CN100503623C

CN100503623C - Process for preparing high-purity butoxy ethyl phosphate

Info

Publication number: CN100503623C
Application number: CNB2006100881599A
Authority: CN
Inventors: 周聚潞
Original assignee: Individual
Current assignee: Individual
Priority date: 2006-06-30
Filing date: 2006-06-30
Publication date: 2009-06-24
Anticipated expiration: 2026-06-30
Also published as: CN1884286A

Abstract

The invention relates to a method for preparing high-purity butoxy triethyl ester phosphate, belonging to method preparing chemical products. It is characterized in that: (1) feed proportioning: preparing phosphorous oxychloride 1 unit and butoxy alcohol 3-10 units to be input into autoclave during synthesis; (2) synthesizing: inputting reactant into autoclave, venting cooling water into jacket; (3) refluxing: heating material in autoclave to 50-90 Deg. C to evaporate part of reactant and product to condensator on upper part of autoclave, HCl in product is extracted out and the left is dropped to autoclave for reaction again; (4) reclaiming: reclaiming excess alcohol after refluxing; (5) neutralizing: neutralizing coarse product with NaOH and Na2CO3. The invention can improve product purity and productivity; reduce production cost and energy consumption and pollution.

Description

The production method of high-purity butoxy ethyl phosphate

Technical field

The present invention relates to the production method of Chemicals, refer in particular to a kind of production method of phosphoric acid ester product.

Background technology

Along with developing rapidly of chemical industry, the use of phosphoric acid ester more and more widely requires also more and more higher.With the triethyl phosphate is example, and it is good fire retardant, abroad, replaces chlorine-containing flame retardant with it in large quantities, and consumption is rising with annual kiloton.Yet it has several shortcomings: it is low to produce yield, and purposes is narrower, and meeting water is hydrolysis, and many aqueous products can not be fire retardant with it, or the like.Will ask for help like this whether can develop a kind of new material, the shortcoming of its without phosphorus triethylenetetraminehexaacetic acid ester has the advantage of triethyl phosphate, has other function again concurrently.By the research and experiment of long period, find that butoxy ethyl phosphate is exactly this fabulous material.How butoxy ethyl phosphate is produced, and is exactly the research contents of this paper.

Summary of the invention

The objective of the invention is to seek a kind of production method of high-purity butoxy ethyl phosphate, to improve the purity and the yield of product; Reduce production costs and energy consumption; Reduce and pollute.

The production method of high-purity butoxy ethyl phosphate is characterized in that:

(1) batching: will be ready to 3～10 parts of reactants of forming of butyl cellosolve by 1 part of Phosphorus Oxychloride, in input reactor when synthetic;

(2) synthetic: the reactant input is had in the reactor of chuck, logical water coolant in the chuck, reactant reacts in reactor, generates most (C ₄H ₉OC ₂H ₄O) ₂POCl and HCl also generate (the C of small part ₄H ₉OC ₂H ₄O) ₃PO; Reaction conditions is: vacuum tightness is not less than-0.090, and temperature of reaction is between 5 ℃～50 ℃, and the reaction times is 2.5h～4h, and adds the catalyzer halide-containing, and the add-on of halide-containing is 0.5 ‰-2 ‰ of a reactant, and unit is a weight percentage; Reaction equation is:

React very fast;

React very slow; Described halide-containing is the mixture of titanium tetrachloride, aluminum chloride, butter of antimony;

(3) reflux: after synthetic, temperature of charge in the reactor is heated to 50 ℃～90 ℃, make partial reaction thing and resultant be evaporated to the condenser that is positioned at above the reactor, HCl in the resultant is depressurized and takes out, fall into again after the remaining condensation and participate in reaction in the reactor again, until generating (C fully ₄H ₉OC ₂H ₄O) ₃PO in reflux course, further finishes following reaction, and continues to get rid of HCl; Vacuum tightness is not less than-0.090 during backflow, and the reaction times is 2h～4h; Reaction equation is:

React very slow;

(4) reclaim: after the end that refluxes, reclaim excessive alcohol in the reactant under negative pressure, during recovery, vacuum tightness is not less than-0.090, and temperature is no more than 150 ℃, and the time is 1h-3h; After recycling alcohol excess, residuum is the raw product of butoxy ethyl phosphate;

(5) neutralization: after recycling excessive alcohol, with NaOH or Na ₂CO ₃Aqueous solution neutralized crude goods, and make it be neutral; In and under normal pressure, carry out NaOH or Na ₂CO ₃Concentration of aqueous solution be 2%～20%, temperature is below 100 ℃, the liquid phase after the neutralization is isolated raw product with settling process.

Re-refine after neutralization, heat up earlier and decompression when refining, make raw product distillation, dehydration after the neutralization, the product that in still-process, vapor pressure is 4 mmhg height, obtain when vapor temperature reaches 222 ℃ is finished product.

Halide-containing is one or more of titanium tetrachloride, aluminum chloride, butter of antimony etc.

Earlier clean raw product before after neutralization, making with extra care, to remove the alkali excessive in the raw product and the salt of generation with clear water.

When synthetic, add the strong reductant of minute quantity, guarantee that the reactant in the reactor reacts under non-oxidizing situation, to reduce the color and luster of product.

When raw product colourity is too high, use activated carbon decolorizing; Activated carbon dosage is 3 ‰ of raw product amount～5 ‰, and the pressure filter inner filtration falls activated carbon filtration then, and is promptly up to standard.

Strong reductant is a kind of in sodium borohydride, potassium boron hydrogen, the lithium boron hydrogen.

Advantage of the present invention is: utilizes present method to assemble when producing, can obtain highly purified butoxy ethyl phosphate, and excessive pure yield foot, and can continue to utilize not waste; The yield height; Energy consumption is few; Can make hydrochloric acid after the HCl water absorbs and use, pollution-free.

Description of drawings

Fig. 1 is a process flow sheet of the present invention.

Embodiment

One, the basic condition of butoxy ethyl phosphate

1, English name: Tributoxyethyl phosphate

2, code name: TBEP

3, molecular formula: C ₁₈H ₃₉O ₇P

4, structural formula:

5, molecular weight: 398

6, main raw material: Phosphorus Oxychloride POCl ₃

Butyl cellosolve C ₄H ₉OC ₂H ₄OH

7, technical indicator

Appearance colorless or light yellow transparent liquid

Color and luster≤80 ^#

20 ℃ 1.020 ± 0.005 of proportion

Acid number mgKOH/g≤1 ± 0.2

Moisture content %≤0.3

Content % 〉=1. 96 2. 99

Refractive index 1.434 ± 0.005

8, purposes: the efficient cryogenic softening agent and the antiager of polyvinyl chloride, synthetic rubber etc.; The additive of floor polishing agent and flow agent; The additive of paint gasoline; The fine solvent of nitrocotton and shellac varnish.Broad spectrum type top grade fire retardant; Special solvent; Paint remover and heat exchange medium.

Two, production technique

1, primitive reaction equation

(1)

(reacting very fast)

(2)

(reacting very slow)

2, idiographic flow

(1) batching

Calculate by theoretical, the Phosphorus Oxychloride of a part adds the butyl cellosolve of 3 molecules, just can synthesize a part butoxy ethyl phosphate.But in actually operating, because alcohol and torpescence so alcohol must be excessive, generally will surpass 50%-200% of calculated value, alcohol is excessive many more, and the purity of product is high more, and yield is high more.

(2) synthetic

In order to discharge resultant HCl, reaction is carried out to positive dirction, to synthesize under negative pressure and carry out, vacuum tightness generally must not be lower than-0.090, and vacuum tightness is high more, and the HCl of discharge is many more.

Temperature of reaction generally is controlled between 5 ℃-50 ℃ to well.

Reaction times is that 2.5h-4h is advisable.

(3) reflux

To react completely in order making, to make (C ₄H ₉OC ₂H ₄O) ₂POCl (chloro phosphoric acid ester) generates (C fully ₄H ₉OC ₂H ₄O) ₃PO must reflux, and in reflux course, further finishes second primitive reaction equation, and continues to get rid of HCl.

Vacuum tightness must not be lower than-0.090, and is high more good more, and temperature is controlled at 50 ℃-90 ℃, and the time is 2h-4h.

(4) reclaim alcohol excess

In order to reduce the boiling point of alcohol, accelerate the recovery speed of alcohol, discharge HCl simultaneously, so the recovery of alcohol excess also must be carried out under negative pressure.

Vacuum tightness must not be lower than-0.090, and is high more good more, and temperature should not surpass 150 ℃, and the time is 1h-3h.

(5) neutralization

Any reaction can not be perfect, and particularly organic compound reaction in the building-up process of this product, still has some side reactions, and (C ₄H ₉OC ₂H ₄O) ₂POCl can not all be converted into C ₁₈H ₃₉O ₇P, HCl can not all be excluded, so must use NaOH (sodium hydroxide) or Na ₂CO ₃The aqueous solution of (anhydrous sodium carbonate) comes the neutralized crude goods, and makes it be neutral.

Neutralization can be carried out under normal pressure, NaOH and Na ₂CO ₃Concentration of aqueous solution can be 2%-20%, controlled temperature is below 100 ℃, liquid phase is separated with simple settling process.

(6) refining

Handle raw product with ordinary method, make it become standard compliant finished product.

Three, several lime lights

Must grasp product boiling point when 4 mmhg are high when 1, making with extra care is 222 ℃

Must add catalyzer when 2, synthesizing, catalyzer is generally halide-containing, and is all good as results of use such as titanium tetrachloride, aluminum chloride, butter of antimony, but catalyzer will mix use, more can improve purity and yield, consumption is generally about 0.5 ‰-2 ‰ of reactant

3, the neutralization best water that finishes cleans, to remove the excessive alkali and the salt of generation.

4, in order to reduce the colourity of product, when synthetic, can add the material of a spot of sodium borohydride one class.

5, finished product colourity is too high, available activated carbon decolorizing.

Claims

1, the production method of high-purity butoxy ethyl phosphate is characterized in that:

(2) synthetic: the reactant input is had in the reactor of chuck, logical water coolant in the chuck, reactant reacts in reactor, generates most (C ₄H ₉OC ₂H ₄O) ₂POCl and HCl also generate (the C of small part ₄H ₉OC ₂H ₄O) ₃PO; Reaction conditions is: vacuum tightness is not less than-0.090, and temperature of reaction is between 5 ℃～50 ℃, and the reaction times is 2.5h～4h, and adds the catalyzer halide-containing, and the add-on of halide-containing is 0.5 ‰-2 ‰ of a reactant, and unit is a weight percentage;

Reaction equation is:

React very fast;

React very slow;

(5) neutralization: after recycling excessive alcohol, with NaOH or Na ₂CO ₃Aqueous solution neutralized crude goods, and make it be neutral; In and under normal pressure, carry out NaOH or Na ₂CO ₃Concentration of aqueous solution be 2%～20%, temperature is below 100 ℃, the liquid phase after the neutralization is isolated raw product with settling process;

After neutralization, re-refine, heat up earlier and decompression when refining, make raw product distillation, dehydration after the neutralization, in still-process, vapor pressure is 4 mmhg height, the product of acquisition when vapor temperature reaches 222 ℃ is finished product, and the technical indicator of described butoxy ethyl phosphate finished product is as follows:

Appearance colorless or light yellow transparent liquid

Color and luster≤80 ^#

20 ℃ 1.020 ± 0.005 of proportion

Acid number mgKOH/g≤1 ± 0.2

Moisture content %≤0.3

Content % 〉=99 of butoxy ethyl phosphate

Refractive index 1.434 ± 0.005.

2, the production method of high-purity butoxy ethyl phosphate as claimed in claim 1 is characterized in that: clean raw product with clear water earlier before making with extra care after neutralization, to remove the alkali excessive in the raw product and the salt of generation.

3, the production method of high-purity butoxy ethyl phosphate as claimed in claim 1 is characterized in that: add the strong reductant of minute quantity when synthetic, guarantee that the reactant in the reactor reacts under non-oxidizing situation, to reduce the color and luster of product.

4, the production method of high-purity butoxy ethyl phosphate as claimed in claim 1 is characterized in that: when raw product colourity is too high, use activated carbon decolorizing; Activated carbon dosage is 3 ‰ of raw product amount～5 ‰, at the pressure filter inner filtration, activated carbon filtration is fallen then, and is promptly up to standard.

5, the production method of high-purity butoxy ethyl phosphate as claimed in claim 3 is characterized in that: strong reductant is a kind of in sodium borohydride, potassium boron hydrogen, the lithium boron hydrogen.