CN111808134B - Method for extracting triphenylphosphine sulfonate from sulfonated product - Google Patents
Method for extracting triphenylphosphine sulfonate from sulfonated product Download PDFInfo
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- CN111808134B CN111808134B CN202010767303.1A CN202010767303A CN111808134B CN 111808134 B CN111808134 B CN 111808134B CN 202010767303 A CN202010767303 A CN 202010767303A CN 111808134 B CN111808134 B CN 111808134B
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- triphenylphosphine
- sulfonate
- extracting
- triphenylphosphine sulfonate
- sulfonated
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 title claims abstract description 214
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012071 phase Substances 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000012074 organic phase Substances 0.000 claims abstract description 23
- 238000004821 distillation Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 20
- 238000001291 vacuum drying Methods 0.000 claims abstract description 19
- -1 alkane compounds Chemical class 0.000 claims abstract description 18
- 239000012670 alkaline solution Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000006277 sulfonation reaction Methods 0.000 claims description 26
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000007791 liquid phase Substances 0.000 claims description 16
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- 239000000047 product Substances 0.000 description 69
- 239000012265 solid product Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for extracting triphenylphosphine sulfonate from a sulfonated product, which comprises the following steps: a) adding water to dilute the sulfonated product until the concentration of sulfuric acid in the mixed solution is 1-5 mol/L, and then adding an extracting agent for extraction to obtain an organic phase; the extracting agent is a mixture of phosphate compounds and alkane compounds; b) neutralizing the organic phase obtained in the step a) by using an alkaline solution, standing and separating to obtain a water phase containing triphenylphosphine sulfonate; c) and c) sequentially carrying out crystallization, impurity removal, reduced pressure distillation and vacuum drying on the water phase containing the triphenylphosphine sulfonate obtained in the step b) to obtain the triphenylphosphine sulfonate. Compared with the prior art, the method adopts the extracting agent with specific composition, and realizes the extraction of the triphenylphosphine sulfonate from the sulfonated product under specific process steps; the method has the advantages of simple process, mild conditions and strong overall operability, and meanwhile, the obtained triphenylphosphine sulfonate has few impurities, higher purity and high yield.
Description
Technical Field
The invention relates to the technical field of organic chemical industry, in particular to a method for extracting triphenylphosphine sulfonate from a sulfonated product.
Background
The ligand which is the most widely applied ligand in the oxo-synthesis reaction is Triphenylphosphine (TPP), and triphenylphosphine is used in the oxo-synthesis reaction, the reaction is a homogeneous reaction, and the catalyst and the product are difficult to separate, so that the deactivation and loss of the noble metal catalyst rhodium are easily caused. The method adopts a sulfonation process to sulfonate triphenylphosphine to form water-soluble triphenylphosphine sulfonate, and then forms a metal organic complex with noble metal rhodium for carbonyl synthesis reaction, so that the original homogeneous reaction heterogenization is an effective measure for solving the problems.
At present, the sulfonation conditions of triphenylphosphine are researched more, and the sulfonation of triphenylphosphine can be realized; however, the method for extracting triphenylphosphine sulfonate from sulfonated products is still imperfect, the extracted triphenylphosphine sulfonate has high impurity content and lower yield, and although some improved methods can improve the purity and yield of the products to a certain extent, the reaction is complex, the conditions are harsh, the products are easy to oxidize and deteriorate, and the operability is poor.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for extracting triphenylphosphine sulfonate from a sulfonated product, which has the advantages of simple process, mild conditions, strong overall operability, less impurities of the obtained triphenylphosphine sulfonate, high purity and high yield.
The invention provides a method for extracting triphenylphosphine sulfonate from a sulfonated product, which comprises the following steps:
a) adding water to dilute the sulfonated product until the concentration of sulfuric acid in the mixed solution is 1-5 mol/L, and then adding an extracting agent for extraction to obtain an organic phase; the extracting agent is a mixture of phosphate compounds and alkane compounds;
b) neutralizing the organic phase obtained in the step a) by using an alkaline solution, standing and separating to obtain a water phase containing triphenylphosphine sulfonate;
c) and c) sequentially carrying out crystallization, impurity removal, reduced pressure distillation and vacuum drying on the water phase containing the triphenylphosphine sulfonate obtained in the step b) to obtain the triphenylphosphine sulfonate.
Preferably, the sulfonated product in step a) is a mixed product after triphenylphosphine sulfonation; the preparation method of the sulfonated product comprises the following steps:
under the condition of stirring, adding 5-10 parts by weight of triphenylphosphine into 20-25 parts by weight of concentrated sulfuric acid, and then introducing 25-30 parts by weight of SO 3 Reacting for 60-80 h at 20-30 ℃ to obtain the mixed sulfonated product containing triphenylphosphine sulfonate.
Preferably, the mass fraction of the phosphate ester compound in the extracting agent in the step a) is 10-100%;
the phosphate ester compound is selected from one or more of triethyl phosphate, tributyl phosphate and tricresyl phosphate;
the alkane compound is selected from one or more of n-hexane, cyclohexane, n-heptane and n-octane.
Preferably, the dosage of the extracting agent in the step a) is 50-400% of the total mass of the mixed solution.
Preferably, the alkaline solution in step b) comprises one or more of aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, aqueous lithium hydroxide solution and aqueous ammonium hydroxide solution; the concentration of the alkaline solution is 1-5 mol/L.
Preferably, the pH value of the neutralization in the step b) is 7-9.
Preferably, the standing time in the step b) is 0.5 h-1.5 h.
Preferably, the crystallization and impurity removal process in the step c) specifically comprises the following steps:
crystallizing the water phase containing the triphenylphosphine sulfonate at the temperature of between 10 ℃ below zero and 30 ℃ for 0.5 to 24 hours, and removing impurities to obtain a liquid phase.
Preferably, the temperature of the reduced pressure distillation in the step c) is 45-95 ℃, and the vacuum degree is 0.04-0.09 MPa.
Preferably, the temperature of the vacuum drying in the step c) is 50-90 ℃, the vacuum degree is 0.04-0.09 MPa, and the time is 4-10 h.
The invention provides a method for extracting triphenylphosphine sulfonate from a sulfonated product, which comprises the following steps: a) adding water to dilute the sulfonated product until the concentration of sulfuric acid in the mixed solution is 1-5 mol/L, and then adding an extracting agent for extraction to obtain an organic phase; the extracting agent is a mixture of phosphate compounds and alkane compounds; b) neutralizing the organic phase obtained in the step a) by using an alkaline solution, standing and separating to obtain a water phase containing triphenylphosphine sulfonate; c) and c) sequentially carrying out crystallization, impurity removal, reduced pressure distillation and vacuum drying on the water phase containing the triphenylphosphine sulfonate obtained in the step b) to obtain the triphenylphosphine sulfonate. Compared with the prior art, the method adopts the extracting agent with specific composition, and realizes the extraction of the triphenylphosphine sulfonate from the sulfonated product under specific process steps; the method has the advantages of simple process, mild conditions and strong overall operability, and meanwhile, the obtained triphenylphosphine sulfonate has few impurities, higher purity and high yield. Experimental results show that the purity of the triphenylphosphine sulfonate obtained by the method provided by the invention is more than 98%, and the yield is more than 95%.
In addition, the method provided by the invention has the advantages of mild process conditions, difficult oxidation and deterioration of products, strong operability and wide application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for extracting triphenylphosphine sulfonate from a sulfonated product, which comprises the following steps:
a) adding water to dilute the sulfonated product until the concentration of sulfuric acid in the mixed solution is 1-5 mol/L, and then adding an extracting agent for extraction to obtain an organic phase; the extracting agent is a mixture of phosphate compounds and alkane compounds;
b) neutralizing the organic phase obtained in the step a) by using an alkaline solution, standing and separating to obtain a water phase containing triphenylphosphine sulfonate;
c) and c) sequentially carrying out crystallization, impurity removal, reduced pressure distillation and vacuum drying on the water phase containing the triphenylphosphine sulfonate obtained in the step b) to obtain the triphenylphosphine sulfonate.
The method comprises the steps of firstly adding water to dilute the sulfonated product until the concentration of sulfuric acid in the mixed solution is 1-5 mol/L, and then adding an extracting agent for extraction to obtain an organic phase. In the present invention, the sulfonation product is preferably a mixed product after sulfonation of triphenylphosphine, that is, a mixed sulfonation product containing triphenylphosphine sulfonate. In the present invention, the preparation method of the sulfonated product is preferably specifically:
under the condition of stirring, adding 5-10 parts by weight of triphenylphosphine into 20-25 parts by weight of concentrated sulfuric acid, and then introducing 25-30 parts by weight of SO 3 Reacting for 60-80 h at 20-30 ℃ to obtain a mixed sulfonated product containing triphenylphosphine sulfonate;
more preferably:
to 22.5 parts by weight of concentrated sulfuric acid, 7.5 parts by weight of triphenylphosphine were added with stirring, and the mixture was stirredThen 28 parts by weight of SO were introduced 3 Reacting for 70h at 25 ℃ to obtain a mixed sulfonated product containing triphenylphosphine sulfonate. The invention treats the concentrated sulfuric acid, the triphenylphosphine and the SO 3 The source of (A) is not particularly limited, and commercially available products or self-products known to those skilled in the art may be used. Triphenylphosphine in concentrated sulfuric acid through SO 3 After sulfonation, the mixed product contains a large amount of sulfuric acid and SO in addition to triphenylphosphine sulfonate 3 The mass content of the triphenylphosphine sulfonate is usually over 70 percent, and concentrated sulfuric acid has strong corrosivity, so that the extraction of the triphenylphosphine sulfonate is difficult.
The method comprises the steps of firstly adding water to dilute the sulfonated product until the concentration of sulfuric acid in the mixed solution is 1-5 mol/L, preferably 2.5-5 mol/L.
In the invention, the extracting agent is a mixture of phosphate compounds and alkane compounds; among them, the mass fraction of the phosphate ester compound is preferably 10% to 100%, more preferably 30% to 70%.
In the present invention, the phosphate ester-based compound is preferably selected from one or more of triethyl phosphate, tributyl phosphate, and tricresyl phosphate, more preferably triethyl phosphate, tributyl phosphate, or tricresyl phosphate; the alkane compound is preferably selected from one or more of n-hexane, cyclohexane, n-heptane and n-octane, more preferably n-octane, n-heptane or cyclohexane. In a preferred embodiment of the present invention, the extracting agent is a mixture of 1: 2 triethyl phosphate and n-octane; in another preferred embodiment of the present invention, the extracting agent is a mixture of 1: 1 tributyl phosphate and n-heptane; in another preferred embodiment of the present invention, the mass ratio of the extracting agent is 32: 17 tricresyl phosphate and cyclohexane; in another preferred embodiment of the present invention, the mass ratio of the extracting agent is 36: 23 tributyl phosphate and cyclohexane. The source of the phosphate ester compound and the alkane compound is not particularly limited in the present invention, and commercially available products or self-prepared products known to those skilled in the art may be used.
In the present invention, the amount of the extractant used is preferably 50% to 400% of the total mass of the mixed solution, more preferably 60% to 150% of the total mass of the mixed solution, and even more preferably 80% to 125% of the total mass of the mixed solution.
The extraction process is not particularly limited, and the technical scheme of extracting by using an extracting agent, which is well known to those skilled in the art, can be adopted; and obtaining an organic phase after extraction and further carrying out subsequent treatment.
After the organic phase is obtained, the obtained organic phase is neutralized by alkaline solution, and the water phase containing the triphenylphosphine sulfonate is obtained by separation after standing. In the present invention, the alkaline solution preferably includes one or more of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous lithium hydroxide solution, and an aqueous ammonium hydroxide solution, more preferably an aqueous sodium hydroxide solution; the concentration of the alkaline solution is preferably 1 to 5mol/L, and more preferably 3 to 5 mol/L.
In the present invention, the neutralization process is preferably specifically:
under the condition of stirring, neutralizing the extracted organic phase by using an alkaline solution until the pH value of the water phase is between 7 and 9, and finishing neutralization;
more preferably:
and under the condition of stirring, neutralizing the extracted organic phase by adopting an alkaline solution until the pH value of the water phase is between 7 and 8, and finishing neutralization. During the above neutralization process, the triphenylphosphine sulfonate is converted into triphenylphosphine sulfonate and transferred to the aqueous phase.
In the invention, because the neutralized product can form oil and water phases, the standing process is adopted to play an important role in obtaining a water phase containing triphenylphosphine sulfonate through subsequent separation; the standing time is preferably 0.5h to 1.5h, and more preferably 1 h.
After the water phase containing the triphenylphosphine sulfonate is obtained, the obtained water phase containing the triphenylphosphine sulfonate is subjected to crystallization, impurity removal, reduced pressure distillation and vacuum drying in sequence to obtain the triphenylphosphine sulfonate. In the present invention, the crystallization and impurity removal process preferably includes:
crystallizing the water phase containing triphenylphosphine sulfonate at-10-30 ℃ for 0.5-24 h, and removing impurities to obtain a liquid phase;
more preferably:
crystallizing the water phase containing the triphenylphosphine sulfonate at 10-20 ℃ for 10-15 h, and removing impurities to obtain a liquid phase.
The invention carries out reduced pressure distillation on the liquid phase after crystallization and impurity removal to remove liquid, and the obtained solid is the crude product of the triphenylphosphine sulfonate. In the invention, the temperature of the reduced pressure distillation is preferably 45-95 ℃, and more preferably 50-95 ℃; the degree of vacuum of the reduced pressure distillation is preferably 0.04 to 0.09MPa, more preferably 0.06 to 0.09 MPa. In the invention, because the liquid phase contains a small amount of organic matters with lower boiling points, in the reduced pressure distillation process, in order to prevent bumping, the distillation temperature and the vacuum degree in the early stage are lower, and the distillation temperature and the vacuum degree in the later stage are higher; reduced pressure distillation is generally carried out by slowly increasing the temperature and the vacuum.
The invention adopts vacuum drying to further remove impurities such as water content and the like, and the obtained solid product is the triphenylphosphine sulfonate. In the present invention, the temperature of the vacuum drying is preferably 50 ℃ to 90 ℃, and more preferably 65 ℃; the vacuum degree of the vacuum drying is preferably 0.04MPa to 0.09MPa, and more preferably 0.09 MPa; the time for vacuum drying is preferably 4 to 10 hours, and more preferably 6 hours.
The method adopts an extracting agent with a specific composition, and realizes extraction of triphenylphosphine sulfonate from a sulfonated product under specific process steps of (dilution of the sulfonated product, extraction, neutralization, standing separation, crystallization and impurity removal, reduced pressure distillation and vacuum drying); the method has the advantages of simple process, mild conditions and strong overall operability, and meanwhile, the obtained triphenylphosphine sulfonate has few impurities, higher purity and high yield. In addition, the method provided by the invention has the advantages of mild process conditions, difficult oxidative deterioration of the product, strong operability and wide application prospect.
The invention provides a method for extracting triphenylphosphine sulfonate from a sulfonated product, which comprises the following steps: a) adding water to dilute the sulfonated product until the concentration of sulfuric acid in the mixed solution is 1-5 mol/L, and then adding an extracting agent for extraction to obtain an organic phase; the extracting agent is a mixture of phosphate compounds and alkane compounds; b) neutralizing the organic phase obtained in the step a) by using an alkaline solution, standing and separating to obtain a water phase containing triphenylphosphine sulfonate; c) and c) sequentially carrying out crystallization, impurity removal, reduced pressure distillation and vacuum drying on the water phase containing the triphenylphosphine sulfonate obtained in the step b) to obtain the triphenylphosphine sulfonate. Compared with the prior art, the method adopts the extracting agent with specific composition, and realizes the extraction of the triphenylphosphine sulfonate from the sulfonated product under specific process steps; the method has the advantages of simple process, mild conditions and strong overall operability, and meanwhile, the obtained triphenylphosphine sulfonate has few impurities, higher purity and high yield. Experimental results show that the purity of the triphenylphosphine sulfonate obtained by the method provided by the invention is more than 98%, and the yield is more than 95%.
In addition, the method provided by the invention has the advantages of mild process conditions, difficult oxidative deterioration of the product, strong operability and wide application prospect.
To further illustrate the present invention, the following examples are provided for illustration. The sulfonation product used in the following examples of the present invention is specifically a mixed product obtained by sulfonating triphenylphosphine, and the obtaining manner (sulfonation experiment) is as follows:
7.5 parts by weight of triphenylphosphine were added to 22.5 parts by weight of concentrated sulfuric acid with stirring, and 28 parts by weight of SO were introduced 3 Reacting at room temperature for 70h to obtain a mixed sulfonated product containing triphenylphosphine sulfonate; the composition contents of each substance are shown in table 1 below.
TABLE 1 composition and content of individual substances in the mixed sulfonated products containing triphenylphosphine sulfonate
| Composition of matter | Content/% |
| Sulfuric acid | 38.79 |
| SO 3 | 36.69 |
| Sulfonated product of triphenylphosphine | 24.52 |
Example 1
Taking 7.5g of triphenylphosphine as an example, the sulfonation experiment is adopted to obtain a mixed sulfonation product (58 g of the total mass) containing triphenylphosphine sulfonate as a sulfonation product; adding 80g of deionized water into the sulfonated product, diluting until the concentration of sulfuric acid in the mixture is 5mol/L, then weighing 50g of triethyl phosphate and 100g of n-octane, adding the triethyl phosphate and the n-octane into the solution for extraction, neutralizing the extracted organic phase with 5mol/L of NaOH solution under the stirring condition until the pH value of the water phase is between 7 and 8, and standing for 1h after the neutralization is finished; then separating to obtain a water phase, and crystallizing for 12 hours at 15 ℃; then removing impurities to obtain a liquid phase, carrying out reduced pressure distillation at the temperature of 50-95 ℃ and the vacuum degree of 0.06-0.09 MPa, and removing the liquid phase to obtain a solid product; finally, vacuum drying is carried out for 6h under the conditions of 65 ℃ and the vacuum degree of 0.09MPa, and 15.94g of solid product (triphenylphosphine sulfonate) is obtained.
Through liquid mass analysis, the product purity is 98.5%, and the yield is 98.1% (the calculation method of the product yield is that the obtained solid product is called m mass 1 And the purity of the product is n by liquid chromatography 1 Theoretically, a product mass of m can be obtained 2 Yield Y ═ m 1 ×n 1 /m 2 )×100％)。
Example 2
Taking 7.5g of triphenylphosphine as an example, the sulfonation experiment is adopted to obtain a mixed sulfonation product (58 g of the total mass) containing triphenylphosphine sulfonate as a sulfonation product; adding 125g of deionized water into the sulfonated product, diluting until the sulfuric acid concentration in the mixture is 3.5mol/L, then weighing 75g of tributyl phosphate and 75g of n-heptane, adding the tributyl phosphate and the n-heptane into the solution for extraction, neutralizing the extracted organic phase with 3mol/L NaOH solution under the stirring condition until the pH value of the water phase is 7-8, and standing for 1h after the neutralization is completed; then separating to obtain a water phase, and crystallizing for 12 hours at 15 ℃; then removing impurities to obtain a liquid phase, carrying out reduced pressure distillation at the temperature of 50-95 ℃ and the vacuum degree of 0.06-0.09 MPa, and removing the liquid phase to obtain a solid product; finally, vacuum drying is carried out for 6h under the conditions of 65 ℃ and 0.09MPa of vacuum degree, and 15.69g of solid product (triphenylphosphine sulfonate) is obtained.
Through liquid mass analysis, the purity of the product is 99.0 percent, and the yield is 96.6 percent.
Example 3
Taking 7.5g of triphenylphosphine as an example, the sulfonation experiment is adopted to obtain a mixed sulfonation product (58 g of the total mass) containing triphenylphosphine sulfonate as a sulfonation product; adding 180g of deionized water into the sulfonated product, diluting until the sulfuric acid concentration in the mixture is 2.5mol/L, then weighing 160g of tricresyl phosphate and 85g of cyclohexane, adding the weighed tricresyl phosphate and the 85g of cyclohexane into the solution for extraction, neutralizing the extracted organic phase with 3mol/L NaOH solution under the stirring condition until the pH value of the aqueous phase is between 7 and 8, and standing for 1h after the neutralization is finished; then separating to obtain a water phase, and crystallizing for 12 hours at 15 ℃; then removing impurities to obtain a liquid phase, carrying out reduced pressure distillation at the temperature of 50-95 ℃ and the vacuum degree of 0.06-0.09 MPa, and removing the liquid phase to obtain a solid product; finally, vacuum drying is carried out for 6h under the conditions of 65 ℃ and the vacuum degree of 0.09MPa, and 15.52g of a solid product (triphenylphosphine sulfonate) is obtained.
Through liquid mass analysis, the purity of the product is 99.1 percent, and the yield is 95.5 percent.
Example 4
Taking 7.5g of triphenylphosphine as an example, the sulfonation experiment is adopted to obtain a mixed sulfonation product (58 g of the total mass) containing triphenylphosphine sulfonate as a sulfonation product; adding 180g of deionized water into the sulfonated product, diluting until the sulfuric acid concentration in the mixture is 2.5mol/L, then weighing 180g of tributyl phosphate and 115g of cyclohexane, adding the weighed tributyl phosphate and cyclohexane into the solution for extraction, neutralizing the extracted organic phase with 3mol/L of NaOH solution under the stirring condition until the pH value of the aqueous phase is between 7 and 8, and standing for 1h after the neutralization is finished; then separating to obtain a water phase, and crystallizing for 12 hours at 15 ℃; then removing impurities to obtain a liquid phase, carrying out reduced pressure distillation at the temperature of 50-95 ℃ and the vacuum degree of 0.06-0.09 MPa, and removing the liquid phase to obtain a solid product; finally, vacuum drying is carried out for 6h under the conditions of 65 ℃ and the vacuum degree of 0.09MPa, and 15.68g of solid product (triphenylphosphine sulfonate) is obtained.
Through liquid mass analysis, the purity of the product is 98.8%, and the yield is 96.5%.
Comparative example 1
Taking 7.5g of triphenylphosphine as an example, the sulfonation experiment is adopted to obtain a mixed sulfonation product (58 g of the total mass) containing triphenylphosphine sulfonate as a sulfonation product; adding 60g of deionized water into the sulfonated product, diluting until the sulfuric acid concentration in the mixture is 6.5mol/L, then weighing 25g of tributyl phosphate and 25g of cyclohexane, adding the weighed tributyl phosphate and cyclohexane into the solution for extraction, neutralizing the extracted organic phase with 3mol/L NaOH solution under the stirring condition until the pH value of the aqueous phase is between 7 and 8, and standing for 1h after the neutralization is finished; then separating to obtain a water phase, and crystallizing for 12 hours at 15 ℃; then removing impurities to obtain a liquid phase, carrying out reduced pressure distillation at the temperature of 50-95 ℃ and the vacuum degree of 0.06-0.09 MPa, and removing the liquid phase to obtain a solid product; finally, vacuum drying is carried out for 6h under the conditions of 65 ℃ and 0.09MPa of vacuum degree, and 12.97g of solid product (triphenylphosphine sulfonate) is obtained.
Through liquid mass analysis, the product purity is 97.6%, and the yield is 78.7%.
The conditions and results of examples 1 to 4 and comparative example 1 are shown in Table 2 below.
TABLE 2 Condition and result data for examples 1-4 and comparative example 1
As can be seen from Table 2, the method for extracting triphenylphosphine sulfonate from sulfonated products provided by the invention has the advantages of less triphenylphosphine sulfonate impurities, higher purity, high yield, better operability and wide application prospect.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for extracting triphenylphosphine sulfonate from sulfonated products comprises the following steps:
a) adding water to dilute the sulfonated product until the concentration of sulfuric acid in the mixed solution is 1-5 mol/L, and then adding an extracting agent for extraction to obtain an organic phase; the sulfonated product is a mixed product after triphenylphosphine sulfonation; the preparation method of the sulfonated product comprises the following steps:
under the condition of stirring, adding 5-10 parts by weight of triphenylphosphine into 20-25 parts by weight of concentrated sulfuric acid, and then introducing 25-30 parts by weight of SO 3 Reacting for 60-80 h at 20-30 ℃ to obtain a mixed sulfonated product containing triphenylphosphine sulfonate; the extracting agent is a mixture of phosphate compounds and alkane compounds; the mass fraction of the phosphate ester compound in the extracting agent is 30-70%;
the phosphate ester compound is selected from one or more of triethyl phosphate, tributyl phosphate and tricresyl phosphate;
the alkane compound is selected from one or more of n-hexane, cyclohexane, n-heptane and n-octane;
b) neutralizing the organic phase obtained in the step a) by adopting an alkaline solution, standing and separating to obtain a water phase containing triphenylphosphine sulfonate;
c) and c) sequentially carrying out crystallization, impurity removal, reduced pressure distillation and vacuum drying on the water phase containing the triphenylphosphine sulfonate obtained in the step b) to obtain the triphenylphosphine sulfonate.
2. The method for extracting triphenylphosphine sulfonate from sulfonated products according to claim 1, wherein the amount of the extractant used in step a) is 50-400% of the total mass of the mixed solution.
3. The method for extracting triphenylphosphine sulfonate from sulfonated products according to claim 1, wherein the alkaline solution in step b) comprises one or more of aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, aqueous lithium hydroxide solution and aqueous ammonium hydroxide solution; the concentration of the alkaline solution is 1-5 mol/L.
4. The method for extracting triphenylphosphine sulfonate from sulfonated products according to claim 1, wherein the pH value of neutralization in step b) is 7-9.
5. The method for extracting triphenylphosphine sulfonate from sulfonated products according to claim 1, wherein the standing time in step b) is 0.5-1.5 h.
6. The method for extracting triphenylphosphine sulfonate from sulfonated products according to claim 1, wherein the crystallization and impurity removal process in step c) is specifically as follows:
crystallizing the water phase containing the triphenylphosphine sulfonate at-10-30 ℃ for 0.5-24 h, and removing impurities to obtain a liquid phase.
7. The method for extracting triphenylphosphine sulfonate from sulfonated products according to claim 1, wherein the temperature of reduced pressure distillation in step c) is 45 ℃ to 95 ℃, and the vacuum degree is 0.04MPa to 0.09 MPa.
8. The method for extracting triphenylphosphine sulfonate from sulfonated products according to claim 1, wherein the temperature of vacuum drying in step c) is 50-90 ℃, the vacuum degree is 0.04-0.09 MPa, and the time is 4-10 h.
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