WO2009127559A1 - Alkyles de sodium solubles, leur procédé de fabrication et leur utilisation en tant qu’initiateurs - Google Patents

Alkyles de sodium solubles, leur procédé de fabrication et leur utilisation en tant qu’initiateurs Download PDF

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Publication number
WO2009127559A1
WO2009127559A1 PCT/EP2009/054152 EP2009054152W WO2009127559A1 WO 2009127559 A1 WO2009127559 A1 WO 2009127559A1 EP 2009054152 W EP2009054152 W EP 2009054152W WO 2009127559 A1 WO2009127559 A1 WO 2009127559A1
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WO
WIPO (PCT)
Prior art keywords
sodium
alkyl
sodium salt
initiators
solvent
Prior art date
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Ceased
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PCT/EP2009/054152
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German (de)
English (en)
Inventor
Franz Niklaus Windlin
Oliver Huttenloch
Christof Mehler
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BASF SE
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BASF SE
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Publication of WO2009127559A1 publication Critical patent/WO2009127559A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/04—Sodium compounds

Definitions

  • the invention relates to soluble in organic solvents sodium alkyl compounds, processes for their preparation, their solutions and their use.
  • alkali organyl compounds are popular reagents.
  • the self-0 shanks of these strong bases depend strongly on the cation.
  • sodium organyls are significantly less oxophilic than lithium organyls.
  • a wide range is commercially available. Solutions of lithium organyls in hydrocarbons such as hexane or in ethers such as THF are particularly advantageous.
  • 5 sodium organyls have so far been scarce because of their poor solubility.
  • sodium organyls are generally insoluble and / or react with the solvents.
  • Lithium organyls are well established reagents in organic synthesis and are the preferred initiators of anionic polymerization. For the preparation of these compounds lithium is needed, which is much more expensive and difficult to access compared to sodium. 0 In the case of anionic polymerization, in particular in block copolymer preparation, very low temperatures are necessary for some monomers, for example acrylates with lithium-containing initiators, in order to achieve the desired polymer qualities. Because of the lower oxophilia, the corresponding products with sodium organyls are accessible even at higher temperatures. Decisive for this application are the handling and the stability of the organyls in solution.
  • the object of the invention is to provide sodium organyls with similar properties in terms of solubility and reactivity as the established lithium organyls by simple chemical reactions of sodium. Due to their lower oxidophilicity, higher selectivity and / or reactivity is expected for certain sodium organylation applications than with lithium organyls.
  • This invention aims to increase the range of soluble sodium organyls for specific applications since only 2-ethylhexylsodium has been found to possess the appropriate handling and stability.
  • R 1 is H or CH 3 R 2 Ci- 5 alkyl
  • R 3 is C 2-6 -alkyl
  • R 2 and R 3 may be linear or branched, e.g. B. ß- or ⁇ -branched or a mixture of linear and branched radicals.
  • R 2 is linear and R 3 is linear, ⁇ - or ⁇ -branched or a mixture thereof.
  • R 1 is preferably hydrogen.
  • R 2 is preferably nC 2-4 alkyl, more preferably n-propyl.
  • R 3 is preferably C 4-6 alkyl, more preferably pentyl, e.g. B. n-pentyl.
  • it is the compound 2-propylheptyl sodium.
  • the object is further achieved by a process for the preparation of these sodium salts, wherein an alkyl halide of the general formula (II)
  • X halogen preferably bromine or chlorine, in particular chlorine and the meanings given for R 1 , R 2 and R 3 with metallic sodium.
  • the reaction can be carried out in a saturated aliphatic or cycloaliphatic hydrocarbon solvent.
  • Particularly suitable hydrocarbons have 7 to 10 C atoms.
  • Particular preference is given to alkanes which have a boiling point of more than 110 ° C.
  • Particularly preferred are pentanes, hexanes, heptanes, n-octane, n-nonane, cyclooctane and petroleum ether. In particular, with cyclooctane high yields are achieved.
  • the amount of solvent may be 0.5 to 1000 times the amount of alkyl halide of the general formula (II), more preferably 5 to 10 times.
  • the invention further relates to the solution of a sodium salt as described above in a saturated aliphatic or cycloaliphatic hydrocarbon as a solvent.
  • a saturated aliphatic or cycloaliphatic hydrocarbon as a solvent.
  • the type and amount of the solvent can be as described above.
  • the invention relates to the use of a sodium salt as described above or a solution as described above as initiators for inorganic polymerization or as a reagent in the synthesis of organic compounds.
  • the reaction of sodium with 2-propylheptyl chloride gives 2-propylheptylsodium in good yields.
  • the sodium is preferably in small pieces, more preferably by melting in a high boiling solvent or under pressure in lower boiling alkanes, e.g. As pentanes, hexanes or heptanes, finely dispersed used.
  • Sodium and 2-propylheptyl chloride are preferably reacted in approximately equimolar amounts, and more preferably with a slight excess of sodium.
  • the reaction is preferably carried out at temperatures between - carried out 78 ° C and 100 0 C, particularly preferably at temperatures between 0 0 C and 50 0 C and particularly preferably at room temperature.
  • the reaction is preferably carried out in a solvent, particularly preferably in a hydrocarbon, especially in a cyclic hydrocarbon.
  • a solvent particularly preferably in a hydrocarbon, especially in a cyclic hydrocarbon.
  • hydrocarbons which are liquid at atmospheric pressure or at higher pressures, so that the dispersion of the sodium is possible therein.
  • the byproduct sodium chloride and excess sodium may be separated from the sodium organyl solution by filtration by known techniques. In order to obtain good yields and a clean product, it is advantageous to carry out the reaction in the absence of oxygen and especially in the absence of water.
  • the product solution can be adjusted to a desired concentration by dilution or concentration, with 0.01M to 10M being preferred and 0.1M to 2M final concentration being particularly preferred.
  • the solution is preferably stored between -100 0 C to 25 ° C, more preferably between -20 0 C and 5 ° C, wherein the solution is preferably in the liquid state at the corresponding temperature.
  • storability also complete exclusion of oxygen and water is important.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un sel de sodium de formule générale (I) Na-CH2-CR1R2R3 (I), avec la signification R1 H ou CH3 ;R2 alkyle en C1-5 ; R3 alkyle en C2-6.
PCT/EP2009/054152 2008-04-14 2009-04-07 Alkyles de sodium solubles, leur procédé de fabrication et leur utilisation en tant qu’initiateurs Ceased WO2009127559A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08154470 2008-04-14
EP08154470.2 2008-04-14

Publications (1)

Publication Number Publication Date
WO2009127559A1 true WO2009127559A1 (fr) 2009-10-22

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/054152 Ceased WO2009127559A1 (fr) 2008-04-14 2009-04-07 Alkyles de sodium solubles, leur procédé de fabrication et leur utilisation en tant qu’initiateurs

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WO (1) WO2009127559A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE557029A (fr) * 1956-06-08
EP0041306A1 (fr) * 1980-06-02 1981-12-09 Texas Alkyls, Inc. Solutions d'alkyl-sodiques dans les hydrocarbures et procédé de préparation de ces solutions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE557029A (fr) * 1956-06-08
EP0041306A1 (fr) * 1980-06-02 1981-12-09 Texas Alkyls, Inc. Solutions d'alkyl-sodiques dans les hydrocarbures et procédé de préparation de ces solutions

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BRAUN D ET AL: "Mechanism of Stereospecific Polymerization of Styrene with Alkali Metal Alkyls", JOURNAL OF POLYMER SCIENCE, POLYMER SYMPOSIA, vol. 4, no. 1, 1963, pages 197 - 209, XP007908947, ISSN: 0022-3832, DOI: 10.1002/polc.5070040118 *
MURAHASHI S ET AL: "An Attempted Preparation of Optically Active Organometallic Compounds as Polymerization Catalysts", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 33, no. 5, 1960, pages 658 - 659, XP002534111, ISSN: 0009-2673, DOI: 10.1246/bcsj.33.658 *
WILLIAMS J L R ET AL: "Crystallizable Polystyrene. I. Polymerization of Styrene with Alfin Catalysts1", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 79, no. 7, 5 April 1957 (1957-04-05), XP002534112, ISSN: 0002-7863, DOI: 10.1021/ja01564a052 *

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