Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/28—Hexyfluoropropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08F216/1466—Monomers containing sulfur
  • C08F216/1475—Monomers containing sulfur and oxygen
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/1397—Single layer [continuous layer]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/21—Circular sheet or circular blank
  • Y10T428/215—Seal, gasket, or packing

Definitions

• the present invention relates to the synthesis of new fluorinated elastomers having very low glass transition temperatures (T g ), good resistance to acids, petroleum and fuels, as well as good processing properties.
• the elastomers of the invention contain hexafluoropropene (hereinafter "HFP"), perfluoro (4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride (hereinafter "PFSO 2 F”) , and vinylidene fluoride (hereinafter "VDF”) and / or a perfluorinated vinyl ether and / or a fluorinated alkene.
• HFP hexafluoropropene
• PFSO 2 F perfluoro (4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride
• VDF vinylidene fluoride
• elastomers are prepared by radical copolymerization of HFP with PFSO 2 F or by radical terpolymerization of HFP with PFSO 2 F and VDF in the presence of various conventional organic initiators, such as peroxides, peresters, diazo or alkyl peroxypivalates.
• organic initiators such as peroxides, peresters, diazo or alkyl peroxypivalates.
• Fluorinated elastomers have a unique combination of extremely advantageous properties. Among these, mention may be made of their thermal resistance, to oxidation, to ultraviolet (UV) rays, to degradation due to aging, to corrosive chemical agents and to fuels. They also have low surface voltages, dielectric constants and refractive indices. They also resist absorption of water. All these properties make them materials of choice in various high-tech applications such as fuel cell components, seals in the aeronautical field, semiconductors in microelectronics, hoses, pipes, pump and diaphragm bodies in the chemical, automotive and petroleum industries. However, there are few elastomers based on hexafluoropropene (HFP).
• HFP hexafluoropropene
• T g temperatures glass transition
• the T g of the abovementioned commercial products generally vary between -10 and -25 ° C.
• the lowest value found in the literature is that of Viton ® B, ie a T g of -26 ° C, which is surprising since the manufacturer announces a T g varying between -5 and -15 ° C for this product.
• the Ausimont company proposed a VDF / pentafluoropropene copolymer (Technoflon ® ) resistant to flames and oxidation, but having no T g below -26 ° C and whose comonomer is difficult to access.
• copolymers containing HFP with tetrafluoroethylene are thermoplastics, while the introduction of another fluorinated monomer such as, for example, trifluorovinyl ethers brings the elastomeric character.
• DuPont suggested a new generation of elastomers based on perfluoroalkyl vinyl ether (PAVE) but which do not contain HFP, and which are resistant to low temperatures.
• copolymers have been produced, such as the copolymer of tetrafluoroethylene (TFE) / perfluoromethyl vinyl ether (PMVE) (Kalrez ®), the T g does not fall below -15 ° C, the TFE / PMVE described in EP 0 077 998, the T g of which are -9 ° C, or TFE / perfluoroalkylvinylether (PAVE) described in US 4,948,853. But it is especially the terpolymers which have even lower T g .
• TFE tetrafluoroethylene
• PMVE perfluoromethyl vinyl ether
• PAVE perfluoroalkylvinylether
• TFE / ethylene / PMVE te ⁇ olymer whose T g is -17 ° C
• the TFE / VDF / PAVE te ⁇ olymer (described in EP 0 131 308)
• TFE / VDF / PMVE te ⁇ olymer Viton GLT ®
• elastomers based on TFE / PAVE / VDF, used as O-rings have very good resistance to polar solvents (EP 0 618 241, Ausimont and Japanese patent -A-3066714 Chem. Abstr., 115: 73436z) .
• Asahi Glass uses this same sulfonated monomer for the manufacture of Flemion ® membranes.
• F 2 C CFO [CF 2 CF (CF 3 ) O] x C 2 F 4 CO 2 CH 3 (for Nafion ® or Aciplex ® membranes when x is 1 and for Flemion membranes ® if x is 0) are also used.
• EP 0 525 685 describes the synthesis of HFP / PMVE / VDF te ⁇ olymers leading to elastomers having a T g equal to -27 ° C (lowest value) unlike that of VDF / HFP copolymers whose T g is from -23 ° C.
• VDF and olefins having from 2 to 4 carbon atoms see EP 0 570 762).
• PFSO 2 F in polymers was determined by elemental analysis. Also, the T g of the te ⁇ olymers are not mentioned.
• the present invention relates to fluorinated elastomers comprising neither of tetrafluoroethylene (TFE), nor of monomer carrying siloxane group, and having glass transition temperatures (T g ) between -36 and -50 ° C and comprising a hexafluoropropene comonomer (HFP) and a comonomer of perfluorosulfonyl fluoride ethoxy propyl vinyl ether (PSEPVE) or perfluoro (4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride (PFSO 2 F).
• TFE tetrafluoroethylene
• T g glass transition temperatures
• HFP hexafluoropropene comonomer
• PSEPVE perfluorosulfonyl fluoride ethoxy propyl vinyl ether
• PFSO 2 F perfluoro (4-methyl-3,6-dioxao
• the fluorinated elastomers according to the invention can also comprise vinylidene fluoride (VDF) and / or fluorinated alkenes and / or perfluorinated vinyl ethers.
• VDF vinylidene fluoride
• Another object of the invention is to know very precisely and without ambiguity the composition of the copolymers according to the invention, that is to say the molar percentages of each of the comonomers present in the copolymers or the te ⁇ olymers.
• the elastomer comprises less than 50% by moles of HFP, preferably, from 10 to 35% by moles, from 15 to 80% by moles of PFSO 2 F, and from 0 to 75% by moles VDF and / or fluorinated alkenes and / or perfluorinated vinyl ethers.
• the invention also relates to a process for the preparation of fluorinated elastomers by copolymerization of hexafluoropropene (HFP) with a perfluorosulfonyl ethoxy propyl vinyl ether fluoride (PSEPVE) or a perfluoro (4-methyl-3,6-dioxaoct-7-ene) ) sulfonyl fluoride (PFSO 2 F), characterized in that the preparation is carried out by radical copolymerization in the presence of an organic initiator at a temperature of between 20 and 200 ° C, for a period of between 2 and 6 hours approximately , and at an initial pressure between 2 and 100 bars, and the pressure is allowed to drop as the monomers are consumed.
• HFP hexafluoropropene
• PSEPVE perfluorosulfonyl ethoxy propyl vinyl ether fluoride
• PFSO 2 F perfluoro (4-methyl-3,6-di
• HFP was chosen for the preparation of the elastomers of the present invention, the latter being a cheaper alkene and easier to use than TFE. Being less expensive, it can therefore be used in larger quantities in the copolymer, which may include as second monomer perfluorosulfonyl ethoxy propyl vinyl ether fluoride (PSEPVE) or perfluoro (4-methyl-3,6-dioxaoct-7- ene) sulfonyl fluoride (PFSO 2 F).
• PSEPVE second monomer perfluorosulfonyl ethoxy propyl vinyl ether fluoride
• PFSO 2 F perfluoro (4-methyl-3,6-dioxaoct-7- ene) sulfonyl fluoride
• the present invention further comprises te ⁇ olymers in which the third comonomer would preferably be VDF, this monomer leading to a low T g , being inexpensive and easy to handle, copolymerizable (reactive) in free radicals; PVDF blocks in the polymer also provide chemical and thermal inertia, as well as better resistance to aging.
• the third comonomer would preferably be VDF, this monomer leading to a low T g , being inexpensive and easy to handle, copolymerizable (reactive) in free radicals; PVDF blocks in the polymer also provide chemical and thermal inertia, as well as better resistance to aging.
• the present invention preferably relates to the synthesis of original fluorinated elastomeric copolymers, based on hexafluoropropene and containing perfluorosulfonyl ethoxy propyl vinyl ether fluoride or perfluoro (4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride , and possibly other fluorinated alkenes, and / or vinylidene fluoride and / or perfluorinated vinyl ethers.
• perfluorosulfonyl ethoxy propyl vinyl ether fluoride or perfluoro (4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride and possibly other fluorinated alkenes, and / or vinylidene fluoride and / or perfluorinated vinyl ethers.
• fluorinated elastomers based on PSEPVE or PFSO 2 F and possibly VDF, perfluorinated alkenes and perfluorinated vinyl ethers is carried out with HFP instead of tetrafluoroethylene (TFE) which is much more expensive.
• TFE tetrafluoroethylene
• the synthesis of fluorinated elastomers of the present invention does not require the use of monomers carrying siloxane groups, the latter generally contributing to a reduction in T g . It is well known in fact that siloxanes have very low T g .
• poly (dimethyl siloxane) s have T g of -120 ° C as generally indicated in the following work: The Siloxane Bond: Physical Properties and Chemical Transformations, MG Voronkov, VP Mileshkevich, and Yu A. Yuzhelevskii, Consultants Bureau, New York (1978).
• the fluorinated elastomers of the present invention have very low T g which, for example, generally varies from -35 to -50 ° C, these elastomers thus being able to find applications in the plastics industry as an implementing agent, or in other advanced industries such as aerospace, electronics or the automotive, petroleum, or transportation of very cold fluids such as liquid nitrogen, liquid oxygen and liquid hydrogen.
• seals of high thermal resistance can be prepared from the present elastomers.
• these elastomers can be used for the manufacture of materials in the energy field, for example for the preparation of fuel cell components such as membranes.
• the field of the present invention extends to all types of processes generally used: emulsion, miniemulsion, microemulsion, bulk, suspension, microsuspension and solution polymerization. All can be used according to their conventional implementation, but solution polymerization was used in a preferential manner, for reasons of ease of implementation in the laboratory only, because in the case of solution polymerization, the pressures of operation are low, around 20 to 40 bars. In the case of emulsion, bulk and suspension polymerization, the operating pressure is higher, ie of the order of 40 to 100 bars.
• the various fluorinated alkenes used have at most four carbon atoms and have the structure R !
• R 2 C CR 3 R 4 where the substituents R are such that at least one of them is fluorinated or perfluorinated.
• This therefore includes: vinyl fluoride (VF), vinylidene fluoride (VDF), trifluoroethylene, chlorotrifluoroethylene (CTFE), bromotrifiuoroethylene, 1- hydropentafluoropropylene, hexafluoroisobutylene, 3,3,3-trifluoropropene, 1,2-dichlorodifluoroethylene, 2-chloro-1,1-difluoroethylene, 1,2-difluoroethylene, 1,1-difluorodichloroethylene and in general all vinyl fluorinated or perfluorinated compounds.
• perfluoro vinyl ethers can also play the role of comonomers.
• PAVE perfluoroalkyl vinyl ethers
• PMVE perfluoromethyl vinyl ether
• PEVE perfluoroethyl vinyl ether
• PPVE perfluoropropyl vinyl ether
• PAAVE perfluoroalkoxy alkyl vinyl ethers
• perfluoroalkoxyalkyl vinyl ethers with carboxylic ends or with sulfonyl fluoride ends such as perfluoro (4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride, can also be used for the synthesis of fluorinated elastomers described in the present invention.
• Mixtures of PAVE and PAAVE may be present in the copolymers.
• the preferred solvents are methyl acetate, acetonitrile and perfluoro-n-hexane in variable amounts of between 30 and 60% by weight.
• the reaction temperature for the copolymerization is preferably between 20 and 200 ° C, more advantageously between 55 and 140 ° C.
• the pressure inside the polymerization autoclave preferably varies between 2 and 100 bars, advantageously between 10 and 100 bars, more precisely between 20 and 35 bars, depending on the experimental conditions.
• initiators are azo (such as AIBN), dialkyl peroxydicarbonates, acetylcyclohexanesulfonyl peroxide, dibenzoyl peroxide, alkyl peroxides, alkyl hydroperoxides, dicumyl peroxide, alkyl perbenzoates and alkyl peroxypivalates.
• dialkyl peroxydicarbonates such as diethyl and di-isopropyl peroxydicarbonates
• alkyl peroxypivalates such as peroxypivalates.
• t-butyl and t-amyl and alkyl peroxide and more particularly still, to alkyl peroxypivalates.
• the initial molar ratio between the initiator and the monomers is between 0.3 and 2%.
• a wide range of cosolvents can be envisaged, the solvents being present in various proportions in the mixture with water, for example from 30 to 70% by weight.
• anionic, cationic or nonionic surfactants can be used in amounts usually varying from 1 to 3% by weight.
• water is generally used as the reaction medium.
• fluorinated monomers are hardly soluble in water, hence the need to use surfactants.
• a cosolvent can be added to increase the solubility of fluorinated comonomers. In the latter case, acetonitrile, acetone or other alkyl alkyl ketones such as methyl ethyl ketone can, for example, be used.
• One of the polymerization methods used can also be by microemulsion as described in EP 0 250 767 or by dispersion, as indicated in US 4,789,717; EP 0 196 904; EP 0 280 312 and EP 0 360 292.
• Chain transfer agents can be generally used to regulate and mainly reduce the molecular weights of the copolymers.
• R F is a perfluorinated group
• alcohols, ethers, esters a list of the various transfer agents used in the telomerization of fluorinated monomers.
• the elastomers of the present invention can be crosslinked using peroxide and triallyl (iso) cyanurate systems when such copolymers contain iodine and / or bromine atoms in the terminal position of the macromolecule.
• Peroxidic systems are well known, such as those described in EP 0 136 596.
• the fluorinated elastomers of said invention can be crosslinked with diamines, bis-amidoximes or polyphenols. These crosslinks are described in Rubber World, 1960. 142. 103; US 4,487,878; Prog. Polym. Sc, 1989. 14, 251; US 5,668,221; Angew. Makromol. Chem., 76/77. 1979. 39; Rubber Age, 103, 1971.
• vulcanization of these elastomers can also be carried out by ionic methods such as those described in US 3,876,654, US 4,259,463,
• VDF (1-83 + L91 + 92 + 1-93 + 95 + ios + l-i 10 + 13 + l-i 16 + 1-127) 2
• Ij is the integration value of the signal located at -i ppm on the 19 F NMR spectrum.
• Tables 1 and 2 show the HFP / PFSO 2 F, VDF / PFSO 2 F and HFP / VDF diades as well as the sequences head-to-tail and head-to-head of VDF unit blocks (respectively -91 and -113, -116 ppm).
• copolymers of such compositions can find applications in the preparation of fuel cell components such as membranes, O-rings, pump co ,s, diaphragms having very good resistance to fuels, petrol, t-butyl methyl ether, alcohols and engine oil, combined with good elastomeric properties, in particular very good resistance to low temperatures.
• fuel cell components such as membranes, O-rings, pump co ,s, diaphragms having very good resistance to fuels, petrol, t-butyl methyl ether, alcohols and engine oil, combined with good elastomeric properties, in particular very good resistance to low temperatures.
• These copolymers also have the advantage of being crosslinkable in the presence of agents conventionally used.
• Example 1 HFP / PFSO 2 F copolymerization (initial molar percentages 80.0 / 20.0)
• a very thick borosilicate Carius tube (length, 150 mm; internal diameter, 16 mm; thickness, 2.0 mm; for a total volume of 14 cm 3 ) containing 0.1158 g (0.50 mmol) of peroxypivalate 75% t-butyl, 2.21 g (4.96 mmol) perfluoro (4-methyl-3,6-dioaoct-7-ene) sulfonyl fluoride (PFSO 2 F) and 2.25 g (0.030 mmol ) of acetonitrile is connected to a vacuum ramp system and purged three times with helium by primary vacuum (100 mm Hg) / helium cycles.
• PFSO 2 F perfluoro (4-methyl-3,6-dioaoct-7-ene)
• HFP hexafluoropropene
• ni H pp represents the mass of HFP initially introduced.
• the yellowish liquid obtained is added dropwise to 35 ml of strongly agitated cold pentane. After being left for 1 hour at 0-5 ° C, the mixture is poured into a separatory funnel. The clear colorless supernatant is removed while the yellow heavy phase is dried at 70 ° C under 1 mm Hg for 2 hours. 1.67 g of a very viscous and clear liquid was obtained, corresponding to a mass yield of 32%.
• the various signals of the 19 F NMR spectrum and their attributions are indicated in Table 1.
• the total reactivity of the sulfonated monomer can be ensured by the absence of the characteristic signal centered at -137.5 ppm assigned to one of its ethylenic fluorine atoms.
• the respective HFP / PFSO 2 F molar percentages in the copolymer are 31.8 / 68.2 according to equation 1.
• the copolymer with the appearance d '' a colorless resin and has a T g of -48 ° C.
• Thermogravimetric analysis (ATG) reveals that the copolymer is thermally stable. In this regard, the temperature recorded for a 5% degradation in air is 155 ° C (Table 3).
• Example 2 HFP / VDF / PFSO 2 F polymerization (initial molar percentages 23/59/18)
• Hastelloy reactor (HC 276), equipped with a gas introduction valve, a release valve, a pressure gauge, an HC 276 rupture disc and stirring magnetic at 700 rpm, 48.5 g (0.11 mol) of PFSO 2 F are introduced; 1.10 g (4.7 mmol) of 75% t-butyl peroxypivalate and 149.8 g of methyl acetate.
• the reactor is closed and its tightness is checked.
• the following cycle is carried out 3 times: the reactor is placed under vacuum, then nitrogen is introduced at 10-15 bars. These cycles allow degassing of the solution. A vacuum of 20 mm Hg is then carried out in the reactor.
• the reactor is then placed in a bath acetone / liquid nitrogen in order to obtain an interior temperature of the reactor close to -80 ° C. Then introduced successively 21.0 g of HFP (0.14 mol) and then 23.0 g of vinylidene fluoride (VDF) (0.36 mol) by double weighing of the reactor. Then this reactor is placed in an oil bath progressively heated to a temperature of 75 ° C which is maintained for 3 hours. The maximum reaction pressure reached is 13 bars. The pressure drop observed at the reaction temperature after 6 hours is 7 bars.
• the 19 F NMR characterization (Table 2) shows the absence of any trace of the sulfonated monomer and made it possible to know the molar percentages of the three comonomers in the te ⁇ olymer equal to 10% of HFP, 71% of VDF and 19% of sulfonated monomer (PFSO 2 F) according to equations 1 and 2.
• the te ⁇ olymer has a T g of -43 ° C. Thermogravimetric analysis
• C 0 [initiator] 0 / ([HFP] 0 + [VDF] 0 + [PFSO 2 F] 0 ).
• the value of C 0 generally varies from 0.1 to 2%.
• TFE Tetrafluoroethylene
• the perfluorinated olefin which enters into the composition of the fluorinated elastomers prepared by said invention is hexafluoropropene; this is much less expensive and much less dangerous than TFE and gives the elastomers obtained good resistance to oxidation, chemical agents, polar solvents and petroleum;
• the fluorinated elastomers in question in the said invention can be prepared from the monomer PFSO 2 F whose copolymerization with HFP and te ⁇ olymerization with HFP and VDF have never been the subject of work described in the literature.
• this sulfonated monomer through its sulfonyl fluoride function, makes it possible to create crosslinking sites in these elastomers;
• the fluorinated elastomers synthesized by the said invention also contain vinylidene fluoride, considerably cheaper and less dangerous than TFE; this monomer makes it possible to drop the glass transition temperature (T g );
• the fluorinated elastomers obtained by this process have very low glass transition temperatures, varying from -36 to -48 ° C. 9 °)
• the fluorinated elastomers of said invention given the presence of the VDF-HFP sequences in the te ⁇ olymers, can be crosslinked with diamines, bis-amidoximes or polyphenols.

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