CN102268038A - Method for synthesizing bis(2,4,4-trimethylpentyl) phosphinic acid with double initiators - Google Patents

Abstract

The invention relates to a method for synthesizing bis(2,4,4-trimethylpentyl) phosphinic acid. The method adopts sodium hypophosphite and diisobutylene as the raw materials, and employs 2, 2'-azobis(2-methylpropionamidine) dihydrochloride and hydrogen peroxide as the radical initiators. With the steps of heating under violent stirring, a period of reaction at a constant temperature, liquid separation, organic phase washing, and vacuum distillation, the object product bis(2,4,4-trimethylpentyl) phosphinic acid can be obtained. The method provided in the invention has the advantages of short reaction time, high conversion rate, simple post-treatment method and atmospheric reaction, etc.

Description

The method of synthetic two (2,4, the 4-tri-methyl-amyl) phospho acid of a kind of dual initiator

Technical field

The present invention relates to a kind of method of synthetic two (2,4, the 4-tri-methyl-amyl) phospho acid.

Technical background

Two (2,4, the 4-tri-methyl-amyl) phospho acid are extraction agents of a kind of acid non-ferrous metal, performance excellence aspect the separation of cobalt nickel, and its structure is as follows:

The synthetic method of two (2,4, the 4-tri-methyl-amyl) phospho acid has multiple, the method that is reoxidized by diisobutylene and phosphuret-(t)ed hydrogen free radical addition of first United States Patent (USP) 4374780 (1983) report:

This method is a two-step reaction, and raw material comprises poisonous, inflammable phosphine gas and strong oxidizer hydrogen peroxide, and equipment and personnel protection are had relatively high expectations, and is unfavorable for large-scale industrial production.

Another is the single stage method by diisobutylene and Hypophosporous Acid, 50 free radical addition of United States Patent (USP) 2006089508 (2006) reports, used initiator is single, can be Diisopropyl azodicarboxylate, benzoyl peroxide, ditertiary butyl peroxide, hydrogen peroxide and sodium carbonate peroxide etc.

This method is generally carried out in autoclave, need in 30 hours, feed the solution of initiator in the reaction process continuously with volume pump, contain 75.3% target product and single substitution product of 12.1% in the product, need purification processes such as further alkali cleaning acidifying, operate consuming timely, loaded down with trivial details, need a large amount of acidic and alkaline waste water of discharging.

CN200810246571 is mixed in proportion sodium hypophosphite, acid, alpha-olefin, adds low temperature or middle temperature type free base initiator and high temperature type free base initiator again, synthetic dialkyl hypophosphorous acid in autoclave.This method need not the alkali cleaning acidifying, has reduced the acidic and alkaline waste water discharging, still needs finish in autoclave but react, and plant and instrument is had relatively high expectations.

Summary of the invention

The present invention aims to provide a kind of method of not having two (2,4, the 4-tri-methyl-amyl) phospho acid of normal pressure synthesis that acidic and alkaline waste water discharges, yield is high.

In view of sodium hypophosphite in the reaction process is to be dissolved in the acetate, and experimental observation is lower to the solubleness of diisobutylene in acetate, and reaction mainly takes place on the interface, so the present invention adopts under the vigorous stirring situation synthetic method of diradical initiator.

By a large amount of experiments, we comform and have found that the combination of two kinds of radical initiators has outstanding effect in the polyradical initiator: a kind of initiator is an azo diisobutyl amidine hydrochloride, different with the azonitrile series products, because of its nitrile group-containing not, degradation production is nontoxic, more steady than other decomposition of initiator simultaneously, the transformation efficiency height, residue and caking do not appear in polymerization process; Another kind of initiator is a hydrogen peroxide, can dissolve each other with acetate, and efficiency of initiation is higher like this, and reaction conditions is therefore more gentle.By the combination of these two kinds of initiators, the reaction times shortens greatly, the more important thing is in condition of normal pressure and can obtain high yield, has obtained beyond thought effect.

Specifically, the present invention realizes by following technical proposal:

A kind of method of synthetic two (2,4, the 4-tri-methyl-amyl) phospho acid comprises the following step:

1) sodium hypophosphite is dissolved in the acetate, adds diisobutylene, in above-mentioned solution, add radical initiator azo diisobutyl amidine hydrochloride and hydrogen peroxide then, be heated to 60-100 ℃ under the vigorous stirring, normal pressure isothermal reaction 3 ~ 5h;

The mol ratio of diisobutylene and sodium hypophosphite is not less than 5, and the mol ratio of acetate and sodium hypophosphite is not less than 1; The mol ratio of azo diisobutyl amidine hydrochloride and sodium hypophosphite is not less than 0.5, and the mol ratio of azo diisobutyl amidine hydrochloride and sodium hypophosphite is not less than 0.5;

2) leave standstill, separatory, the washing organic phase gets two (2,4, the 4-tri-methyl-amyl) phospho acid of target product after the vacuum distilling.

In order to reach better technique effect, the mol ratio of sodium hypophosphite, diisobutylene, acetate, azo diisobutyl amidine hydrochloride and hydrogen peroxide is 1:5～10:1.2～1.5:0.5:0.5.

Above process can be schematically as follows:

Present method is compared with previous methods, has advantage such as do not need pressurization, the reaction times is short, transformation efficiency is high, product purity is high, degradation production is nontoxic and post-treating method is simple.

Embodiment

Example 1

In being housed, the 500mL four-hole bottle of mechanical stirring, thermometer and reflux condensing tube adds 25.0g (0.28mol) sodium hypophosphite, 25.0g acetate and 209.5g (containing alpha-olefin 1.40mol) diisobutylene (alpha-olefin content is 75%) successively, add the hydrogen peroxide of 37.9g (0.14mol) azo diisobutyl amidine hydrochloride and 15.9g (0.14mol) 30%, be heated to 60 ℃ under the vigorous stirring.Behind the isothermal reaction 3h, reduce to room temperature, standing demix is told aqueous lower floor solution.The upper solution washing adds 100mL deionization washing 3 times.β-alkene and a small amount of unreacted alpha-olefin are removed in underpressure distillation, get two (2,4, the 4-tri-methyl-amyl) the phospho acid 63.6g of product, yield 78.2%.Warp ³¹The P-NMR assay products consists of:

Two (2,4, the 4-tri-methyl-amyl) phospho acid 81.6% of target product

Single substituent 2,4,4-tri-methyl-amyl phosphonous acid 12.2%.

Example 2

Press the method for example 1, temperature of reaction changes 80 ℃ into, and other method is constant.Two (2,4, the 4-tri-methyl-amyl) phospho acid 71.8g, yield 88.3%.Warp ³¹The P-NMR assay products consists of:

Two (2,4, the 4-tri-methyl-amyl) phospho acid 91.3% of target product

Single substituent 2,4,4-tri-methyl-amyl phosphonous acid 5.9%.

Example 3

Press the method for example 1, temperature of reaction changes 100 ℃ into, and other method is constant.Two (2,4, the 4-tri-methyl-amyl) phospho acid 67.6g, yield 83.1%.Warp ³¹The P-NMR assay products consists of:

Two (2,4, the 4-tri-methyl-amyl) phospho acid 86.2% of target product

Single substituent 2,4,4-tri-methyl-amyl phosphonous acid 7.6%.

Example 4

Press the method for example 1, the reaction times changes 4h into, and other method is constant.Two (2,4, the 4-tri-methyl-amyl) phospho acid 75.3g, yield 92.6%.Warp ³¹The P-NMR assay products consists of:

Two (2,4, the 4-tri-methyl-amyl) phospho acid 92.7% of target product

Single substituent 2,4,4-tri-methyl-amyl phosphonous acid 5.3%.

Example 5

Press the method for example 1, the reaction times changes 5h into, and other method is constant.Two (2,4, the 4-tri-methyl-amyl) phospho acid 77.3g, yield 95.1%.Warp ³¹The P-NMR assay products consists of:

Two (2,4, the 4-tri-methyl-amyl) phospho acid 95.5% of target product

Single substituent 2,4,4-tri-methyl-amyl phosphonous acid 3.9%.

Claims (2)

1. the synthetic method of two (2,4, the 4-tri-methyl-amyl) phospho acid, it is a raw material with sodium hypophosphite and diisobutylene, is solvent with acetate, it is characterized in that comprising the following step:

1) sodium hypophosphite is dissolved in the acetate, adds diisobutylene, in above-mentioned solution, add radical initiator azo diisobutyl amidine hydrochloride and hydrogen peroxide then, be heated to 60-100 ℃ under the vigorous stirring, normal pressure isothermal reaction 3 ~ 5h;

Wherein, the mol ratio of diisobutylene and sodium hypophosphite is not less than 5, the mol ratio of acetate and sodium hypophosphite is not less than 1, and the mol ratio of azo diisobutyl amidine hydrochloride and sodium hypophosphite is not less than 0.5, and the mol ratio of azo diisobutyl amidine hydrochloride and sodium hypophosphite is not less than 0.5;

2) leave standstill, separatory, the washing organic phase gets two (2,4, the 4-tri-methyl-amyl) phospho acid of target product after the vacuum distilling.

2. according to two (2 described in the claim 1,4, the 4-tri-methyl-amyl) synthetic method of phospho acid is characterized in that the mol ratio of sodium hypophosphite, diisobutylene, acetate, azo diisobutyl amidine hydrochloride and hydrogen peroxide is 1:5～10:1.2～1.5:0.5:0.5.