WO2012136679A1 - Composition de zinc dialkylé et procédé de préparation de zinc dialkylé - Google Patents

Composition de zinc dialkylé et procédé de préparation de zinc dialkylé Download PDF

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Publication number
WO2012136679A1
WO2012136679A1 PCT/EP2012/056114 EP2012056114W WO2012136679A1 WO 2012136679 A1 WO2012136679 A1 WO 2012136679A1 EP 2012056114 W EP2012056114 W EP 2012056114W WO 2012136679 A1 WO2012136679 A1 WO 2012136679A1
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WO
WIPO (PCT)
Prior art keywords
zinc
dialkyi
alkene
liquid composition
solids
Prior art date
Application number
PCT/EP2012/056114
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English (en)
Inventor
Alexey Borisovich ZAITSEV
Huh-Sun Chiou
Richard Herman Woudenberg
Original Assignee
Akzo Nobel Chemicals International B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel Chemicals International B.V. filed Critical Akzo Nobel Chemicals International B.V.
Publication of WO2012136679A1 publication Critical patent/WO2012136679A1/fr

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Classifications

    • 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
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc compounds

Definitions

  • the present invention relates to a dialkyi zinc composition, a process for making dialkyi zinc, and specific uses of the dialkyi zinc composition.
  • dialkyi zinc has grown because of its use as a catalyst or reagent in polymerization processes and pharmaceutics manufacturing and its use in the production of solar cells and semiconductor devices.
  • a problem observed in liquid dialkyi zinc and its compositions is the formation of solids of metallic zinc. These solids may cause plugging in equipment in which dialkyi zinc is used, resulting in production down times.
  • the stability, in particular the thermal stability, of these compositions therefore needs improvement.
  • the present invention therefore relates to a thermally stable liquid composition
  • a thermally stable liquid composition comprising dialkyi zinc and 1 ppm to 20 wt% of an alkene, based on the weight of the entire composition.
  • the liquid composition according to the present invention is thermally stable, which means that the liquid composition can be stored under nitrogen atmosphere ( ⁇ 2 ppm oxygen) and exclusion of light at 80°C for 20 hours without any significant change in its chemical or physical constitution, apart from the potential formation of some metallic zinc. Said metallic zinc formation should, however, be less than under the same conditions in the same composition not containing said alkene.
  • the alkene contains 2-200 carbon atoms, more preferably 2-100, even more preferably 2-50, more preferably 5-20 carbon atoms, and most preferably 5-10 carbon atoms.
  • alkenes includes monoalkenes, conjugated or non-conjugated dienes, trienes, and tetraenes, cycloalkenes, cycloalkedienes, cyclotrienes, cyclotetraenes, and di-, tri- and tetra-substituted ethylene with alkyl-, alkenyl-, aryl- and/or heteroatom-containing substituents. Cycloalkenes, cyclodienes, cyclotrienes, and cyclotetraenes are the most preferred type of alkenes.
  • Suitable monoalkenes are 1 -hexene, 1 -octene, 3-heptene (both cis- and trans-), 1 -octadecene, trans-4-octene, cis-4-octene, isobutene, and methylene cyclohexane.
  • dienes examples include 1 ,7-octadiene, isoprene and trans,trans-1 ,4- diphenyl-1 ,3-butadiene.
  • Suitable cycloalkenes, cycloalkadienes, -trienes, and -tetraenes are cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclopentadiene, dicyclopentadiene, 1 ,2,3,4,5-pentamethylcyclopentadiene, 1 ,4-cyclohexadiene, 1 ,5-dicyclooctadiene, 1 ,3,5,7-cyclooctatetraene, 1 ,6-diphenyl-1 ,3,5-hexatriene, and substituted versions thereof such as 1 -methyl-1 ,4-cyclohexadiene, 1 -methyl-1 - cyclohexene, and 4-methylcyclohexene.
  • cyclopentene, cyclohexene, trans,trans-1 ,4-diphenyl-1 ,3-butadiene, 1 ,2,3,4,5-pentamethylcyclopentadiene, 1 ,4- cyclohexadiene, 1 -methyl-1 ,4-cyclohexadiene, 1 ,3,5,7-cyclooctatetraene, and 1 ,6- diphenyl-1 ,3,5-hexatriene are preferred.
  • the most preferred are 1 ,4- cyclohexadiene and 1 -methyl-1 ,4-cyclohexadienes.
  • bicyclic alkenes such as bicyclo[5.3.0]decapentaene and 3- ethenyl(bicyclo[4.2.0]-octa-1 ,3,5-triene)
  • tricyclic alkenes such as tricyclo[3.3.2.0(2,8)]deca-3,6,9-triene, tricyclo[12.3.2.0(1 , 16)]nonadec-14(19)-ene, tricyclo[5.5.0.0(2,8)]dodeca-4,10-diene, 1 ,2, 3,4,5,6, 7, 8-octamethyl- tricyclo(4.2.0.0(2, 5))octa-3,7-diene, and 5-vinyl-tricyclo(8.2.2.2(4,7))hexadeca- 1 (13), 4(16), 5, 7(15), 10(14), 1 1 -hexaene, and tetracyclic alkenes such as tetracyclo[14.2.2.2(
  • Di-, tri- and tetra-substituted ethylene with alkyl-, alkenyl- aryl- and/or heteroatom- containing substituents can also be used as alkenes in the process of the present invention, just like mono-substituted ethylenes, phenylethylene (styrene), alpha- methylphenylethylene, cyanoethylene (acrylonitrile), vinylpyridines, chloroethylene, fluoroethylene, chloroprene, vinyl acetate, allyl acetate, allyl chloride, allylfluoride, allyl cyanide, allyl alcohol, diallyl ether, allylethyl ether, vinyl ethers and vinyl esters, vinyl amines and vinyl amides, vinyl sulfides, vinylsilanes, divinyl zinc, trivinylaluminium, divinylmagnesium, trivinylboron, acrylic acid, its esters and amides, and methacrylic acid
  • the alkene is present in the composition in an amount of at least 1 ppm, preferably at least 0.001 wt%, more preferably at least 0.0025 wt%, even more preferably at least 0.005 wt%, even more preferably at least 0.01 wt%. even more preferably at least 0.2 wt%, even more preferably at least 0.3 wt%, and most preferably at least 0.5 wt%.
  • the alkene is present in the composition in an amount of not more than 20 wt%, preferably not more than 10 wt%, more preferably not more than 5 wt%, and most preferably not more than 1 wt%.
  • Dialkyi zinc has the formula R 2 Zn, in which R denotes an alkyl group. This alkyl group preferably has 1 -50 carbon atoms, more preferably 1 -10 carbon atoms, and most preferably is ethyl.
  • R denotes an alkyl group. This alkyl group preferably has 1 -50 carbon atoms, more preferably 1 -10 carbon atoms, and most preferably is ethyl.
  • Other compounds that can be present in the composition according to the present invention include other organometallic compounds and solvents.
  • organometallic compounds examples include diethylaluminium chloride, triethylaluminium, and other aluminium organics.
  • suitable solvents are aromatic and aliphatic hydrocarbons, ethers, and amines. Specific examples of suitable solvents are n-hexane, cyclohexane, n- heptane, n-octane, n-decane, n-dodecane, n-tetradecane, 2-methylhexane, 3- methylhexane, 2,2-dimethylpentane, 2,2,3-trimethylbutane, 3-ethylpentane, decahydronaphthalene, benzene, toluene, xylene, methylnaphthalene, diethylether, THF, dioxane, and triethylamine.
  • composition according to the present invention is prepared by adding the alkene to liquid dialkyi zinc or a solution of dialkyi zinc, or vice versa, in the absence of air.
  • Alkenes can be used in the production of dialkyi zinc to reduce fouling during its production process by suppressing thermal decomposition of the dialkyi zinc during distillation.
  • Dialkyi zinc is generally prepared by reacting zinc dihalide (e.g. ZnCI 2 ) with trialkyl aluminium to form both dialkyi zinc and dialkyi aluminium halide. Dialkyi zinc can be removed from the resulting reaction mixture by distillation. This process has been disclosed in various documents, e.g. US 3,124,604 and EP 2 223 024. The reaction is generally performed at temperatures of 20-100°C, preferably 20-70°C. In the process according to the present invention, the alkene is added either (i) to the reaction mixture comprising zinc halide and/or dialkyi zinc, either before or after completion of the formation of the dialkyi zinc, or (ii) to dialkyi zinc prior to or during the distillation.
  • zinc dihalide e.g. ZnCI 2
  • the alkene has a boiling point within about 5°C of the boiling point of the dialkyi zinc.
  • Such alkenes prevent dialkyi zinc decomposition in vapours as well as in the bottoms.
  • the boiling points of dialkyi zincs are generally in the range 40-150°C.
  • the boiling point of diethyl zinc is 1 18 °C. It should be noted that the term "boiling point" in this specification refers to the boiling point at atmospheric pressure.
  • the use of an alkene with a significantly higher (at least 5°C higher) or significantly lower (at least 5°C lower) boiling point is desired.
  • alkenes with such lower boiling points also prevents dialkyi zinc decomposition in vapours; whereas the use of alkenes with such higher boiling points reduces decomposition of dialkyi zinc in the bottoms.
  • the liquid composition according to the present invention finds use in various industries, including the polymerization industry, nuclear industry, electronics industry, and for the manufacture of solar cells, semiconductor devices, and pharmaceuticals.
  • the alkene not only stabilizes the liquid compositions according to the present invention, but also reduces zinc formation during processes in which this composition is used as DEZ source.
  • Thermal stability tests were conducted as follows. In a glove box under nitrogen atmosphere ( ⁇ 2 ppm oxygen), a 10 ml vial was filled with 3 ml diethyl zinc (DEZ; 3 ml) and optionally alkene and the vial was closed with a cap with a Teflon coated membrane. The vials were covered by aluminium foil in order to prevent light- induced decomposition. The vials were heated in an oil bath at 80°C for 24 hours. After cooling down to room temperature, the samples were examined visually for solids formation.
  • DEZ diethyl zinc
  • Solids were filtered off from crude DEZ with a fine fritted filter flask.
  • the clear crude DEZ solution was kept in a bottle wrapped with aluminium foil to block out the light.
  • a 250 ml 3-neck round bottom flask equipped with a thermocouple and a magnetic stirring bar was used for the experiments.
  • the typical charges for the experiments were 100 g filtered crude DEZ solution and 5 g alkene for each run.
  • the reaction mixtures were heated at 1 10°C for 24 hours. During the entire experiment, the 250 ml reaction flask was wrapped with purple rags to block out the light. After this heating, the reaction mixtures were cooled down to room temperature and carefully decanted. The gray solids that had been formed were washed three times with heptanes and dried overnight in the glovebox.

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

Abstract

L'invention concerne une composition de zinc dialkylé thermiquement stable comprenant 1 ppm à 20% en poids d'un alcène, sur base du poids de la composition entière.
PCT/EP2012/056114 2011-04-07 2012-04-04 Composition de zinc dialkylé et procédé de préparation de zinc dialkylé WO2012136679A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201161472924P 2011-04-07 2011-04-07
US61/472,924 2011-04-07
EP11163099 2011-04-20
EP11163099.2 2011-04-20

Publications (1)

Publication Number Publication Date
WO2012136679A1 true WO2012136679A1 (fr) 2012-10-11

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124604A (en) 1956-02-21 1964-03-10 New organic zinc compounds and a proc-
FR2274624A1 (fr) * 1974-06-17 1976-01-09 Texas Alkyls Inc Procede pour la recuperation d'halogenures de dialkylaluminium a partir de melanges contenant du zinc soluble
US4732992A (en) * 1986-12-22 1988-03-22 Stauffer Chemical Company Method for recovery of alkylaluminum halides
EP2223024A1 (fr) 2007-12-21 2010-09-01 BSH Bosch und Siemens Hausgeräte GmbH Condenseur destiné à un appareil frigorifique
EP2223924A1 (fr) * 2008-11-12 2010-09-01 Nippon Aluminium Alkyls, Ltd. Procédé pour la production de monohalogénure de dialkylaluminium
EP2280015A1 (fr) * 2008-04-30 2011-02-02 Nippon Aluminium Alkyls, Ltd. Procédé de fabrication de dialkyle zinc et de monohalogénure de dialkyle aluminium

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124604A (en) 1956-02-21 1964-03-10 New organic zinc compounds and a proc-
FR2274624A1 (fr) * 1974-06-17 1976-01-09 Texas Alkyls Inc Procede pour la recuperation d'halogenures de dialkylaluminium a partir de melanges contenant du zinc soluble
US4732992A (en) * 1986-12-22 1988-03-22 Stauffer Chemical Company Method for recovery of alkylaluminum halides
EP2223024A1 (fr) 2007-12-21 2010-09-01 BSH Bosch und Siemens Hausgeräte GmbH Condenseur destiné à un appareil frigorifique
EP2280015A1 (fr) * 2008-04-30 2011-02-02 Nippon Aluminium Alkyls, Ltd. Procédé de fabrication de dialkyle zinc et de monohalogénure de dialkyle aluminium
EP2223924A1 (fr) * 2008-11-12 2010-09-01 Nippon Aluminium Alkyls, Ltd. Procédé pour la production de monohalogénure de dialkylaluminium

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHARETTE A B ET AL: "Acyloxymethylzinc reagents: Preparation, reactivity, and solid-state structure of this novel class of cyclopropanating reagents [12]", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 2001 US LNKD- DOI:10.1021/JA0109287, vol. 123, no. 33, 2001, pages 8139 - 8140, XP002639551, ISSN: 0002-7863 *
DEHMLOW E. V., STÜTTEN J.: "ON THE STEREOSELECTIVITY OF IODOCARBENE AND -CARBENOID ADDITIONS TO CYCLIC ALKENES", TETRAHEDRON LETTERS, vol. 32, no. 43, 1991, pages 6105 - 6108, XP002639552 *
HOYE THOMAS R., EKLOV BRIAN M., VOLOSHIN MIKHAIL: "No-D NMR Spectroscopy as a Convenient Method for Titering Organolithium (RLi), RMgX, and LDA Solutions", ORGANIC LETTERS 18 MAR 2004 LNKD- PUBMED:15012073, vol. 6, no. 15, 2004, pages 2567 - 2570, XP002639550 *
KACPRZYNSKI M A ET AL: "Cu-catalyzed asymmetric allylic alkylations of aromatic and aliphatic phosphates with alkylzinc reagents. An effective method for enantioselective synthesis of tertiary and quaternary carbons", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 20040901 US LNKD- DOI:10.1021/JA0478779, vol. 126, no. 34, 1 September 2004 (2004-09-01), pages 10676 - 10681, XP002639549, ISSN: 0002-7863 *

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