Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/14—Unsaturated ethers
  • C07C43/17—Unsaturated ethers containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
  • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
  • C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/30—Compounds having groups
  • C07C43/313—Compounds having groups containing halogen

Definitions

• the present invention relates to perfluorinated allyl ethers and higher homologs and their preparation. These monomers are valuable comonomers for fluoroelastomers with enhanced low temperature properties.
• Perfluoro allyl ethers are known, e.g., Krespan Carl G.; DuPont de Nemours, U.S. 4,273,728 or Emel 'yanov et al, Zh. Org. Khim, (1994) 39(8) 1266-70 and Amimoto et al, Daikin U.S. 4,379,901.
• Long chain allyl ethers provide in fluoroelastomers excellent low temperature properties (see Worm et al, U.S. Patent 5,891,965).
• Rf groups containing such oxygen atoms are referred to as perfluoroalkyleneoxy groups.
• R preferably contains from 1-20, more preferably from 1 to 10, carbon atoms in the backbone.
• Rf can also contain additional terminal unsaturation sites.
• the perfluorinated allyl ethers may be either linear or branched.
• the perfluorinated allyl ethers are linear.
• the term perfluorinated means that all of the carbon-bonded hydrogen atoms have been replaced with fluorine and any unsaturated carbon-carbon bonds have been saturated with fluorine.
• One embodiment of the invention includes a process for the preparation of a perfluorinated ether of the formula m has a value of from 1-4 and R f is a linear or branched perfluorinated aliphatic group that may contain oxygen atoms, the process comprising the steps of
• a perfluorinated allyl ether is produced by a process comprising the steps of:
• step (c) fluorinating the chlorinated intermediate to provide a perfluorinated product of step (b), and
• step (d) dechlorinating the product of step (c) to provide the perfluorinated allyl ether.
• allyl alcohol used in the reaction to produce the hydrogen-containing precursor described above is at least partially replaced by H0CH 2 CHC1CH 2 C1
• a still further embodiment of the invention provides perfluoro allyloxy compounds selected from the group consisting of
• the perfluorinated allyl ethers prepared according to the present in dention are useful in the preparation of fluoroelastomers, especially those that are used at low temperatures Such elastomers are known. See, for example, U S Patent 5,891,965 (Worm and Guerra) The exact process used to make the perfluorinated ether is dependent upon the type of ether desired. However, there are certain process steps common to each of the embodiments of the invention Fluorination of the precursors may be accomplished by either electrochemical fluorination (ECF) or direct fluorination (DF) ECF is described in U.S. Patent 2,713,593 and in WO 98/50603.
• ECF electrochemical fluorination
• DF direct fluorination
• Fluorination of the precursors can be done by electrochemical fluorination as previously described. However, direct fluorination is preferred due to fewer side products and improved yields.
• the solvents for fluorination are mostly perfluorinated compounds and/or fluorochloro compounds, e.g. perfluoromethylmorpholine, Freon 1 13, etc.
• a perfluorinated allyl ether may be prepared by a process comprising the steps of:
• step (c) dechlorinating the fluorinated product of step (c) either in the presence of a metallic reducing agent or by an electrochemical means to provide the desired perfluoroallylether.
• the 1,2-dichloro alkyl ether moiety may be a 1,2-dichloro propyl ether moiety, a 1,2-dichloro butyl ether moiety, a 1,2-dichloro pentyl ether moiety, etc. depending upon the homolog desired.
• a 1,2-dichloro propyl ether moiety will yield an allyl ether in this context and is a preferred starting material.
• the hydrogen-containing precursor employed in this preparation can be partially fluorinated. The fluorination occurring in step (b) will replace all carbon-bonded hydrogen atoms with fluorine and also saturate with fluorine any unsaturated carbon-carbon bonds.
• the corresponding allyl ether made from such a precursor may contain more than one unsaturation site
• An additional starting material is also possible in this reaction sequence This includes using H0CH CHC1CH 2 C1 in place of at least a portion of the allyl alcohol
• Suitable olefins or reactants for the addition to allylalcohol include tetrafluoroethylene, hexafluoropropene, perfluoroalkyl vinyl ethers, such as perfluoromethylvinylether, perfluoropropylvinylether or perfluoroalkyl vinyl ethers as described in a copending application identified as Attorney Docket No 54856USA7A
• Perfluoro alkyl allyl ethers are also useful
• the preferred bases to catalyze the addition are alkali hydroxides KOH, NaOH, or NaOMe Solvents for the reaction include N,N-d ⁇ alkyl carboxylic acid amides or cyclic amides as described in U S Patent No 4,433, 180 (von Werner)
• Specific examples of perfluoro allyl ethers or allyloxy compounds that may be made by this route include
• the resulting perfluorodichloro compounds are dechlo ⁇ nated by metals, such as, for example zinc, Mg/HgCl 2 , Mg/Hgl or LAH/T ⁇ Cl Zn is the preferred agent, with the reaction done in dimethyl formamide (DMF) at higher temperatures (e.g , 100-150° C)
• DMF dimethyl formamide
• the alternative method is electrochemical dechlorination as described by Dapperheld in EP 293 856 and EP 334 796.
• Methoxyethanol (lOOg, 1.3 mol) was stirred with 51.3g NaOH and 0.6g Adogen 464 (methyltrialkyl (C -C 10 ) ammonium chloride, available from Aldrich Chemical Co ) and 155. lg (1.3 mol) allyl bromide was slowly added with cooling initially and finally with external heating to 40°C.
• Adogen 464 methyltrialkyl (C -C 10 ) ammonium chloride, available from Aldrich Chemical Co
• allyl bromide was slowly added with cooling initially and finally with external heating to 40°C.
• Hexafluoropropene (HFP) was reacted at room temperature with a mixture of allylalcohol in dimethylformamide KOH- powder and a slight increase in pressure.
• the isolated allylether (bp 95° C) was chlorinated with Cl in Freon 113 at 30° C to provide a chlorinated intermediate. Without isolation, the chlorinated intermediate was fluorinated by using a tubular reactor described in U.S. 5,488,142. After fluorination the solvent was distilled off and the remaining liquid was dropped in a stirred mixture of Zn in DMF at 150° C. The perfluoroallylether that resulted was condensed and rectified to obtain a higher purity. A boiling point (bp) of 60° C was measured.
• the allylethers in Table 1 were prepared in a manner similar to Example 5 except the HFP was replaced by the listed starting fluorinated olefin.

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1999
  • 1999-12-22 US US09/470,034 patent/US6255535B1/en not_active Expired - Lifetime
• 2000
  • 2000-05-12 WO PCT/US2000/013116 patent/WO2001046108A1/en not_active Ceased
  • 2000-05-12 AU AU47128/00A patent/AU4712800A/en not_active Abandoned
  • 2000-05-12 DE DE60026022T patent/DE60026022T2/de not_active Expired - Lifetime
  • 2000-05-12 EP EP00928975A patent/EP1240126B1/en not_active Expired - Lifetime
  • 2000-05-12 CA CA002393460A patent/CA2393460A1/en not_active Abandoned
  • 2000-05-12 JP JP2001546622A patent/JP2003518052A/ja active Pending
• 2002
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