CN104402923A - One-step synthesis method of dialkylphosphinic acid mixture - Google Patents
One-step synthesis method of dialkylphosphinic acid mixture Download PDFInfo
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- CN104402923A CN104402923A CN201410652534.2A CN201410652534A CN104402923A CN 104402923 A CN104402923 A CN 104402923A CN 201410652534 A CN201410652534 A CN 201410652534A CN 104402923 A CN104402923 A CN 104402923A
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Abstract
The invention discloses a one-step synthesis method of dialkylphosphinic acid mixture. The one-step synthesis method comprises the steps as follows: diisobutylene and hypophosphorous acid solution are taken as raw materials; addition reaction is initiated through ultraviolet light at low temperature, wherein the molar percentage content of bi(1,1,3,3-tetramethylbutyl) phosphinic acid in a purified product is greater than 10 percent; except bi(2,2,4-trimethylpentyl) phosphinic acid and bi(1,1,3,3-tetramethylbutyl) phosphinic acid, the molar percentage content of other phosphorus compounds is lower than 1 percent. The one-step synthesis method has the advantages and positive effects that the production process is safe in technology, simple in procedures, low in cost, easy to control, high in efficiency and low in pollution, and solves the limitation of single use of bi(2,2,4-trimethylpentyl) phosphinic acid or bi(1,1,3,3-tetramethylbutyl) phosphinic acid in industrial application.
Description
Technical field
The invention belongs to organic chemical synthesis technical field, particularly a kind of one-step synthesis of dialkyl phosphinic acid mixture.
Background technology
United States Patent (USP) 4374780 discloses the synthetic method of two (2,4,4-tri-methyl-amyl) phospho acid (trade(brand)name Cyanex 272) and reports that this compound is widely used in cobalt, nickel from sulphur or subchloride medium and is separated.In this patent, RobertsonA.J. adopts free radical to cause addition, the reaction of hydrogen peroxide oxidation two-step approach, obtains two (2,4,4-tri-methyl-amyl) phospho acid.Under reaction pressure is 2.0-4.9 Mpa condition, be initiator with Diisopropyl azodicarboxylate, only have 2,4,4-2,4,4-Trimethyl-1-pentene-1 and phosphuret-(t)ed hydrogen generation addition reaction, then utilize hydrogen peroxide that intermediate product oxidation is generated target compound.Main containing two (2 in this product, 4,4-tri-methyl-amyl) phospho acid, list (2,4,4-tri-methyl-amyl) phospho acid and three (2,4,4-tri-methyl-amyl) phospho acid, the product only containing two (2,4,4-tri-methyl-amyl) phospho acid is obtained after purifying.In actual applications, Cyanex 272 has certain limitation and defect, and namely Cyanex 272 can become thickness gradually and be difficult to use, the 70-75% of maximum its theoretical maximum ability of load in technological process after Supported Co.United States Patent (USP) 5925784 discloses two (1,1,3,3-tetramethyl butyl) synthetic method of phospho acid, report this compound to separation of cobalt, nickel, there is good performance and practical application time carrying capacity can reach 100%, be two (2,4,4-tri-methyl-amyl) the good substitute products of phospho acid, this invention with phosphuret-(t)ed hydrogen and diisobutylene for raw material, by acid catalysis addition, hydrogen peroxide oxidation two-step approach preparation two (1,1,3,3-tetramethyl butyl) phospho acid.But some attribute of pure two (1,1,3,3-tetramethyl butyl) phospho acid limits its industrial application: as, be solid under room temperature, in conventional aromatic series and aliphatic solvent, solubleness is limited.According to two (1,1,3,3-tetramethyl butyl) phospho acid characteristic that room temperature is dissolved each other in two (2,4,4-tri-methyl-amyl) phospho acid, be expected to both utilizations and coexist and the solution foregoing problems that acts synergistically.As known from the above, reported two (2,4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) synthetic method of phospho acid is different, and being two-step synthesis, therefore invention one comprises two (2,4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) one-step synthesis of mixture of phospho acid is significant.
Summary of the invention
The invention provides a kind of one-step synthesis of dialkyl phosphinic acid mixture, namely one comprises two (2,4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) one-step synthesis of mixture of phospho acid is production technique of a kind of high efficiency, low cost.
Technical scheme of the present invention:
With diisobutylene and Hypophosporous Acid, 50 solution for raw material, utilize UV-light to cause synthesis one under low temperature and comprise two (2,4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) single stage method of mixture of phospho acid, comprise the steps:
Diisobutylene is mixed with Hypophosporous Acid, 50 solution and fully stirs, ultra violet lamp is utilized to carry out addition reaction 15-30h under cryogenic, one-step synthesis method comprises two (2,4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) the thick product of mixture of phospho acid, by thick product after alkali cleaning, acidifying and distilation, obtain light yellow liquid product.
The weight percent concentration of described Hypophosporous Acid, 50 solution is 30-90%.
The amount ratio of described diisobutylene and sodium hypophosphite solution is 0.1 ~ 10ml: 1g.
Described addition reaction temperature is 30-80 DEG C.
Described ultraviolet lamp power is 50 ~ 500W.
Described soda-wash solution is weight percentage the NaOH solution of concentration 1-40% or Na
2sO
4solution.
Described souring soln is sulfuric acid, hydrochloric acid or nitric acid, and the weight percent concentration of souring soln is 1-36%, and the volume ratio of souring soln and thick product is 1: 0.005-10.
The processing parameter of described distillation: pressure is-0.1 ~-0.01MPa, and temperature is 60-300 DEG C.
Comprise two (2 in described light yellow liquid product simultaneously, 4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) phospho acid, wherein two (1,1,3,3-tetramethyl butyl) molar content of phospho acid is greater than 10%, and other P contained compound molar content is lower than 1%.
Advantage of the present invention and positively effect: this production technique comprises two (2 by one-step synthesis method one under low-temperature atmosphere-pressure, 4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) mixture of phospho acid, production process has process safety, step is simple, cost is low, easy to control, efficiency is high and pollute the advantages such as few.
Embodiment
Below in conjunction with embodiment, the present invention is further described, but they are not impose any restrictions the present invention.Here only point out, the reagent used in the present invention and testing apparatus, except indicating the source especially, are the commercially available universal product.
Embodiment 1:
An one-step synthesis for dialkyl phosphinic acid mixture, with diisobutylene and Hypophosporous Acid, 50 solution for raw material, utilize UV-light cause addition reaction and synthesize under low temperature, operation steps is as follows:
200ml diisobutylene is mixed with the Hypophosporous Acid, 50 solution (60%w/w) of 300g and fully stirs, be heated to 60 DEG C, 20h is reacted under 100 W ultra violet lamps, obtain and comprise two (2,4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) the thick product of mixture of phospho acid; Get 50ml thick product 20ml NaOH solution (5%w/w) and carry out alkali cleaning 2 times; Then 15ml sulphuric acid soln (10%w/w) is used to carry out acidifying; Finally the thick product after acidifying is carried out vacuum distillation under-0.8MPa and 100 DEG C condition, namely obtain light yellow liquid product.
The detection of product:
Pass through
31p-NMR analyzes, and product composition (molar content) is as follows:
Two (2,4,4-tri-methyl-amyl) Hypophosporous Acid, 50 85.4%,
Two (1,1,3,3-tetramethyl butyl) phospho acid 13.6%,
Other P contained compound < 1%.
Embodiment 2:
An one-step synthesis for dialkyl phosphinic acid mixture, with diisobutylene and Hypophosporous Acid, 50 solution for raw material, utilize UV-light cause addition reaction and synthesize under low temperature, operation steps is as follows:
200ml diisobutylene is mixed with the Hypophosporous Acid, 50 solution (80%w/w) of 300g and fully stirs, be heated to 50 DEG C, 20h is reacted under 200W ultra violet lamp, obtain and comprise two (2,4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) the thick product of mixture of phospho acid; Get 50ml thick product 20ml Na
2sO
4solution (8%w/w) carries out alkali cleaning 2 times; Then 15ml hydrochloric acid soln (30%w/w) is used to carry out acidifying; Finally the thick product after acidifying is carried out vacuum distillation under-0.8MPa and 100 DEG C condition, namely obtain light yellow liquid product.
The detection of product:
Pass through
31p-NMR analyzes, and product composition (molar content) is as follows:
Two (2,4,4-tri-methyl-amyl) Hypophosporous Acid, 50 80.5%,
Two (1,1,3,3-tetramethyl butyl) phospho acid 18.5%,
Other P contained compound < 1%.
Embodiment 3:
An one-step synthesis for dialkyl phosphinic acid mixture, with diisobutylene and Hypophosporous Acid, 50 solution for raw material, utilize UV-light cause addition reaction and synthesize under low temperature, operation steps is as follows:
300ml diisobutylene is mixed with the Hypophosporous Acid, 50 solution (90%w/w) of 300g and fully stirs, be heated to 80 DEG C, 15h is reacted under 500W ultra violet lamp, obtain and comprise two (2,4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) the thick product of mixture of phospho acid; Get 50ml thick product 20ml NaOH solution (10%w/w) and carry out alkali cleaning 2 times; Then 15ml sulphuric acid soln (20%w/w) is used to carry out acidifying; Finally the thick product after acidifying is carried out vacuum distillation under-0.8MPa and 100 DEG C condition, namely obtain light yellow liquid product.
The detection of product:
Pass through
31p-NMR analyzes, and product composition (molar content) is as follows:
Two (2,4,4-tri-methyl-amyl) Hypophosporous Acid, 50 71.2%,
) two (1,1,3,3-tetramethyl butyl) phospho acid 27.8%,
Other P contained compound < 1%.
The present invention discloses a kind of one-step synthesis of dialkyl phosphinic acid mixture, those skilled in the art are by using for reference present disclosure, the links such as appropriate change operational path realize, although method of the present invention is described by preferred embodiment, person skilled obviously can change method as herein described or reconfigure not departing from content of the present invention and scope, realizes net result.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are all deemed to be included in content of the present invention and scope.
Claims (4)
1. an one-step synthesis for dialkyl phosphinic acid mixture, is characterized in that: with diisobutylene and Hypophosporous Acid, 50 solution for raw material, utilizes UV-light to cause addition reaction, realize one-step synthesis method and obtain target product under low temperature.Concrete operation step is as follows:
Diisobutylene is mixed with Hypophosporous Acid, 50 solution and fully stirs, ultra violet lamp is utilized to carry out addition reaction 15-30h under cryogenic, one-step synthesis method comprises two (2,4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) mix product of phospho acid, then after alkali cleaning, acidifying and distilation, obtain light yellow liquid product.
2. the one-step synthesis of dialkyl phosphinic acid mixture according to claim 1, is characterized in that: the weight percent concentration of described Hypophosporous Acid, 50 solution is 30-90%.
3. the one-step synthesis of dialkyl phosphinic acid mixture according to claim 1, it is characterized in that: in light yellow liquid product, comprise two (2 simultaneously, 4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) phospho acid, wherein two (1,1,3,3-tetramethyl butyl) molar content of phospho acid is greater than 10%.
4. the one-step synthesis of dialkyl phosphinic acid mixture according to claim 1, it is characterized in that: except two (2 in light yellow liquid product, 4,4-tri-methyl-amyl) phospho acid and two (1,1,3,3-tetramethyl butyl) other phosphorus compound molar content beyond phospho acid is lower than 1%.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4632741A (en) * | 1984-09-06 | 1986-12-30 | Economics Laboratory, Inc. | Synthesis of alkyl phosphinate salts and bis(alkyl) phosphinate salts |
| US5872279A (en) * | 1995-03-07 | 1999-02-16 | Nippon Chemical Industrial Co., Ltd. | Bis(1,1,3,3-tetramethylbutyl) phosphinic acid compound, a production method thereof and an extracting agent |
| US20090165598A1 (en) * | 2006-06-14 | 2009-07-02 | Yuehui Zhou | Novel phosphinic acids and their sulfur derivatives and methods for their preparation |
| CN101891762A (en) * | 2010-06-30 | 2010-11-24 | 南开大学 | Preparation method and application of diethyl phosphinates |
| CN102372740A (en) * | 2011-12-06 | 2012-03-14 | 南开大学 | Preparation method for di(2,4,4-trimethyl pentyl) hypophosphorous acid |
| CN102746334A (en) * | 2012-07-13 | 2012-10-24 | 南开大学 | Preparation method of diisobutyl phosphinic acid aluminum |
| CN103613613A (en) * | 2013-11-08 | 2014-03-05 | 常熟新特化工有限公司 | Preparation method of dialkyl sodium hypophosphite |
| CN103772429A (en) * | 2014-01-16 | 2014-05-07 | 常熟新特化工有限公司 | Method for preparing bis(2,4,4-trimethylpentyl) phosphinic acid from hydrogen phosphide as byproduct in sodium hypophosphite production process |
-
2014
- 2014-11-14 CN CN201410652534.2A patent/CN104402923A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4632741A (en) * | 1984-09-06 | 1986-12-30 | Economics Laboratory, Inc. | Synthesis of alkyl phosphinate salts and bis(alkyl) phosphinate salts |
| US5872279A (en) * | 1995-03-07 | 1999-02-16 | Nippon Chemical Industrial Co., Ltd. | Bis(1,1,3,3-tetramethylbutyl) phosphinic acid compound, a production method thereof and an extracting agent |
| US20090165598A1 (en) * | 2006-06-14 | 2009-07-02 | Yuehui Zhou | Novel phosphinic acids and their sulfur derivatives and methods for their preparation |
| CN101891762A (en) * | 2010-06-30 | 2010-11-24 | 南开大学 | Preparation method and application of diethyl phosphinates |
| CN102372740A (en) * | 2011-12-06 | 2012-03-14 | 南开大学 | Preparation method for di(2,4,4-trimethyl pentyl) hypophosphorous acid |
| CN102746334A (en) * | 2012-07-13 | 2012-10-24 | 南开大学 | Preparation method of diisobutyl phosphinic acid aluminum |
| CN103613613A (en) * | 2013-11-08 | 2014-03-05 | 常熟新特化工有限公司 | Preparation method of dialkyl sodium hypophosphite |
| CN103772429A (en) * | 2014-01-16 | 2014-05-07 | 常熟新特化工有限公司 | Method for preparing bis(2,4,4-trimethylpentyl) phosphinic acid from hydrogen phosphide as byproduct in sodium hypophosphite production process |
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Application publication date: 20150311 |