EP2013143A1 - Verfahren zur herstellung von bortrifluoridkomplexen - Google Patents

Verfahren zur herstellung von bortrifluoridkomplexen

Info

Publication number
EP2013143A1
EP2013143A1 EP07731866A EP07731866A EP2013143A1 EP 2013143 A1 EP2013143 A1 EP 2013143A1 EP 07731866 A EP07731866 A EP 07731866A EP 07731866 A EP07731866 A EP 07731866A EP 2013143 A1 EP2013143 A1 EP 2013143A1
Authority
EP
European Patent Office
Prior art keywords
complexes
boron trifluoride
complexing agent
static mixer
temperature
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP07731866A
Other languages
English (en)
French (fr)
Inventor
Philippe Joubert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
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 Arkema France SA filed Critical Arkema France SA
Publication of EP2013143A1 publication Critical patent/EP2013143A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/12—Fluorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/06—Boron halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type

Definitions

  • the present invention relates to a process for producing boron trifluoride complexes.
  • complexing agents are generally compounds comprising oxygen, nitrogen, phosphorus or sulfur, for example water, ethers, alcohols, ketones, acids, amines, phosphines and the thiols.
  • trifluoride is the most widely used. Many applications rely on its strong Lewis acid properties.
  • Boron trifluoride (BF 3 ) is an agent of outstanding interest for organic synthesis because of the variety of reaction types it allows and the large number of compounds that can react.
  • Boron trifluoride is often used for its catalytic action, for example in Friedel and Crafts alkylation reactions, esterification reactions and in the "nitration" and sulphonation of aromatic compounds. Boron trifluoride is used as an initiator of olefin polymerization in combination with proton donors. Boron trifluoride is also used to catalyze the isomerization of alkenes, alkanes.
  • the boron trifluoride complexes are generally prepared batchwise in a stirred reactor.
  • the complexing agent is introduced in the liquid state into a vessel equipped with a stirrer and equipped with a heat exchanger, for example a jacket or an internal coil in which circulates a coolant.
  • Boron trifluoride is introduced in the gaseous state into the complexing agent liquid by means of a diving stick. Since this reaction is highly exothermic, stirring must be maintained in order to control and avoid losses of boron trifluoride and / or complexing agent.
  • the temperature of the heat transfer fluid must be regulated so as to maintain the reaction medium in the liquid state, and at the lowest possible temperature in order to minimize material losses by volatilization and in some cases corrosion of the reactor.
  • the critical molar ratio is in the vicinity of 0.5, corresponding to a specific weight of 32-36%.
  • the boron trifluoride titer is less than 36% by weight in the medium, there is a risk of polymerization, partial or total, of the complexing agent tetrahydrofuran and thus degradation of the final product, for example an abnormally viscous high and very strong coloration.
  • the present invention provides a novel process for the manufacture of boron trifluoride complexes which makes it possible to solve all or part of the aforementioned drawbacks.
  • the subject of the present invention is a process for the production of boron trifluoride complexes comprising a step in the course of which the boron trifluoride is brought into contact with the complexing agent in at least one static mixer and a step of isolating the complexes. thus obtained.
  • the contacting step it is preferable to operate in the presence essentially of boron trifluoride, of the complexing agent and possibly of boron trifluoride complexes.
  • the complexing agent is, in general, compounds comprising oxygen, nitrogen, phosphorus or sulfur and preferably chosen from water, ethers, alcohols, ketones, acids, amines, phosphines and thiols.
  • the complexing agent may be introduced into the static mixer in the gaseous or liquid state or dissolved in a solvent.
  • the contact temperature of the boron trifluoride with the complexing agent can vary within wide limits. This temperature is preferably at least 1 to 5 ° C higher than the melting temperature of the complex. A temperature between 10 and 50 ° C may also be suitable.
  • the complexes leaving the liquid state of the static mixer are then advantageously solidified suddenly in order to limit their thermal decomposition.
  • This solidification can be implemented using a drum or band scale or any other rapid cooling process.
  • the boron trifluoride is introduced in the gaseous state and advantageously under an absolute pressure of between 1 and 100 bar, into the static mixer.
  • a pressure of between 1 and 10 bar is particularly preferred.
  • the process can be carried out both discontinuously and continuously. However, it is preferred to operate continuously.
  • the process makes it possible to prepare complexes in a wide range of boron trifluoride / complexing agent molar ratio, for example from 0.01 to 1, but is aimed in particular at the boron trifluoride boron trifluoride / complexing agent molar ratio complexes. between 0.5 and 1.
  • the complexing agents are advantageously chosen from water, dimethyl ether, diethyl ether, methanol, ethanol, butanol, propanol, isopropanol, phenol, acetic acid, propionic acid and monoethylamine. tetrahydrofuran.
  • any type of static dual envelope mixer may be suitable.
  • Static mixers with fixed elements of helical structure or with alternately inverted steps can be mentioned in particular.
  • the choice of the number of elements depends on the desired homogeneity of the mixture, while the size of the elements depends on the desired working regime, which can be turbulent, transient or laminar.
  • the process according to the present invention makes it possible to obtain quantitative yields and / or high volume productivities.
  • the temperature control is easy thus reducing side reactions and / or corrosion that can lead to a partial or total deterioration of the quality of the desired product.
  • the present invention makes it possible to continuously produce solid and liquid boron trifluoride complexes.
  • the residence time in the mixer is defined as the ratio of the effective volume of the mixer / total gas flow.
  • the residence time, in the absence of reaction, in the static mixer is 0.2 s.
  • the temperature of the flow leaving the static mixer is between 19 and 21 ° C.
  • 450 g of liquid product containing 59.5% of boron trifluoride and of density 1 are obtained. 237 kg / l.
  • Example 2 ( Figure 2)
  • the receptacle (6) used to recover the outflow (3) of the static mixer (4) initially contains 250 g of methanol.
  • 48.6 g / hr of gaseous boron trifluoride (1) is fed continuously into a double jacketed static mixer (4) and, using a pump (7) of the liquid, at a rate of 100 ml / h.
  • the residence time, in the absence of reaction, is 0.4 s.
  • 523 g of liquid complex BF 3 are recovered. 2 CH 3 OH titrating 52.19% BF 3 and density 1, 22 kg / l.
  • Example 3 ( Figure 3)
  • the static mixer (8) is fed continuously firstly from the complex receptacle (6) initially containing 50 g of complex BF 3 -diethylether (47.3% BF 3 ), by means of a pump (7) debiting 76 g / h, secondly diethylether (9) by means of the pump delivering 76 g / h.
  • the static mixer (4) is fed at the same time by the liquid flow (2) leaving the first static mixer (8) and by the gaseous BF 3 (68 g / h). At a flow rate of BF 3 of 68 g / h corresponds to a residence time of 0.5 seconds in the static mixer (4), in the absence of a reaction.
  • a cooling fluid (temperature + 18 ° C.) circulates inside the double envelopes of the static mixers in order to eliminate the calories released during the exothermic reaction of complexation of BF 3 with diethyl ether. After 2 h 26 min of test, and emptying the receptacle (6) equipped with a condenser (5), 400 g of liquid complex of density 1, 12 kg / l, and grading 47.17% of BF are recovered. 3 (stoichiometric composition of complex 1 BF 3 - 1 (C 2 H 2 ) 2 O: 47.82% BF 3 ).
  • Example 3 is repeated except that the receptacle initially contains 50 g of complex BF 3 / CH 3 COOH and that the static mixer (8) is supplied with complex by means of the pump (7) with a flow rate of 53. g / h and with acetic acid with a flow rate of 46.6 g / h.
  • the gas flow rate of BF 3 is 45 g / h and the residence time, in the absence of reaction, is 0.7 s.
  • EXAMPLE 5 At atmospheric pressure, boron trifluoride (gas) (1) is fed continuously at atmospheric pressure into a jacketed static mixer (1) at a rate of 102 g / h and liquid THF (2) at reason of 110 g / h. The temperature of the refrigerant feeding the double envelope of the static mixer is 10 0 C. The liquid flow (3) leaving the static mixer is then recovered in a container (6) provided with a condenser (5).
  • the residence time, in the absence of reaction, in the mixer is static of 0.3 s.
  • the temperature of the flow leaving the static mixer is between 19 and 21 ° C.
  • 2 h 10 min of test one obtains 459 g of liquid complex BF 3 THF very little colored and low viscosity, grading 48.15. % boron trifluoride and mass volume 1, 261 kg / l.
  • Samples were taken at the end of 30, 60 and 150 minutes, and the densities were respectively 1, 260, 1, 257 and 1, 263 corresponding to weightings in BF 3 of 48.1, 47.8 and 48.4%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP07731866A 2006-04-28 2007-04-04 Verfahren zur herstellung von bortrifluoridkomplexen Withdrawn EP2013143A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0603837A FR2900402B1 (fr) 2006-04-28 2006-04-28 Procede de fabrication de complexes de trifluorure de bore
PCT/FR2007/051063 WO2007125232A1 (fr) 2006-04-28 2007-04-04 Procédé de fabrication de complexes de trifluorure de bore

Publications (1)

Publication Number Publication Date
EP2013143A1 true EP2013143A1 (de) 2009-01-14

Family

ID=37467575

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07731866A Withdrawn EP2013143A1 (de) 2006-04-28 2007-04-04 Verfahren zur herstellung von bortrifluoridkomplexen

Country Status (3)

Country Link
EP (1) EP2013143A1 (de)
FR (1) FR2900402B1 (de)
WO (1) WO2007125232A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102911195A (zh) * 2012-10-31 2013-02-06 江峰 三氟化硼四氢呋喃的制备方法
CN111675730A (zh) * 2020-06-22 2020-09-18 东营合益化工有限公司 一种三氟化硼二甲醚络合物的制备方法
CN114409686B (zh) * 2022-01-27 2023-11-07 上海化工研究院有限公司 一种用于制备三氟化硼络合物的系统及方法

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Publication number Priority date Publication date Assignee Title
BE1006694A5 (fr) * 1991-06-22 1994-11-22 Basf Ag Procede de preparation de polyisobutenes extremement reactifs.
DE4306384A1 (de) * 1993-03-02 1994-09-08 Basf Ag Chlorfreie, nicht-trocknende Isobuten-Dien-Copolymere
DE10028585A1 (de) * 2000-06-14 2001-12-20 Basf Ag Verfahren zur Herstellung von Polyisobutenen
DE10125583A1 (de) * 2001-05-25 2002-11-28 Basf Ag Verfahren zur Herstellung von Homo- und Copolymeren des Isobutens
JP2004352913A (ja) * 2003-05-30 2004-12-16 Mitsubishi Gas Chem Co Inc ポリオキシメチレン樹脂組成物の製造方法

Non-Patent Citations (1)

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Title
See references of WO2007125232A1 *

Also Published As

Publication number Publication date
WO2007125232A1 (fr) 2007-11-08
FR2900402B1 (fr) 2008-07-18
FR2900402A1 (fr) 2007-11-02

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