• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    The invention relates to the chemistry of organophosphorus compounds with a C – P bond, namely, to a method for producing sulfonated triphenylphosphines, which are used as water-soluble ligands, which allow the formation of complexes with input and output group metals, which can be used as a catalyst. Ditch upon receipt of aldehydes by hydroformylation of olefins. Phosphoresis by-the-day-to-day phosphine or de-cyclymethylsulfoxide, in the atmosphere of an inert gas, the organic phase is determined and processed by its alkali. The invention allows be about; dess due to the processing of the hydrolyzate extractant. 2 hp ff, 1 ill. 2 tab.
    公开号:SU1279532A3
    申请号:SU3635273
    申请日:1983-08-30
    公开日:1986-12-23
    发明作者:Сабо Жан-Луи
    申请人:Рон-Пуленк Шими Де Баз (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for the preparation of sulfonated triphenylphosphines of the general formula
    (ZOZN) pz (lS03M) ni
    where M is a cation of lithium, sodium, potassium or an uni-act;
    P |, p, p - integers, one
    forged or different, I g 5
    O or 1, and
    n, + hj + n 2 or 3.
    Sulfonated triarylphosphines are used as water-soluble ligands that allow the formation of complexes with transition metals, such as rhodium, in water, and these solutions can be used as catalysts, for example, to synthesize aldehydes by hydroforming olefins.
    The purpose of the invention is to simplify the process, which is achieved by the fact that sulphonated triphenylphosphine processes the extragentone
    The drawing shows a scheme in which a continuous flow can occur. extractant treatment process,
    The extraction battery 1, which consists of six stages, is fed to the third stage through line 2 a stream of dilute hydrolyzate containing 350 g / l H2SO4 and 30 g / l sulfonated triphenylphosphine (TFPS), determined by iodometric titration and consisting of TFFTS (24 g / l) and TFFDS (6 g / l), the corresponding amounts of which are determined by NMR spectrum. Flow rate 500.
    A tributyl phosphate (TBP) flow at a flow rate of 100 and a LINE 4 flow into the flow of water at a flow rate of 20 cm are fed into the battery through line 3, and water provides for the repeated extraction of sulfuric acid entrained with tributyl phosphate along with TFPS. 5 is a raffinate flow comprising TFPS and sulfuric acid 0.06 and 335 g / l, respectively.
    From the battery 1 through line 6 flows TBF containing TFPS, which then enters the battery 7 regeneration, fed, in addition, the countercurrent through line 8 with a solution of 1.05 n "caustic soda with a flow rate of 85.
    0
    15
    0
    25
    thirty

    50
    From battery 7, line 9 leads to a flow at a rate of 102 cm / h of TFPS sodium salt solution, constituting the reaction product. This solution contains 160 g / l of sodium salt TFPS, i.e. 132 g of trisodium salt TFPT and 28 g of disodium salt TFFDS, as well as 625 mg / l and less than 300 mg / l of chlorine ions.
    Part of the flow can be diverted via line 9, in which case this tap will make up the supply flow through line 4 of the battery 1 o
    Example 1, Method for producing a hydrolyzate.
    A 500 ml Erlenmeyer flask is charged with 200 g of sulfuric acid, brand Rh ne-ponlens Ncrmapi r (minimum 95%). Cool to 6 ° C in an ice-water bath with stirring. Slowly load 100 g of triphenylphosphine (TFF) Fluka rigs (minimum 98%). After dissolving half of the TFF, the temperature of the sulfuric acid is raised to complete the dissolution.
    A flask placed in a thermostatic bath is charged with 1 liter of Nordhausen sulfuric acid of the Prola bo brand (20 wt.% SOj) (1860 g) and cooled with stirring approximately up to by adding ice to the thermostatic bath. When the temperature reaches 6 ° C, add slowly min)
    (min) solution of TFF - sulfuric acid 35ta. Set the bath temperature to 26 ° C and leave for 90 hours with slow stirring in a weak argon flow.
    Cool the thermostat with
    40
    55
    ice to a temperature in the flask 6 C and pour in 90 g of distilled water for 1 h.
    A hydrolyzate is obtained containing 2022 g of 100% sulfuric acid (89.83%), 37 g of water (1.65%) and 192 g of sulfonated triphenylphosphine derivatives, consisting of 140 g of three metasulfophenyl; (ospina (TFPTS), 32.5 g di (methacylphenip) -phenylphosphine (TFFDS) and 19 g three-oxide (metasulfophenyl:) phosphine (OTPPTS).
    Extraction of hydrolyzed sulphate in an inert atmosphere, the extras being degassed beforehand.
    Example 2. Starting from 1 liter of the hydrolyzate of the reaction mixture, prepared according to the method described in Example I, and containing 1712 g of sulfur 3129532
    Acidic acid and 116 g of sulfonated triphenylphosphine (TFPS), consisting of 94 g of TFPTS and 22 g of TFFDS. This 1 liter of hydrolyzate is diluted with 4 l of water.
    The solution is brought into contact with 1 liter of 3 tributyl phosphate (TBP) and, after separation of the raffinate, is again brought into contact with 1 liter of TBP. The raffinate after the second extraction contains 1.9 g TFPS, i.e. yield after extraction in vbay 98%. 0
    Both fractions of the extraction are combined, then regenerated with 250 cm 10 n. sodium hydroxide solution and get a solution containing 130 g of sodium salt TFPS, consisting of 25 g sodium salt -5 TFDS and 105 g sodium salt TFTS, as well as 129 g sodium sulfate "
    Example 3. Starting from the same hydrolyzate as in example 2, the process is carried out in the same way, but with 1 liter (Y-octanol. 20 After the second extraction, the raffinate contains 5 g of TFPS, the extraction yield is 95%.
    Both extraction fractions are combined.
    0.17; trisodium salt, OTFPTS 0.012. The aqueous phase also contains 2.1% TBP; which can be removed by washing with a solvent.
    The proposed method makes it possible to effectively remove OTFTNS, which contributes to an increase in the purity of the obtained target product.
    Example 5 Into the extraction battery 1, which includes six steps, the third step injects through line 2 a stream of dilute hydrolyzate containing 350 g / l N, 50 and 30 g / l, DFT, determined by volumetric iodometric analysis and of 24 g / l TfWbTC and 6 g / l TFFDS, the corresponding amounts of which are determined by the P31 NMR spectrum. This stream 2 has a flow rate of 500.
    The battery is also loaded with a countercurrent through line 3 with a TBP flow with a flow rate of 100 cm / h and through line 4 with a flow of water with a flow rate of 20 cm / h, which the latter provides afterwards is then regenerated with 250 cm 10 n. extraction of sulfuric acid sodium to obtain a solution containing 250 g of sodium sulfate and 125 g of sodium salt TFPS, consisting of 101 g salt fjaTpHH TFFTS and 25 g sodium salt TFFDS.
    Example 4. In an extraction battery comprising four stages, a stream of dilute hydrolysis is introduced into the second stage, containing
    350 g / l HjSO ,, and sulfonated triphenylphosphine derivatives, mol / l: TFFTS 3, DFFS 9.1-10; OFTFS 5.3-10-
    Used battery is supplied by counter current


    current TBP (tributyl phosphate) with flow

    cm / h and flow -V4.
    water with flow
    ON 20 cm
    The raffinate water flow comes out of the battery, containing 335 g / l and sulfonated triphenyl-45 derivatives, mol / l: TFFTS iO; T (#lC less than
    ten ; OFTFTS 4.4-10
    From the battery also enters the TBF stream, loaded with DPSS, which then enters the regenerative battery, 50 loaded with a countercurrent of 5.8 n. sodium hydroxide solution at a rate
    .13 /
    15 cm / h
    Of
    this battery comes the flow of water-55 TFTS 136; dikalieva salt DFF
    a solution of sodium salt TFPS, which is a product containing, mol / L: trisodium salt TFFTS 0.64; disodium salt TFFDS
    27, as well as, mg / l: potassium sulphate 720; chlorine ions below 300.
    Example 7. The flow on line 6 formed by TBP, loaded
    0.17; The trisodium salt of OTFPTS 0.012 The aqueous phase also contains 2.1% TBP; which can be removed by washing with a solvent.
    The proposed method makes it possible to effectively remove OTFTNS, which contributes to an increase in the purity of the obtained target product.
    Example 5 Into the extraction battery 1, which includes six steps, the third step injects through line 2 a stream of dilute hydrolyzate containing 350 g / l N, 50 and 30 g / l, DFT, determined by volumetric iodometric analysis and of 24 g / l TfWbTC and 6 g / l TFFDS, the corresponding amounts of which are determined by the P31 NMR spectrum. This stream 2 has a flow rate of 500.
    The battery is also loaded with countercurrent through line 3 with a flow of TBP with a flow rate of 100 cm / h and through line 4 with a flow
    Inia 8
    you and co-extract TBP with DFF.
    From battery 1, line 5 leaves the stream, which consists of raffinate and contains 0.06 g / l DFPS and 335 r / j.
    .
    From the battery 1 through line 6 comes the flow TBF, loaded with DPSS, which then enters the regeneration battery 7, loaded with countercurrent
    lines 8
    in concentration / h
    f
    1 mol / l ammonia solution with a flow rate of 90 cm. From this battery 7, a flow through line 9 comes with a flow rate of 105 cm / h of an ammonium salt TFPS solution, which is a product containing, g / l: TFTP-125 triammonium salt; diammonium salt TFFDS 26, as well as, mg / l: ammonium sulfate 550; chlorine ions less than 300.
    f
    Example 6. The flow through line 6 formed by TBP, immersed with TFPS, feeds the regeneration battery 7 loaded with countercurrent through line 8 with potassium oxide solution at a concentration of 1 mol / l with a flow rate of 90.
    From the battery 7 comes out on line 9 stream with a flow rate of 105 solution containing, g / l: trikaliev salt
    TFFTS 136; dikalieva salt DFF
    27, as well as, mg / l: potassium sulphate 720; chlorine ions below 300.
    Example 7. The flow on line 6 formed by TBP, loaded
    five
    TFPS, feeds the battery 7 regenerated, loaded with counterflow with a solution of lithium hydroxide at a concentration of 1 mol / l at a rate of 90
    From battery 7, line 9 leaves a flow with a flow rate of 105 cm / h of a solution of the following solution. G / l: trilitium salt TFFTS 117 dilithium salt TFFDS 25 and also, mg / l: line sulfate 450; and chlorine ions less than 300.
    Example 8 Starting from the hydrolysate of Example 2 and implementing the following experiments, consisting of bringing a liter of hydrolyzate and 1 liter of solvent into contact: Four emitted solvent are as follows: dibutylphosphonate (DBP); dioctyl methylphosphinate (DAMP); trioctylphosphine oxide (TOPO) in the form of a 30% solution in an aromatic hydrocarbon oil fraction (for example, 5 under the name Solvessc 150); H - decylmethylsulfoxy (DMSO) in the form
    about
     solution in Solvesso 150, After separation of the phases, the corresponding distribution coefficients H ,, SO ,, and TFPS are determined (Ph., up to 4 - fcfc. Table 1 shows the distribution coefficients H ,, ЯО and ТФФС.
    T a 6 l and c a


    Extractant | Rc | R,.
    fsrv
    0.27 0.28 0.28 0.28
    50 85 10 10
    Example 9: Use this hydrolyzate of Example 2 and dilute it to vary the concentration of sulfuric acid. This hydrolyzate is extracted with TBP with a volume ratio of phases equal to i.
    The distribution coefficients determined after the phase separation are given in Tablg 2 o
    table 2
    6
    Continuation of table 2,
    权利要求:
    Claims (4)
    [1]
    The invention relates to a process for the preparation of sulfonated triphenylphosphines of the general formula (ZOZN) pz (lS03M) ni where M is a cation of lithium, sodium, potassium, or an actin; P |, p, p - integers, equal to or 1, with coke or different, p, + Hj + n 2 or 3. I g 5 Sulfonated triarylphosphines are used as water-soluble ligands that allow the formation of complexes with transition metals for example, with rhodium, in water, and these solutions can be used as catalysts, for example, for the synthesis of aldehydes by hydroformylation of olefins. The purpose of the invention is to simplify the process, which is achieved by the fact that sulfonated triphenylphosphine treats extractively. In the drawing, a diagram is shown along which a continuous process can proceed. the process of treatment with the extractant, to the extraction battery 1 consisting of six steps, is fed to the third step through line 2 a stream of dilute hydrolyzate containing 350 g / l H2SO4 and 30 g / l sulfated triphenylphosphine (TFPS), determined by iodometric titration and consisting from TFFTS (24 g / l) and TFFDS (6 g / l), the corresponding amounts of which are determined by NMR spec. Flow rate 500. A flow of tributyl phosphate (TBP) at a flow rate of 100 and a LINE 4 flow of water at a flow rate of 20 cm is also supplied to the battery in flow line 3, and water provides for the repeated extraction of sulfuric acid entrained with tributyl phosphate together with TFPS. , constituting the raffinate, with the content of TPPS and sulfuric acid, 0.06 and 335 g / l, respectively. From the battery 1 through line 6 flows TBF containing TFPS, which then enters the battery 7 regeneration, fed, in addition, against the current through line 8 with a solution of 1.05 n "caustic soda at a rate of 85. From battery 7, line 9 leads to a flow at a rate of 102 cm / h of TFPS sodium salt solution, constituting the reaction product. This solution contains 160 g / l of sodium salt TFPS, i.e. 132 g of trisodium salt TFPT and 28 g of disodium salt TFFDS, as well as 625 mg / l and less-300 mg / l of chlorine ions. Part of the flow can be diverted via line 9, in which case this tap will make up the supply flow through line 4 of battery 1 of Example 1, Method for preparing a hydrolyzate. A 500 ml Erlenmeyer flask is charged with 200 g of sulfuric acid, brand Rh ne-ponlens Ncrmapi r (minimum 95%). Cool to 6 ° C in an ice-water bath with stirring. Slowly load 100 g of triphenylphosphine (TFF) Fluka rigs (minimum 98%). After dissolving half of the TFF, the temperature of the sulfuric acid is raised to complete the dissolution. A flask placed in a thermostatic bath is charged with 1 liter of Prolabo Nordhausen sulfuric acid (20 wt.% SOj) (1860 g) and cooled with stirring until approx. By adding ice to the thermostatic bath. When the temperature reaches 6 ° C, slowly dissolve the min) (min) solution of TFF - sulfuric acid. The bath temperature was set at 26 ° C and left for 90 hours with slow stirring in a weak argon flow. Cool the thermostat with ice to a temperature in the flask of 6 ° C and pour in 90 g of distilled water for 1 hour. A hydrolyzate is obtained containing 2022 g of 100% sulfuric acid (89.83%), 37 g of water (1.65%) and 192 g of sulfonated triphenylphosphine derivatives, consisting of 140 g of three metasulfophenyl; (osfina (TFPTS), 32.5 g of di (methacylphenip) -phenylfosfine (TFFDS) and 19 g of tri (metasulfophenyl:) -phosphine oxide (OTPPS). Extraction of hydrolyzate in an inert atmosphere, and the extractants previously degassed.
    [2]
    2. Starting from 1 liter of the hydrolyzate of the reaction mixture obtained by the method described in example I, and containing 1712 g of sulfuric acid and 116 g of sulfonated triphenylphosphine (TFPS), consisting of 94 g of TFPTS and 22 g of TFFDS. This 1 liter of hydrolyzate is diluted with 4 l of water. The solution is brought into contact with 1 L of tributyl phosphate (TBP) and, after separation of the raffinate, is again brought into contact with 1 L of TBP. The raffinate after the second extraction contains 1.9 g TFPS, i.e. yield after extraction in vbay 98%. Both fractions of the extraction are then combined to regenerate 250 cm 10 n. sodium hydroxide solution and get a solution containing 130 g of sodium salt TFPS, consisting of 25 g sodium salt TFFDS and 105 g sodium salt TFTS, and also 129 g sodium sulfate "Example
    [3]
    3. Starting from the same hydrolyzate as in example 2, the process is carried out in the same way, but with 1 liter (Y-octanol. The raffinate after the second extraction contains 5 g of TFPS, the extraction yield is 95%. Both extraction fractions are then regenerated 250 see 10 N sodium oxide and get a solution containing 250 g of sodium sulfate and 125 g of sodium salt TFPS, consisting of 101 g salt fjaTpHH TFFTS and 25 g sodium salt TFFDS.
    [4]
    4. In the extraction battery, which includes four stages, the second stage introduces a stream of dilute hydrolysis containing 350 g / l HjSO ,, and sulfonated triphenylphosphine derivatives, mol / l: TFFTS 3, TFFDS 9.1-10; OFTFS 5.3–10-B battery is supplied with a countercurrent flow TBP (tributyl phosphate) with a flow rate of cm / h and a flow of water with a flow of -V4. The raffinate water flow comes out of the battery, containing 335 g / l and sulfonated trifenium derivatives, mol / l: TFFTS iO; T (№lC less 10; OFTPS 4.4 and 10-10 The TBF flow, loaded with TFFS, also enters a regenerative battery loaded with a countercurrent of 5.8 n sodium hydroxide solution with a flow rate of 1–3 / 15 cm / h. This battery leaves a stream of water-55% solution of sodium salt TFPS, which is a product containing, mol / l : trisodium salt TFFTS 0.64; disodium salt TFFDS 32 0.17; trisodium salt OTFPTS 0.012, Water phase with It also contains 2.1% TBP; which can be removed by washing with a solvent. The proposed method effectively removes the OTFPT that enhances the purity of the obtained target product. Example 5, In an extraction battery 1 including six steps, the third stage is introduced through line 2, a stream of dilute hydrolyzate containing 350 g / l N, 50 and 30 g / l, TFFS, determined by volumetric iodometric analysis and consisting of 24 g / l TfWbTC and 6 g / l TFFDS, the corresponding quantities of which are determined by P31 NMR Spectrum This stream 2 has a flow rate of 500. The battery is also loaded with a countercurrent through line 3 with TBP flow with a flow rate of 100 cm / h and through line 4 with a flow of water with a flow rate of 20 cm / h, the latter providing for the repeated extraction of sulfuric acid and co-extracting TBP with TFFDS. From battery 1, line 5 leaves the stream, which consists of raffinate and contains 0.06 g / l DFPS and 335 r / j. . From battery 1, line 6 leaves a TBF flow loaded with DPSS, which then enters the regenerative battery 7 loaded with countercurrent through line 8 with ammonia solution at a concentration / hr. Traces of 1 mol / l with a flow rate of 90 cm. From this battery 7, a flow through line 9 comes with a flow rate of 105 cm / h of an ammonium salt TFPS solution, which is a product containing, g / l: TFTPA 125 triammonium salt; diammonium salt TFFDS 26, as well as, mg / l: ammonium sulfate 550; chlorine ions less than 300. f Example 6. The flow through line 6 formed by TBP, immersed with TFFS, feeds the regeneration battery 7 loaded with countercurrent through line 8 with potassium oxide solution at a concentration of 1 mol / l with a flow rate of 90. From the battery 7 comes out through line 9 a flow with a flow rate of 105 solution containing, g / l: trikaliyev salt TFFTS 136; Dicalium salt TFFDS 27, as well as, mg / l: potassium sulfate 720; chlorine ions are lower than 300. Example 7. The flow through line 6 formed by TBP loaded with 5 DFPS feeds the regeneration battery 7 by charging with a solution of lithium hydroxide at a concentration of 1 mol / l at a rate of 90 From the battery 7 through line 9 leaves the flow with a flow rate of 105 cm / h of the solution of the following solution. g / l: trilithium salt TFFTS 117 dilithium salt TFFDS 25 and, mg / l: sulfate line 450; and chlorine ions less than 300. Example 8, Starting from the hydrolyzate of Example 2 and implementing the following experiments, consisting of bringing into contact 1 liter of hydrolyzate and 1 liter of solvent. Four emitted solvents are the following: dibutylphosphonate (DBP); dioctyl methylphosphinate (DAMP); trioctylphosphine oxide (TOPO) in the form of a 30% solution in an aromatic hydrocarbon oil fraction (available under the brand name Solvessc 150); H - decylmethylsulfoxy (DMSO) as a solution in Solvesso 150. After separation of the phases, the corresponding distribution coefficients H ,, SO ,, and TFPS are determined. (Ph p., Up to 4 - fcfc) Table 1 shows the distribution coefficients H, Y0 and TFPS. Extractive | Pc | P, Example 9, Use hydrolyzate of Example 2 and dilute it to change the concentration of sulfuric acid. This hydrolyzed extract TBP with a volume ratio of phases equal to i. Coefficients the distributions determined after the phase separation are given in tablg 2 o Table 32 Continued from table 2, Forms la INVENTION 1. A process for preparing sulphonated triphenylphosphine of general formula --R 0 - CHO) pz S where M - cation of lithium, sodium, potassium or ammonium; (1–25 centigrade bottles, identical or different, O or 1, moreover, P (+ + n + n 2 or 3, by sulfonating triphenylphosphine with oleum in an inert gas atmosphere and hydrolysis of the reaction mixture to form a hydrolyzate containing sulfuric acid and sulfonated triphenylphosphine, About tl and h and y with and there 5 that, in order to simplify the process, the hydrolyzate is treated with an extractant selected from the group: tributylphos (1) at, and -octanol, butyldibutylphosphinate, dioctyl-metaphosphonate, tri oxide (h-octyl ) fosfina or n-decylmethylsulfoxide, in an inert rasaj atmosphere, are separated from the aqueous phase and the organic phase are treated with water with an alkali solution, followed by separation of an aqueous solution of sulfonated triphenylphosphine or its salt. 2, The method according to claim 1, characterized in that the hydrolyzate is diluted to 3-10 N with sulfuric acid, 3, The method according to claims and 2, characterized in that the organic phase is washed with water before treatment with alkali.
    /
    eight
    X
    /
    /
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    同族专利:
    公开号 | 公开日
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    CA1192574A|1985-08-27|
    ES8405023A1|1984-05-16|
    EP0104967A1|1984-04-04|
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    EP0104967B1|1985-10-16|
    BR8304701A|1984-04-10|
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    JPS5984895A|1984-05-16|
    DE3361033D1|1985-11-21|
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    ES2459790B1|2012-11-07|2015-04-27|Universitat Autònoma De Barcelona|Carboxylic triphenylphosphines|
    CN103254232B|2013-05-27|2016-05-18|成都欣华源科技有限责任公司|The preparation method of water-soluble threephosphine|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8214862A|FR2532318B1|1982-08-31|1982-08-31|PROCESS FOR THE PREPARATION OF SULPHONE TRIARYLPHOSPHINES|
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