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
  • C08F214/22—Vinylidene fluoride
• • 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
  • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
  • C08F261/06—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers 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
  • C08F214/22—Vinylidene fluoride
  • C08F214/222—Vinylidene fluoride 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
  • C08F214/26—Tetrafluoroethene
  • C08F214/262—Tetrafluoroethene 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
  • C08F214/26—Tetrafluoroethene
  • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/02—Alkylation
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/04—Reduction, e.g. hydrogenation
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/10—Acylation
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/12—Hydrolysis
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
• • 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
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
• • 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
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains

Definitions

• This invention relates to diacrylate copolymers of formula
• oligomer comprising copolyrnerized units of tetrafluoroethylene and perfluoro(methyl vinyi ether), and iv) an oligomer comprising copolyrnerized units of tetrafluoroethylene and a hydrocarbon olefin, R' is H or -CHs, n is 1-4, and wherein said oligomer has a number average molecular weight of 1000 to 25,000 dalto ⁇ s.
• Dif ⁇ nctional low molecular weight (number average molecular weight between 1000 and 25,000 daitons) copolymers of vinyfidene fluoride (VF 2 ) with perfluoro(methyl vinyi ether) (PMVE) and d ⁇ functionat copolymers of tetrafluoroethylene (TFE) with PMVE have been disclosed in US 20090105435 A1.
• a functional group is located at each end of the copolymer main chain (sometimes referred to as "telechelic").
• Functional groups disclosed include iodine, ally!, hydroxy!, carboxy! and nitrile.
• Another aspect of the Invention is a process for the manufacture of a teiechelic diacryiate copolymer, said process comprising;
• said oligomer selected from the group consisting of i) an oligomer comprising copolymerized units of vinylidene fluoride and perfluoro(methy[ vinyl ether), ii) an oligomer comprising copolymerized units of vinylidene fluoride and hexafluoropropylene, iii) an oligomer comprising copolymerized units of tetrafluoroethylene and
• the present invention is directed to tow molecular weight, teleche ⁇ c diacrylate fluoropoiyrners and a process for the manufacture of said polymers.
• diacrylate is meant that the fluoropoiyrners contain either two acryiate groups or two meihacryiate groups per polymer chain.
• the acryiate or methacrylate groups are located at both ends of the main polymer chains.
• main chain is meant the longest chain of copolymerized monomer units, Le. not side chains or branches.
• Oligomer, R is selected from the group consisting of ⁇ an oligomer comprising copoiymerized units of vinylidene fluoride and perfiuoro(methyl vinyi ether), ii) an oligomer comprising copoiymerized units of vinylidene fluoride and
• oligomer, R may further comprise at least one additional comonomer, different from the other two comonomers.
• VF vinylidene fluoride
• HFP hexafluoropropylene
• TFE tetrafluoroethyiene
• PMVE perfluoro ⁇ methyl vinyi ether
• oligomers that may be employed in the fluoropoiyrners of the invention (and the diols used to make them) include, but are not limited to TFE/PMVE, VF 2 ZPMVE, VF 2 /TFE/PMVE 5
• OOCCR' CH ? .
• Diols of formula HO-(CH 2 VR-(CH 2 ) H -OH may be made from a multi-step process beginning with the corresponding ⁇ , to-d ⁇ iodo oligomers of formula l-R-l prepared generally as described in U.S. 20090105435 Al .
• the diiodo oligomers may be ethyieneaied (or ailylated) by reaction, in the presence of a radical initiator, with ethylene ⁇ or ally! alcohol, followed by the selective reduction of the iodine atoms).
• the resulting oligomers may then be hydrolyzed to form the dials.
• Fiuoropolymers of this invention are useful in forming crosslinked fluoropoiymor networks having good flexibility, chemical resistance and thermal properties.
• Number average molecular weight (Mn) was determined by size exclusion chromatography (SEC). Samples were dissolved in THF.
• Tetrahydrofuran was used as eluent, with a flow rate of 0.8 mL min "1 .
• Standards were monodispersed poly(styrene) (PS) or polymethylmethacrylate), purchased from Polymer Laboratories or other vendors.
• Fluofopoiymer and oligomer compositions and microstruclures were determined by 1 "F and 1 H NMR.
• the NMR spectra were recorded on a Bruker AC 200, AC, 250 and AC 400 (200, 250 and 400 MHz)
• R is po!y(v ⁇ nylide ⁇ e fiuoride-co- perfluorofmethyl vinyl ether) [i.e. poty(VF 2 -co-PMVE)3, was made by the process of the invention.
• the dioi oligomer employed in the fluoropolymer manufacturing process was made from a multi-step process, beginning with a telechelic diiodo oligomer of formula [-(VF ? -co-PMVE)-L The latter was made by the process disclosed in U.S. 20090105435 A1. This diiodo oligomer contained 73.2 mol% VF2 and 26.8 mol% PMVE and had a number average molecular weight of 2450 daltons.
• Hastelloy (HC-276) autoclave equipped with inlet and outlet valves, a manometer and a rupture disc, was degassed and pressurized with 30 bar of nitrogen Io check for leaks. Then, a 0.5 mm Hg vacuum was operated for 5 minutes (min.) and subsequently an argon atmosphere was applied. Such a procedure of autoclave degassing was repeated five times. Under vacuum, 5,0 g (2.87 x 10 '2 moles) of t- butylperoxypivalate (TBPPi), 50 mL of f-butanoi and 100.0 g (0.077 moles) of the above-described telechelic diiodo oligomer were transferred into the autoclave.
• TBPPi t- butylperoxypivalate
• 100.0 g 0.077 moles
• the teiechelic I-(VF2 ⁇ co-PMVE)-f oligomer starting material was the same as that employed in Example 1.
• the reaction mixture was filtered through sintered glass (G5) to remove white solid such as BuaS ⁇ K, BugSnF or B ⁇ aSnl.
• the solvents were removed on a rotary vacuum evaporator (4QX/2Q mm Hg).
• the crude product was dissolved in 50 ml of butanone and washed with water (2 x 50 ml).
• the organic layer was dried over MgS ⁇ 4 which was then filtered through sintered glass (G4).
• the butanone was partly removed on a rotary vacuum evaporator and residue was precipitated from penta ⁇ e. After cooling 12 hours at 4"C 1 pentane was carefully removed from the precipitated product by decantation.
• a 100 mi three-neck round bottom flask equipped with a reflux condenser and a magnetic stirrer was charged with 5.03 g (3.33 mmoies) of the above-prepared bis ⁇ propyi alcohol), 25 mi of THF, 4,5g of poiy ⁇ vinylpo!ypyroiidone), 5 mg (0.045 mmoies) of hydroq ⁇ inone and cooled to 0 0 C, Then aeryloyl chloride (4.456 g, 4 ml, 50 mmoies) was added dropwise in three closes (2 nil, 1 ml & 1 mf).
• the reaction temperature was increased to 40 n C; the two subsequent additions were completed after elapsed times of 5 and 22 hours.
• An additional amount of poiy(viny!po!ypyro!idone) (4.5 g) was then added to the reaction mixture.
• the reaction was conducted under nitrogen atmosphere at 40 0 C for 48 hours.
• the reaction mixture was filtered through sintered giass (G4) to remove poiy(viny!poiypyrolidone).
• the filtered po!y(viny!po!ypyrol ⁇ done) was washed with THF.
• the solvent was partly removed by rotary evaporation and residue was precipitated from pentane.

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

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• 2009
  • 2009-07-16 US US12/504,267 patent/US8394905B2/en not_active Expired - Fee Related
• 2010
  • 2010-06-10 JP JP2012520643A patent/JP5513614B2/ja not_active Expired - Fee Related
  • 2010-06-10 WO PCT/US2010/038102 patent/WO2011008381A1/en not_active Ceased
  • 2010-06-10 EP EP10725342.9A patent/EP2454294B1/en not_active Not-in-force
  • 2010-06-10 CN CN2010800320870A patent/CN102471411A/zh active Pending
• 2012
  • 2012-11-14 US US13/676,201 patent/US8575300B2/en not_active Expired - Fee Related

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