and that of the curing agent typically between 0.5 and 15 phr and preferably between 1 and 6 phr.
- Aromatic or aliphatic polyhydroxylated compounds, or derivatives thereof, may be used as curing agents; examples thereof are described, notably, in EP 335705 A MINNESOTA MINING & MFG [US] + 19891004 and US 4233427 RHONE POULENC IND 19801111 .
- the aromatic rings may be substituted with one or more chlorine, fluorine or bromine atoms, or with carbonyl, alkyl or acyl groups.
- Bisphenol AF is particularly preferred.
- an adduct between an accelerator and a curing agent in a mole ratio of from 1:2 to 1:5 and preferably from 1:3 to 1:5, the accelerator being one of the organic onium compounds having a positive charge, as defined above, and the curing agent being chosen from the compounds indicated above, in particular dihydroxy or polyhydroxy or dithiol or polythiol compounds; the adduct being obtained by melting the product of reaction between the accelerator and the curing agent in the indicated mole ratios, or by melting the mixture of the 1:1 adduct supplemented with the curing agent in the indicated amounts.
- an excess of the accelerator, relative to that contained in the adduct may also be present.
- adduct 1,1-diphenyl-1-benzyl-N-diethylphosphoranamine and tetrabutylphosphonium; particularly preferred anions are bisphenol compounds in which the two aromatic rings are bonded via a divalent radical chosen from perfluoroalkyl groups of 3 to 7 carbon atoms, and the OH groups are in the para position.
- a method suitable for the preparation of an adduct as above described is described in European patent application EP 0684277 A AUSIMONT SPA [IT] 19951129 , which is included herein in its entirety by reference.
- ingredients generally added to the ionically curable composition comprising fluoroelastomer (A) of the invention, when curing via ionic route are : i) one or more mineral acid acceptors chosen from those known in the ionic curing of vinylidene fluoride copolymers, typically comprised in amounts of 1-40 parts per 100 parts of fluoroelastomer (A); ii) one or more basic compounds chosen from those known in the ionic curing of vinylidene fluoride copolymers, typically added in amounts of from 0.5 to 10 parts per 100 parts of fluoroelastomer (A).
- the basic compounds mentioned in point ii) are commonly chosen from the group constituted by Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , metal salts of weak acids, for instance Ca, Sr, Ba, Na and K carbonates, benzoates, oxalates and phosphites and mixtures of the abovementioned hydroxides with the above mentioned metal salts; among the compounds of the type i), mention may be made of MgO.
- the above mentioned amounts of the mixture are relative to 100 phr of fluoroelastomer (A).
- other conventional additives such as fillers, thickeners, pigments, antioxidants, stabilizers and the like, may then be added to the curing mixture.
- Mixed peroxidic/ionic curing can be achieved by simultaneously introducing in the curable composition one or more peroxide, as above detailed, and one or more curing agent and one or more accelerator suitable for ionic curing, as well known in the art.
- the fluoroelastomer (A) comprises recurring units derived from ethylenically unsaturated compounds comprising cyanide groups of type (CSM-2) as above detailed, organotin compounds or diaromatic amine compounds, as notably described in US 4394489 DU PONT 19830719 (disclosing allyl-, propargyl- and allenyl- tin curatives), US 5767204 NIPPON MEKTRON KK 19980616 (providing bis(aminophenyl) compounds represented by formula: wherein A is an alkylidene group having 1 to 6 carbon atoms or a perfluoroalkylidene group having 1 to 10 carbon atoms and X and Y are a hydroxyl group or an amino group) and US 5789509 DU PONT 19980804 (disclosing tetraalkyltin, tetraaryltin compounds, bis(aminophenols) and bis(aminothiophenols)).
- This type of vulcanization may be combined with a vulcanization of peroxide type, in the case where the fluoroelastomer matrix contains iodinated and/or brominated end groups, as described notably in US 5447993 DU PONT 19950905 .
- the invention pertains to cured articles obtained from the fluoroelastomer (A). Said cured articles are generally obtained by moulding and curing the peroxide curable composition, as above detailed.
- the invention pertains to a method for processing fluoroelastomer (A) according any of liquid injection moulding technique, screen printing technique, form-in-place technique. These techniques are described above.
- Example 1 Preparation of fluoroelastomer A-1.
- the reactor was heated and maintained at a set-point temperature of 70°C.
- TFE tetrafluoroethylene
- VDF vinylidene fluoride
- APS ammonium persulfate
- Fluoroelastomer of Example 1 was compounded with the additives in a Speedmixer. Plaques were cured in a pressed mould and then post-treated in an air circulating oven in conditions (time, temperature) below specified. The tensile properties have been determined on specimens punched out from the plaques, according to the DIN 53504 S2 Standard. M100 is the tensile strength in MPa at an elongation of 100 %; TS is the tensile strength in MPa; EB is the elongation at break in %. The Shore A hardness (3") (HDS) has been determined on 3 pieces of plaque piled according to the ASTM D 2240 method. Compression set values have been determined on 3 disks punched out from the plaques piled according to the ASTM D 395-B method. Curing recipe and conditions and properties of cured sample are summarized, respectively, in tables 1 and 2.
- Table 1 A-1 (from Ex. 1) wt parts 100 Trigonox 101 1 phr 1.5 Taicros 2 phr 3.0 Carbon black 3 N991 phr 20
- Example 2 Preparation of fluoroelastomer A-2. Same procedure as detailed in Example 1 was repeated, but a mixture of TFE (11% moles) and VDF (89% moles) was added to reach a final pressure of 11 bar (1.1 MPa) and 62 g of C 4 F 8 I 2 as chain transfer agent were introduced, the gaseous mixture continuously fed was TFE (7% moles) and VDF (93% moles) up to a total of 850 g, and 650 g of monomer (M1) in 20 portions of 32.5 g, starting from the beginning of the polymerization and for every 5% increase in the conversion of gaseous mixture, were fed to the reactor. Furthermore, 0.36 g of APS at 15% of conversion of gaseous mixture and 0.7 g of APS at 25% of conversion of gaseous mixture were also fed. The properties of the obtained polymer are summarized in table 3.
- the reactor was heated and maintained at a set-point temperature of 80°C.
- a mixture of TFE (7.7% moles), VDF (48.7% moles) and hexafluoropropene (HFP) (43.6% moles) was then added to reach a final pressure of 31 bar (3.1 MPa).
- 152 g of C 4 F 8 I 2 as chain transfer agent and 2.05 g of APS as initiator were then introduced.
- Pressure was maintained at set-point of 31 bar by continuous feeding of a gaseous mixture of TFE (11% moles), VDF (70% moles) and HFP (19% moles) up to a total of 3500 g. Then the reactor was cooled, vented and the latex recovered.
- the latex was coagulated by freezing and subsequent thawing, the polymer separated from the aqueous phase, washed with demineralised water and dried in a convection oven at 100°C for 16 hours.
- the properties of the obtained polymer are summarized in table 3.
- the reactor was heated and maintained at a set-point temperature of 80°C.
- a mixture of TFE (13.3% moles), VDF (17.8% moles) and HFP (68.9% moles) was then added to reach a final pressure of 31 bar (3.1 MPa).
- 57.3 g of C 4 F 8 I 2 as chain transfer agent and 1.2 g of APS as initiator were then introduced.
- Pressure was maintained at set-point of 31 bar by continuous feeding of a gaseous mixture of TFE (25% moles), VDF (48% moles) and HFP (27% moles) up to a total of 1500 g. Then the reactor was cooled, vented and the latex recovered.
- the latex was coagulated by freezing and subsequent thawing, the polymer separated from the aqueous phase, washed with demineralised water and dried in a convection oven at 100°C for 16 hours.
- the properties of the obtained polymer are summarized in table 3.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
According to the former technique, a woven mesh is generally used for supporting a stencil. Said stencil thus provides open areas enabling transferring a liquid precursor of the elastomer ink (either neat or as a solution) as a sharp-edged image onto a substrate. To this aim, a roller or squeegee is generally moved across the screen stencil, forcing or pumping the liquid ink past the threads of the woven mesh in the open areas. Subsequent curing and optionally evaporating/drying the solvent carrier enables fixing the elastomer into target shape. Within this processing technique, the use of liquid or low viscosity elastomers could enable avoiding the use of liquid carriers, with substantial advantages in equipment simplicity, environmental friendliness and processing speed.
- containing up to 1 % wt of iodine or bromine;
- having a number averaged molecular weight of more than 25 000;
- further comprising recurring units derived from comprising fluorine containing monomers, among which mention is made of perfluorinated vinyl ethers of formula CF2=CF-O-X, with X being a perfluoroalkyl C1-C3 or a group of formula -(CF2CFYO)n-Rf, with n= 1-4, Y = F or CF3 and Rf being a C1-C3 perfluoroalkyl.
CFX’=CX”OCF2ORf formula (I)
wherein X' and X", equal to or different from each other, are independently H or F; and Rf is selected from the group consisting of C1-C6 (per)fluoroalkyls, linear or branched; C5-C6 cyclic (per)fluoroalkyls ; and C2-C6 (per)fluorooxyalkyls, linear or branched, comprising from 1 to 3 catenary ethereal oxygen atoms [monomer (M)].
- C2-C8 fluoro- and/or perfluoroolefins, such as tetrafluoroethylene (TFE), hexafluoropropene (HFP), pentafluoropropylene, and hexafluoroisobutylene;
- C2-C8 hydrogenated monofluoroolefins, such as vinyl fluoride;
- 1,2-difluoroethylene, vinylidene fluoride (VDF) and trifluoroethylene (TrFE);
- (per)fluoroalkylethylenes complying with formula CH2=CH-Rf0, in which Rf0 is a C1-C6 (per)fluoroalkyl or a C1-C6 (per)fluorooxyalkyl having one or more ether groups ;
- chloro- and/or bromo- and/or iodo-C2-C6 fluoroolefins, like chlorotrifluoroethylene (CTFE);
- fluoroalkylvinylethers complying with formula CF2=CFORf1 in which Rf1 is a C1-C6 fluoro- or perfluoroalkyl, e.g. -CF3, -C2F5, -C3F7 ;
- hydrofluoroalkylvinylethers complying with formula CH2=CFORf1 in which Rf1 is a C1-C6 fluoro- or perfluoroalkyl, e.g. -CF3, -C2F5, -C3F7 ;
- fluoro-oxyalkylvinylethers different from formula (I) and complying with formula CF2=CFOX0, in which X0 is a C1-C12 oxyalkyl, or a C1-C12 (per)fluorooxyalkyl having one or more ether groups, like perfluoro-2-propoxy-propyl;
- functional fluoro-alkylvinylethers complying with formula CF2=CFOY0, in which Y0 is a C1-C12 alkyl or (per)fluoroalkyl, or a C1-C12 oxyalkyl or a C1-C12 (per)fluorooxyalkyl, said Y0 group comprising a carboxylic or sulfonic acid group, in its acid, acid halide or salt form;
- fluorodioxoles, of formula : wherein each of Rf3, Rf4, Rf5, Rf6, equal or different 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, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3.
CF2=CFOCF2OR’f formula (I)
wherein R’f is selected from the group consisting of C1-C6 perfluoroalkyls, linear or branched; C5-C6 cyclic perfluoroalkyls ; and C2-C6 perfluorooxyalkyls, linear or branched, comprising from 1 to 3 catenary ethereal oxygen atoms.
(M1) CF2=CFOCF2O-CF3;
(M2) CF2=CFOCF2O-CF2CF3;
(M3) CF2=CFOCF2O-CF2CF2OCF3,
with the monomer (M) of formula (M1) being generally preferred.
(1) VDF-based copolymers, comprising recurring units derived from VDF, from the monomer (M) and optionally from at least one additional (per)fluorinated monomer different from monomer (M) and VDF [comonomer (C)];
(2) TFE-based copolymers, comprising recurring units derived from TFE, from the monomer (M) and optionally from at least one additional (per)fluorinated monomer different from monomer (M) and TFE [comonomer (C)].
- if the fluoroelastomer (A) is a VDF-based copolymer, comonomer (C) is not VDF; and
- if the fluoroelastomer (A) is aTFE-based copolymer, comonomer (C) is not TFE.
(1) VDF-based copolymers, comprising recurring units derived from VDF, recurring units derived from monomer (M) and optionally at least one comonomer selected from the group consisting of the followings classes :
(a) C2-C8 perfluoroolefins , such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), hexafluoroisobutylene;
(b) hydrogen-containing C2-C8 olefins, such as vinyl fluoride (VF), trifluoroethylene (TrFE), perfluoroalkyl ethylenes of formula CH2 = CH-Rf, wherein Rf is a C1‑C6 perfluoroalkyl group;
(c) C2-C8 chloro and/or bromo and/or iodo-fluoroolefins such as chlorotrifluoroethylene (CTFE);
(d) (per)fluoroalkylvinylethers (PAVE) of formula CF2 = CFORf, wherein Rf is a C1-C6 (per)fluoroalkyl group, e.g. CF3, C2F5, C3F7;
(e) (per)fluoro-oxy-alkylvinylethers of formula CF2 = CFOX, wherein X is a C1-C12 ((per)fluoro)-oxyalkyl comprising catenary oxygen atoms, e.g. the perfluoro-2-propoxypropyl group;
(f) (per)fluorodioxoles having formula : wherein Rf3, Rf4, Rf5, Rf6, equal or different from each other, are independently selected among fluorine atoms and C1-C6 (per)fluoroalkyl groups, optionally comprising one or more than one oxygen atom, such as notably -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3; preferably, perfluorodioxoles;
(g) C2-C8 non-fluorinated olefins (Ol), for example ethylene and propylene; and
(2) TFE-based copolymers, comprising recurring units derived from TFE, recurring units derived from monomer (M) and, optionally, from at least one comonomer selected from the group consisting of classes (c), (d), (e), (g),as above detailed.
- from 5 to 35 % moles, preferably from 7 to 30 % moles, more preferably from 15 to 25 % moles of recurring units derived from monomer (M);
- from 0.5 to 35 % moles, preferably from 1 to 30 % moles, more preferably from 2 to 25 % moles of recurring units derived from at least one C2-C8 perfluoroolefin, typically selected from tetrafluoroethylene (TFE), hexafluoropropylene (HFP), hexafluoroisobutylene, preferably from TFE;
with the provisio that the sum of recurring units derived from monomer (M) and from the perfluoroolefin is of at least 10 % moles, preferably at least 15 % moles, more preferably at least 17% moles;
and
- from 90 to 30 % moles, preferably from 85 to 40 % moles, more preferably from 83 to 50 % moles of recurring units derived from VDF.
(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 C1-5 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 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; preferably E is a –(CF2)m- group, with m being an integer from 3 to 5; a preferred bis-olefin of (OF-2) type is F2C=CF-O-(CF2)5-O-CF=CF2.
(OF-3) wherein E, A and B have the same meaning as above defined; R5, R6, R7, equal or different from each other, are H, F or C1-5 alkyl or (per)fluoroalkyl group.
the polydispersity index (PDI), which is hereby expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn).
(CSM-1) iodine or bromine containing monomers of formula: wherein each of AHf, equal to or different from each other and at each occurrence, is independently selected from F, Cl, and H; BHf is any of F, Cl, H and ORHf B, wherein RHf B is a branched or straight chain alkyl radical which can be partially, substantially or completely fluorinated or chlorinated; each of WHf equal to or different from each other and at each occurrence, is independently a covalent bond or an oxygen atom; EHf is a divalent group having 2 to 10 carbon atom, optionally fluorinated; RHf is a branched or straight chain alkyl radical, which can be partially, substantially or completely fluorinated; and RHf is a halogen atom selected from the group consisting of Iodine and Bromine; which may be inserted with ether linkages; preferably E is a –(CF2)m- group, with m being an integer from 3 to 5;
(CSM-2) ethylenically unsaturated compounds comprising cyanide groups, possibly fluorinated.
(CSM1-A) iodine-containing perfluorovinylethers of formula: with m being an integer from 0 to 5 and n being an integer from 0 to 3, with the provisio that at least one of m and n is different from 0, and Rfi being F or CF3; (as notably described in patents
(CSM-1B) iodine-containing ethylenically unsaturated compounds of formula:
CX1X2=CX3-(CF2CF2)-I
wherein each of X1, X2 and X3, equal to or different from each other, are independently H or F; and p is an integer from 1 to 5; among these compounds, mention can be made of CH2=CHCF2CF2I, I(CF2CF2)2CH=CH2, ICF2CF2CF=CH2, I(CF2CF2)2CF=CH2;
(CSM-1C) iodine-containing ethylenically unsaturated compounds of formula:
CHR=CH-Z-CH2CHR-I
wherein R is H or CH3, Z is a C1-C18 (per)fluoroalkylene radical, linear or branched, optionally containing one or more ether oxygen atoms, or a (per)fluoropolyoxyalkylene radical; among these compounds, mention can be made of CH2=CH-(CF2)4CH2CH2I, CH2=CH-(CF2)6CH2CH2I, CH2=CH-(CF2)8CH2CH2I, CH2=CH-(CF2)2CH2CH2I;
(CSM-1D) bromo and/or iodo alpha-olefins containing from 2 to 10 carbon atoms such as bromotrifluoroethylene or bromotetrafluorobutene described, for example, in
(CSM2-A) perfluorovinyl ethers containing cyanide groups of formula CF2=CF-(OCF2CFXCN)m-O-(CF2)n-CN, with XCN being F or CF3, m being 0, 1, 2, 3 or 4; n being an integer from 1 to 12;
(CSM2-B) perfluorovinyl ethers containing cyanide groups of formula CF2=CF-(OCF2CFXCN)m’-O-CF2—CF(CF3)-CN, with XCN being F or CF3, m’ being 0, 1, 2, 3 or 4.
Specific examples of 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
- bromo and/or iodo alpha-olefins containing from 2 to 10 carbon atoms such as bromotrifluoroethylene or bromotetrafluorobutene described, for example, in
- iodo and/or bromo fluoroalkyl vinyl ethers (as notably described in patents
- iodinated and/or brominated chain-transfer agent(s); suitable chain-chain transfer agents are typically those of formula Rf(I)x(Br)y, in which Rf 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
- alkali metal or alkaline-earth metal iodides and/or bromides, such as described notably in patent
(a) curing coagents, in amounts generally of between 0.5 % and 10 % and preferably between 1 % and 7 % by weight relative to the polymer; among these 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
(b) optionally, a metallic compound, in amounts of between 1 % and 15 % and preferably between 2 % and 10 % by weight relative to the weight of the polymer, chosen from oxides or hydroxides of divalent metals, for instance Mg, Zn, Ca or Pb, optionally combined with a salt of a weak acid, for instance Ba, Na, K, Pb, Ca stearates, benzoates, carbonates, oxalates or phosphites;
(c) optionally, acid acceptors of the metal non-oxide type, such as 1,8‑bis(dimethylamino)naphthalene, octadecylamine, etc., as notably described in
(d) optionally, other conventional additives, such as fillers, thickeners, pigments, antioxidants, stabilizers, processing aids, and the like.
i) one or more mineral acid acceptors chosen from those known in the ionic curing of vinylidene fluoride copolymers, typically comprised in amounts of 1-40 parts per 100 parts of fluoroelastomer (A);
ii) one or more basic compounds chosen from those known in the ionic curing of vinylidene fluoride copolymers, typically added in amounts of from 0.5 to 10 parts per 100 parts of fluoroelastomer (A).
In a 5 litres reactor equipped with a mechanical stirrer operating at 630 rpm, 3.5 l of demineralized water and 35 ml of a microemulsion, previously obtained by mixing 8.3 ml of a perfluoropolyoxyalkylene having acidic end groups of formula: CF2ClO(CF2-CF(CF3)O)n(CF2O)mCF2COOH, wherein n/m = 10, having average molecular weight of 600, 2.2 ml of a 30 % v/v NH4OH aqueous solution, 19.6 ml of demineralised water and 4.9 ml of GALDEN® D02 perfluoropolyether of formula:
CF3O(CF2CF(CF3)O)n(CF2O)mCF3 with n/m = 20, having average molecular weight of 450, were introduced.
The reactor was heated and maintained at a set-point temperature of 70°C. 50 g of monomer (M1) of formula CF2=CF-O-CF2-O-CF3 were introduced, and a mixture of tetrafluoroethylene (TFE) (25.9% moles) and vinylidene fluoride (VDF) (74.1% moles) was then added to reach a final pressure of 11 bar (1.1 MPa). 56 g of 1,4-diiodoperfluorobutane (C4F8I2) as chain transfer agent and 0.7 g of ammonium persulfate (APS) as initiator were then introduced. Pressure was maintained at set-point of 11 bar by continuous feeding of a gaseous mixture of TFE (20.5% moles) and VDF (79.5% moles) up to a total of 740 g, and 760 g of monomer (M1) in 20 portions of 38 g, starting from the beginning of the polymerization and for every 5% increase in the conversion of gaseous mixture, were also fed to the reactor. Then the reactor was cooled, vented and the latex recovered. The latex was coagulated by freezing and subsequent thawing, the polymer separated from the aqueous phase, washed with demineralised water and dried in a convection oven at 100°C for 16 hours. The properties of the obtained polymer are summarized in table 3.
The tensile properties have been determined on specimens punched out from the plaques, according to the DIN 53504 S2 Standard.
M100 is the tensile strength in MPa at an elongation of 100 %;
TS is the tensile strength in MPa;
EB is the elongation at break in %.
The Shore A hardness (3") (HDS) has been determined on 3 pieces of plaque piled according to the ASTM D 2240 method.
Compression set values have been determined on 3 disks punched out from the plaques piled according to the ASTM D 395-B method.
Curing recipe and conditions and properties of cured sample are summarized, respectively, in tables 1 and 2.
A-1 (from Ex. 1) | wt parts | 100 |
Trigonox 1011 | phr | 1.5 |
Taicros2 | phr | 3.0 |
Carbon black3 N991 | phr | 20 |
- 1: 2,5-dimethyl-2,5-di-t-butyl-peroxy-hexane, commercially available from AkzoNobel; 2: Triallyl isocyanurate, commercially available from Evonik; 3: C-black N991.
Property | unit | Ex. 1 |
Moulding/curing: 5 min at 170°C Post-cure: 4h at 180°C |
||
Mechanical properties on S2 samples | ||
TS | MPa | 5.1 |
M100 | MPa | 1.3 |
EB | % | 150 |
HDS | ShA | 59 |
Compression set after post-cure 4h at 180°C | ||
C-SET | % | 27 |
Same procedure as detailed in Example 1 was repeated, but a mixture of TFE (11% moles) and VDF (89% moles) was added to reach a final pressure of 11 bar (1.1 MPa) and 62 g of C4F8I2 as chain transfer agent were introduced, the gaseous mixture continuously fed was TFE (7% moles) and VDF (93% moles) up to a total of 850 g, and 650 g of monomer (M1) in 20 portions of 32.5 g, starting from the beginning of the polymerization and for every 5% increase in the conversion of gaseous mixture, were fed to the reactor. Furthermore, 0.36 g of APS at 15% of conversion of gaseous mixture and 0.7 g of APS at 25% of conversion of gaseous mixture were also fed. The properties of the obtained polymer are summarized in table 3.
In a 10 litres reactor equipped with a mechanical stirrer operating at 545 rpm, 6 l of demineralized water and 60 ml of a microemulsion, previously obtained by mixing 13 ml of a perfluoropolyoxyalkylene having acidic end groups of formula: CF2ClO(CF2-CF(CF3)O)n(CF2O)mCF2COOH, wherein n/m = 10, having average molecular weight of 600, 4.6 ml of a 30 % v/v NH4OH aqueous solution, 34.6 ml of demineralised water and 7.8 ml of GALDEN® D02 perfluoropolyether of formula:
CF3O(CF2CF(CF3)O)n(CF2O)mCF3 with n/m = 20, having average molecular weight of 450, were introduced.
The reactor was heated and maintained at a set-point temperature of 80°C. A mixture of TFE (7.7% moles), VDF (48.7% moles) and hexafluoropropene (HFP) (43.6% moles) was then added to reach a final pressure of 31 bar (3.1 MPa). 152 g of C4F8I2 as chain transfer agent and 2.05 g of APS as initiator were then introduced. Pressure was maintained at set-point of 31 bar by continuous feeding of a gaseous mixture of TFE (11% moles), VDF (70% moles) and HFP (19% moles) up to a total of 3500 g. Then the reactor was cooled, vented and the latex recovered. The latex was coagulated by freezing and subsequent thawing, the polymer separated from the aqueous phase, washed with demineralised water and dried in a convection oven at 100°C for 16 hours. The properties of the obtained polymer are summarized in table 3.
In a 5 litres reactor equipped with a mechanical stirrer operating at 630 rpm, 3.5 l of demineralized water and 35 ml of a microemulsion, previously obtained by mixing 7.6 ml of a perfluoropolyoxyalkylene having acidic end groups of formula: CF2ClO(CF2-CF(CF3)O)n(CF2O)mCF2COOH, wherein n/m = 10, having average molecular weight of 600, 2.7 ml of a 30 % v/v NH4OH aqueous solution, 20.2 ml of demineralised water and 4.5 ml of GALDEN® D02 perfluoropolyether of formula:
CF3O(CF2CF(CF3)O)n(CF2O)mCF3 with n/m = 20, having average molecular weight of 450, were introduced.
The reactor was heated and maintained at a set-point temperature of 80°C. A mixture of TFE (13.3% moles), VDF (17.8% moles) and HFP (68.9% moles) was then added to reach a final pressure of 31 bar (3.1 MPa). 57.3 g of C4F8I2 as chain transfer agent and 1.2 g of APS as initiator were then introduced. Pressure was maintained at set-point of 31 bar by continuous feeding of a gaseous mixture of TFE (25% moles), VDF (48% moles) and HFP (27% moles) up to a total of 1500 g. Then the reactor was cooled, vented and the latex recovered. The latex was coagulated by freezing and subsequent thawing, the polymer separated from the aqueous phase, washed with demineralised water and dried in a convection oven at 100°C for 16 hours. The properties of the obtained polymer are summarized in table 3.
Same procedure as detailed in Example 4 was repeated, but a mixture of TFE (6.1% moles), perfluoromethylvinylether (MVE) (33.4% moles) and VDF (60.5% moles) was added to reach a final pressure of 31 bar (3.1 MPa), 64.7 g of C4F8I2 as chain transfer agent and 0.8 g of APS as initiator were introduced, and the gaseous mixture continuously fed was TFE (8% moles), MVE (18% moles) and VDF (74% moles). The properties of the obtained polymer are summarized in table 3.
Run | unit | 1 | 2 | 3C | 4C | 5C |
Monomer composition | ||||||
TFE | %mol | 19.2 | 6 | 11 | 24 | 6 |
VDF | %mol | 59.4 | 76.5 | 70 | 53 | 76.5 |
HFP | %mol | 19 | 23 | |||
MVE | %mol | 17.5 | ||||
MOVE§ | %mol | 21.4 | 17.5 | |||
Fluorine content | %w | 65.2 | 63.0 | 67.16 | 69.9 | |
Hydrogen content | %w | 1.1 | 1.6 | 1.66 | 1.15 | 1.8 |
Iodine content | %w | 1.4 | 1.6 | 1.9 | 1.8 | 1.5 |
GPC (Molecular weight) | ||||||
Mn | Dalton | 15200 | 16900 | 14100 | 12400 | 13500 |
Mw | Dalton | 20300 | 25300 | 24300 | 17700 | 20800 |
PdMWD | 1.3 | 1.5 | 1.7 | 1.4 | 1.5 | |
PPR (parallel plates rheology): Complex viscosity at 40°C at variable shear rate | ||||||
0.5 rad/s | Pa×s | 333 | 1098 | 5406 | 30539 | 3402 |
5 rad/s | Pa×s | 333 | 846 | 5113 | 17674 | 3102 |
50 rad/s | Pa×s | 328 | 659 | 3084 | 7750 | 2122 |
PPR (parallel plates rheology): Complex viscosity at 80°C at variable shear rate | ||||||
0.5 rad/s | Pa×s | 24 | 31 | 176 | 124 | 1152 |
5 rad/s | Pa×s | 24 | 30 | 175 | 105 | 112 |
50 rad/s | Pa×s | 23 | 30 | 173 | 98 | 111 |
Claims (15)
- A low viscosity curable (per)fluoroelastomer [fluoroelastomer (A)] having a number-averaged molecular weight of 3 000 to 45 000 , said (per)fluoroelastomer comprising at least 1 % moles, with respect to the total moles of recurring units, of recurring units derived from at least one (per)fluoromethoxyalkylvinylether of formula (I):CFX’=CX”OCF2ORf formula (I)wherein X' and X", equal to or different from each other, are independently H or F; and Rf is selected from the group consisting of C1-C6 (per)fluoroalkyls, linear or branched; C5-C6 cyclic (per)fluoroalkyls ; and C2-C6 (per)fluorooxyalkyls, linear or branched, comprising from 1 to 3 catenary ethereal oxygen atoms [monomer (M)], and further comprising recurring units derived from at least one (per)fluorinated monomer different from monomer (M).
- The fluoroelastomer (A) of claim 1, wherein monomer (M) is a perfluoromethoxyalkylvinylether of formula (I):CF2=CFOCF2OR’f formula (I)wherein R’f is selected from the group consisting of C1-C6 perfluoroalkyls, linear or branched; C5-C6 cyclic perfluoroalkyls ; and C2-C6 perfluorooxyalkyls, linear or branched, comprising from 1 to 3 catenary ethereal oxygen atoms.
- The fluoroelastomer of claim 2, wherein monomer (M) is selected from the group consisting of:(M1) CF2=CFOCF2O-CF3;(M2) CF2=CFOCF2O-CF2CF3;(M3) CF2=CFOCF2O-CF2CF2OCF3.
- The fluoroelastomer (A) of claim 1, wherein fluoroelastomer (A) is selected from the group consisting of:(1) VDF-based copolymers, comprising recurring units derived from VDF, from the monomer (M) and optionally from at least one additional (per)fluorinated monomer different from monomer (M) and VDF [comonomer (C)];(2) TFE-based copolymers, comprising recurring units derived from TFE, from the monomer (M) and optionally from at least one additional (per)fluorinated monomer different from monomer (M) and TFE [comonomer (C)].
- The fluoroelastomer (A) of claim 4, wherein said comonomer (C) is selected from the group consisting of:- C2-C8 fluoro- and/or perfluoroolefins, such as tetrafluoroethylene (TFE), hexafluoropropene (HFP), pentafluoropropylene, and hexafluoroisobutylene;- C2-C8 hydrogenated monofluoroolefins, such as vinyl fluoride;- 1,2-difluoroethylene, vinylidene fluoride (VDF) and trifluoroethylene (TrFE);- (per)fluoroalkylethylenes complying with formula CH2=CH-Rf0, in which Rf0 is a C1-C6 (per)fluoroalkyl or a C1-C6 (per)fluorooxyalkyl having one or more ether groups ;- chloro- and/or bromo- and/or iodo-C2-C6 fluoroolefins, like chlorotrifluoroethylene (CTFE);- fluoroalkylvinylethers complying with formula CF2=CFORf1 in which Rf1 is a C1-C6 fluoro- or perfluoroalkyl, e.g. -CF3, -C2F5, -C3F7 ;- hydrofluoroalkylvinylethers complying with formula CH2=CFORf1 in which Rf1 is a C1-C6 fluoro- or perfluoroalkyl, e.g. -CF3, -C2F5, -C3F7 ;- fluoro-oxyalkylvinylethers different from formula (I) and complying with formula CF2=CFOX0, in which X0 is a C1-C12 oxyalkyl, or a C1-C12 (per)fluorooxyalkyl having one or more ether groups, like perfluoro-2-propoxy-propyl;- functional fluoro-alkylvinylethers complying with formula CF2=CFOY0, in which Y0 is a C1-C12 alkyl or (per)fluoroalkyl, or a C1-C12 oxyalkyl or a C1-C12 (per)fluorooxyalkyl, said Y0 group comprising a carboxylic or sulfonic acid group, in its acid, acid halide or salt form;- fluorodioxoles, of formula : wherein each of Rf3, Rf4, Rf5, Rf6, equal or different 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, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3,with the provision that:- if the fluoroelastomer (A) is a VDF-based copolymer, comonomer (C) is not VDF; and- if the fluoroelastomer (A) is aTFE-based copolymer, comonomer (C) is not TFE.
- The fluoroelastomer (A) of claims 4 or 5, comprising at least 3 % moles, preferably at least 5 %, more preferably at least 10 % moles, with respect to the total moles of recurring units, of recurring units derived from monomer (M).
- The fluoroelastomer (A) of anyone of claims 4 to 6, wherein the sum of recurring units derived from monomer (M) and comonomer (C) represents at least 10 % moles, preferably at least 15 % moles, more preferably at least 17 % moles, with respect to the total amount of recurring units of fluoroelastomer (A).
- The fluoroelastomer (A) of claim 7, said fluoroelastomer being selected from the group consisting of VDF-based copolymers comprising (with respect to total moles of recurring units of fluoroelastomer (A)):- from 5 to 35 % moles, preferably from 7 to 30 % moles, more preferably from 15 to 25 % moles of recurring units derived from monomer (M);- from 0.5 to 35 % moles, preferably from 1 to 30 % moles, more preferably from 2 to 25 % moles of recurring units derived from at least one C2-C8 perfluoroolefin, typically selected from tetrafluoroethylene (TFE), hexafluoropropylene (HFP), hexafluoroisobutylene, preferably from TFE;with the provisio that the sum of recurring units derived from monomer (M) and from the perfluoroolefin is of at least 10 % moles, preferably at least 15 % moles, more preferably at least 17% moles;and- from 90 to 30 % moles, preferably from 85 to 40 % moles, more preferably from 83 to 50 % moles of recurring units derived from VDF.
- The fluoroelastomer (A) of anyone of the preceding claims, having a number-averaged molecular weight of at least 7 000, preferably at least 10 000, more preferably at least 12 000.
- The fluoroelastomer (A) of anyone of the preceding claims, having a number-averaged molecular weight of at most 40 000, preferably at most 35 000, more preferably at most 30 000.
- The fluoroelastomer (A) of anyone of the preceding claims, said fluoroelastomer comprising cure sites as pendant groups bonded to certain recurring units (cure-site containing recurring units).
- The fluoroelastomer (A) of claim 11, wherein said cure-site containing recurring units are selected from the group consisting of:(CSM-1) iodine or bromine containing monomers of formula: wherein each of AHf, equal to or different from each other and at each occurrence, is independently selected from F, Cl, and H; BHf is any of F, Cl, H and ORHf B, wherein RHf B is a branched or straight chain alkyl radical which can be partially, substantially or completely fluorinated or chlorinated; each of WHf equal to or different from each other and at each occurrence, is independently a covalent bond or an oxygen atom; EHf is a divalent group having 2 to 10 carbon atom, optionally fluorinated; RHf is a branched or straight chain alkyl radical, which can be partially, substantially or completely fluorinated; and RHf is a halogen atom selected from the group consisting of Iodine and Bromine; which may be inserted with ether linkages; preferably E is a –(CF2)m- group, with m being an integer from 3 to 5;(CSM-2) ethylenically unsaturated compounds comprising cyanide groups, possibly fluorinated.
- The fluoroelastomer (A) of anyone of the preceding claims, said fluoroelastomer comprising iodine or bromine cure site in an amount of 0.001 to 10 % wt.
- The fluoroelastomer (A) of claim 13, wherein said iodine or bromine cure sites are comprised as pending groups bound to the backbone of the fluoroelastomer (A) polymer chain and/or are comprised as terminal groups of said polymer chain.
- The fluoroelastomer (A) of claims 13 or 14, wherein said fluoroelastomer (A) is obtained by addition to the polymerization medium during fluoroelastomer manufacture of anyone of:- iodinated and/or brominated chain-transfer agent(s); suitable chain-chain transfer agents are typically those of formula Rf(I)x(Br)y, in which Rf 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; and- alkali metal or alkaline-earth metal iodides and/or bromides.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013543697A JP6333554B2 (en) | 2010-12-20 | 2011-12-13 | Low viscosity fluoroelastomer |
US13/993,782 US9458272B2 (en) | 2010-12-20 | 2011-12-13 | Low viscosity fluoroelastomers |
CN201180067934.1A CN103370346B (en) | 2010-12-20 | 2011-12-13 | low viscosity fluoroelastomer |
EP11794746.5A EP2655441B1 (en) | 2010-12-20 | 2011-12-13 | Low viscosity fluoroelastomers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10195983.1 | 2010-12-20 | ||
EP10195983 | 2010-12-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012084587A1 true WO2012084587A1 (en) | 2012-06-28 |
Family
ID=43773716
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2011/072520 WO2012084587A1 (en) | 2010-12-20 | 2011-12-13 | Low viscosity fluoroelastomers |
Country Status (5)
Country | Link |
---|---|
US (1) | US9458272B2 (en) |
EP (1) | EP2655441B1 (en) |
JP (2) | JP6333554B2 (en) |
CN (1) | CN103370346B (en) |
WO (1) | WO2012084587A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017216035A1 (en) | 2016-06-13 | 2017-12-21 | Solvay Specialty Polymers Italy S.P.A. | Curable fluoroelastomer composition |
EP3858875A4 (en) * | 2018-09-28 | 2022-06-29 | Agc Inc. | Fluorine-containing copolymer and method for producing same |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105814102A (en) * | 2013-12-11 | 2016-07-27 | 3M创新有限公司 | Highly fluorinated elastomers |
CN106488934B (en) * | 2014-05-12 | 2019-09-03 | 索尔维特殊聚合物意大利有限公司 | Method for controlled fusion fluorine monomer |
JP6947486B2 (en) | 2016-05-09 | 2021-10-13 | スリーエム イノベイティブ プロパティズ カンパニー | Hydrofluoroolefins and how to use them |
US11725071B2 (en) | 2017-09-27 | 2023-08-15 | Arkema Inc. | Copolymers of halogenated olefins and halogenated co-monomers |
CN115449008B (en) * | 2018-10-18 | 2023-10-24 | 大金工业株式会社 | Fluorine-containing elastomer, crosslinkable composition, and molded article |
Citations (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3752787A (en) | 1972-01-28 | 1973-08-14 | Du Pont | Fluoroelastomer composition containing a triarylphosphorane vulcanization accelerator |
US3876654A (en) | 1970-12-23 | 1975-04-08 | Du Pont | Fluoroelastomer composition |
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 |
US4233427A (en) | 1978-01-16 | 1980-11-11 | Rhone-Poulenc Industries | Elastomeric organopolysiloxane block copolymers and non-elastomeric organosilicic copolymer blocks therefor |
US4243770A (en) | 1977-04-08 | 1981-01-06 | Daikin Kogyo Co., Ltd. | Cross linkable fluorine-containing polymer and its production |
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 |
US4281092A (en) | 1978-11-30 | 1981-07-28 | E. I. Du Pont De Nemours And Company | Vulcanizable fluorinated copolymers |
US4394489A (en) | 1982-02-25 | 1983-07-19 | E. I. Du Pont De Nemours & Co. | Fluoroelastomer curatives |
EP0120462A1 (en) | 1983-03-22 | 1984-10-03 | Montedison S.p.A. | Accelerators for vulcanizing vinylidene fluoride elastomeric copolymers |
EP0136596A2 (en) | 1983-09-07 | 1985-04-10 | AUSIMONT S.p.A. | Covulcanizable compositions of fluoroelastomers based on vinylidene fluoride and tetrafluoroethylene-propylene copolymers |
US4564662A (en) | 1984-02-23 | 1986-01-14 | Minnesota Mining And Manufacturing Company | Fluorocarbon elastomer |
EP0182299A2 (en) | 1984-11-22 | 1986-05-28 | Asahi Kasei Kogyo Kabushiki Kaisha | A curable fluoroelastomer composition |
EP0199138A2 (en) | 1985-03-28 | 1986-10-29 | Daikin Industries, Limited | Novel fluorovinyl ether and copolymer comprising the same |
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 |
EP0335705A1 (en) | 1988-04-01 | 1989-10-04 | Minnesota Mining And Manufacturing Company | Fluoroelastomer composition |
US4943622A (en) | 1987-06-04 | 1990-07-24 | Nippon Mektron, Limited | Process for producing peroxide-vulcanizable, fluorine-containing elastomer |
EP0410351A1 (en) | 1989-07-24 | 1991-01-30 | AUSIMONT S.p.A. | Curable mixtures of fluoroelastomers containing bromine or iodine and of organic peroxides |
US5173553A (en) | 1989-07-10 | 1992-12-22 | Ausimont S.R.L. | Fluoroelastomers endowed with improved processability and process for preparing them |
EP0661304A1 (en) | 1993-12-29 | 1995-07-05 | AUSIMONT S.p.A. | Fluoroelastomers comprising monomeric units deriving from a bis-olefin |
US5447993A (en) | 1994-04-19 | 1995-09-05 | E. I. Du Pont De Nemours And Company | Perfluoroelastomer curing |
EP0684277A1 (en) | 1994-05-27 | 1995-11-29 | AUSIMONT S.p.A. | Curable fluoroelastomeric compositions |
EP0708797A1 (en) | 1993-07-16 | 1996-05-01 | E.I. Du Pont De Nemours And Company | High purity fluoroelastomer compositions |
WO1997005122A1 (en) | 1995-07-26 | 1997-02-13 | E.I. Du Pont De Nemours And Company | Fluorinated alkenyltriazines and their use as crosslinking agents |
WO1998015583A1 (en) | 1996-10-04 | 1998-04-16 | Bayer Aktiengesellschaft | Liquid fluoric rubber |
US5767204A (en) | 1994-10-21 | 1998-06-16 | Nippon Mektron Limited | Fluorine-containing elastomer composition |
US5789489A (en) | 1996-11-25 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Fast-curing perfluoroelastomer composition |
US5789509A (en) | 1996-11-25 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Perflouroelastomer composition having improved processability |
EP0860436A1 (en) | 1997-02-25 | 1998-08-26 | Ausimont S.p.A. | Compounds containing triazine ring |
US5852125A (en) | 1996-06-03 | 1998-12-22 | Bayer Aktiengesellschaft | Fluororubber, a process for its production and its use, as well as a process for producing fluororubber moldings and/or coatings |
EP1148072A2 (en) | 2000-04-21 | 2001-10-24 | Ausimont S.p.A. | Fluoroelastomers |
US20030166807A1 (en) | 1999-05-28 | 2003-09-04 | Harrison David B. | Rapidly crosslinking fluoropolymer |
WO2009027213A1 (en) * | 2007-08-29 | 2009-03-05 | Solvay Solexis S.P.A. | (per)fluoroelastomeric compositions |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19740633A1 (en) | 1997-09-16 | 1999-03-18 | Bayer Ag | Production of low-viscosity fluoro-rubber |
ITMI20012164A1 (en) * | 2001-10-18 | 2003-04-18 | Ausimont Spa | FLUORO-ELASTOMERS |
ITMI20012165A1 (en) * | 2001-10-18 | 2003-04-18 | Ausimont Spa | perfluoroelastomers |
JP2004163927A (en) * | 2002-10-25 | 2004-06-10 | Mitsubishi Rayon Co Ltd | Plastic optical fiber and plastic optical fiber cable |
JP2004219579A (en) * | 2003-01-10 | 2004-08-05 | Mitsubishi Rayon Co Ltd | Plastic optical fiber and plastic optical fiber cable |
US20050124773A1 (en) * | 2003-12-09 | 2005-06-09 | Tang Phan L. | Extrudable fluoroelastomer composition |
ITMI20040830A1 (en) * | 2004-04-27 | 2004-07-27 | Solvay Solexis Spa | VULCANIZABLE FLUOROELASTOMERS |
ITMI20041572A1 (en) * | 2004-07-30 | 2004-10-30 | Solvay Solexis Spa | TFE-BASED THERMOPROCESSABLE CAPOLYMERS |
JP5584123B2 (en) * | 2007-09-14 | 2014-09-03 | スリーエム イノベイティブ プロパティズ カンパニー | Ultra low viscosity iodine-containing amorphous fluoropolymer |
-
2011
- 2011-12-13 WO PCT/EP2011/072520 patent/WO2012084587A1/en active Application Filing
- 2011-12-13 EP EP11794746.5A patent/EP2655441B1/en not_active Not-in-force
- 2011-12-13 CN CN201180067934.1A patent/CN103370346B/en not_active Expired - Fee Related
- 2011-12-13 US US13/993,782 patent/US9458272B2/en active Active
- 2011-12-13 JP JP2013543697A patent/JP6333554B2/en not_active Expired - Fee Related
-
2018
- 2018-01-12 JP JP2018003050A patent/JP2018087341A/en active Pending
Patent Citations (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3876654A (en) | 1970-12-23 | 1975-04-08 | Du Pont | Fluoroelastomer composition |
US3752787A (en) | 1972-01-28 | 1973-08-14 | Du Pont | Fluoroelastomer composition containing a triarylphosphorane vulcanization accelerator |
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 |
US4243770A (en) | 1977-04-08 | 1981-01-06 | Daikin Kogyo Co., Ltd. | Cross linkable fluorine-containing polymer and its production |
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 |
US4233427A (en) | 1978-01-16 | 1980-11-11 | Rhone-Poulenc Industries | Elastomeric organopolysiloxane block copolymers and non-elastomeric organosilicic copolymer blocks therefor |
US4281092A (en) | 1978-11-30 | 1981-07-28 | E. I. Du Pont De Nemours And Company | Vulcanizable fluorinated copolymers |
US4394489A (en) | 1982-02-25 | 1983-07-19 | E. I. Du Pont De Nemours & Co. | Fluoroelastomer curatives |
EP0120462A1 (en) | 1983-03-22 | 1984-10-03 | Montedison S.p.A. | Accelerators for vulcanizing vinylidene fluoride elastomeric copolymers |
EP0136596A2 (en) | 1983-09-07 | 1985-04-10 | AUSIMONT S.p.A. | Covulcanizable compositions of fluoroelastomers based on vinylidene fluoride and tetrafluoroethylene-propylene copolymers |
US4564662A (en) | 1984-02-23 | 1986-01-14 | Minnesota Mining And Manufacturing Company | Fluorocarbon elastomer |
EP0182299A2 (en) | 1984-11-22 | 1986-05-28 | Asahi Kasei Kogyo Kabushiki Kaisha | A curable fluoroelastomer composition |
EP0199138A2 (en) | 1985-03-28 | 1986-10-29 | Daikin Industries, Limited | Novel fluorovinyl ether and copolymer comprising the same |
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 |
US4943622A (en) | 1987-06-04 | 1990-07-24 | Nippon Mektron, Limited | Process for producing peroxide-vulcanizable, fluorine-containing elastomer |
EP0335705A1 (en) | 1988-04-01 | 1989-10-04 | Minnesota Mining And Manufacturing Company | Fluoroelastomer composition |
US5173553A (en) | 1989-07-10 | 1992-12-22 | Ausimont S.R.L. | Fluoroelastomers endowed with improved processability and process for preparing them |
EP0410351A1 (en) | 1989-07-24 | 1991-01-30 | AUSIMONT S.p.A. | Curable mixtures of fluoroelastomers containing bromine or iodine and of organic peroxides |
EP0708797A1 (en) | 1993-07-16 | 1996-05-01 | E.I. Du Pont De Nemours And Company | High purity fluoroelastomer compositions |
EP0661304A1 (en) | 1993-12-29 | 1995-07-05 | AUSIMONT S.p.A. | Fluoroelastomers comprising monomeric units deriving from a bis-olefin |
US5447993A (en) | 1994-04-19 | 1995-09-05 | E. I. Du Pont De Nemours And Company | Perfluoroelastomer curing |
EP0684277A1 (en) | 1994-05-27 | 1995-11-29 | AUSIMONT S.p.A. | Curable fluoroelastomeric compositions |
US5767204A (en) | 1994-10-21 | 1998-06-16 | Nippon Mektron Limited | Fluorine-containing elastomer composition |
WO1997005122A1 (en) | 1995-07-26 | 1997-02-13 | E.I. Du Pont De Nemours And Company | Fluorinated alkenyltriazines and their use as crosslinking agents |
US5852125A (en) | 1996-06-03 | 1998-12-22 | Bayer Aktiengesellschaft | Fluororubber, a process for its production and its use, as well as a process for producing fluororubber moldings and/or coatings |
WO1998015583A1 (en) | 1996-10-04 | 1998-04-16 | Bayer Aktiengesellschaft | Liquid fluoric rubber |
US5789509A (en) | 1996-11-25 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Perflouroelastomer composition having improved processability |
US5789489A (en) | 1996-11-25 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Fast-curing perfluoroelastomer composition |
EP0860436A1 (en) | 1997-02-25 | 1998-08-26 | Ausimont S.p.A. | Compounds containing triazine ring |
US20030166807A1 (en) | 1999-05-28 | 2003-09-04 | Harrison David B. | Rapidly crosslinking fluoropolymer |
EP1148072A2 (en) | 2000-04-21 | 2001-10-24 | Ausimont S.p.A. | Fluoroelastomers |
WO2009027213A1 (en) * | 2007-08-29 | 2009-03-05 | Solvay Solexis S.P.A. | (per)fluoroelastomeric compositions |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017216035A1 (en) | 2016-06-13 | 2017-12-21 | Solvay Specialty Polymers Italy S.P.A. | Curable fluoroelastomer composition |
EP3858875A4 (en) * | 2018-09-28 | 2022-06-29 | Agc Inc. | Fluorine-containing copolymer and method for producing same |
Also Published As
Publication number | Publication date |
---|---|
JP2013545860A (en) | 2013-12-26 |
US20130261249A1 (en) | 2013-10-03 |
EP2655441B1 (en) | 2015-11-18 |
CN103370346B (en) | 2016-12-14 |
US9458272B2 (en) | 2016-10-04 |
EP2655441A1 (en) | 2013-10-30 |
CN103370346A (en) | 2013-10-23 |
JP6333554B2 (en) | 2018-05-30 |
JP2018087341A (en) | 2018-06-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2655441B1 (en) | Low viscosity fluoroelastomers | |
JP4795685B2 (en) | Peroxide curable fluoroelastomer | |
EP1031607B1 (en) | Fluoroelastomer compositions | |
EP2718338B1 (en) | Hyperbranched fluoroelastomer additive | |
CN110214155B (en) | Fluorinated block copolymers derived from nitrile cure site monomers | |
EP2373734B1 (en) | (per)fluoroelastomer composition | |
EP2443194B1 (en) | Low temperature curable amorphous fluoropolymers | |
US8242210B2 (en) | (Per)fluoroelastomeric compositions | |
EP2627683B1 (en) | Fluoroelastomers | |
KR20110128834A (en) | Perfluoroelastomer | |
KR102120657B1 (en) | Peroxide-curable fluoropolymer composition including solvent and method of using the same | |
WO2014206955A1 (en) | Fluoroelastomers | |
WO2013023983A1 (en) | Milling process | |
KR101022727B1 (en) | Fluoroelastomers with improved permeation resistance and method for making the same | |
EP2373735B1 (en) | Vulcanized (per)fluoroelastomer sealing articles | |
EP3484953B1 (en) | Fluoroelastomer composition | |
EP3469018A1 (en) | Curable fluoroelastomer composition | |
EP3532541B1 (en) | Fluoroelastomer composition |
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: 11794746 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011794746 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13993782 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2013543697 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |