CN101775033B - Preparation method of phosphite ester by using dividing wall tower reaction rectification technique - Google Patents
Preparation method of phosphite ester by using dividing wall tower reaction rectification technique Download PDFInfo
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- CN101775033B CN101775033B CN201010011479A CN201010011479A CN101775033B CN 101775033 B CN101775033 B CN 101775033B CN 201010011479 A CN201010011479 A CN 201010011479A CN 201010011479 A CN201010011479 A CN 201010011479A CN 101775033 B CN101775033 B CN 101775033B
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Abstract
The present invention discloses a preparation method of phosphite ester by using a dividing wall tower reaction rectification technique, comprising the following steps: selecting phosphorous acid, a reactant alcohol and a water carrying agent as raw materials, the dosage of the reactant alcohol is 2 to 9 times the demand of the reaction; adding the raw materials into a reactor which is additionally provided with a dividing wall-typed rectifying tower for reaction, the reaction temperature is between 80 to 160 DEG C, leading cooling water into the overhead condenser timely, distilling off the lowest binary azeotrope formed by the water of the reaction and the reactant alcohol or the lowest ternary azeotrope formed by the water of the reaction, the reactant alcohol and the water carrying agent from the tower top, leading the distillate into a stratifying device after condensation, leading the oil phase into the side communicated with the reactor and leading the aqueous phase into the other side; stopping the backflow when the amount of the water in the aqueous phase reaches the preconcerted amount, distilling off the excessive reactant alcohol; stopping the heat when no distillate appears on the tower top, and the product let out from the tower bottom is phosphite ester. The invention has fast reaction speed, high product purity and fewer by-products.
Description
Technical field
The invention belongs to fine chemistry industry auxiliary agent, midbody technical field, have the preparation method who relates to a kind of improved phosphorous acid esters.
Background technology
At present the production of the phosphorous acid ester in fine chemistry industry auxiliary agent, midbody field is raw material with volatile phosphorus trichloride and corresponding alcohol all, also adopts toluene etc. as solvent in many technologies, under 50-70 ℃ of low temperature, reacts.When alcohol is excessive, obtain tris phosphite and a large amount of hydrogenchloride and by product alkyl chloride; When pure quantity not sufficient and in the presence of hydrogenchloride tris phosphite can be decomposed into phosphorous acid diester and corresponding alkyl chloride; After reaction finishes; Steam hydrogenchloride and alkyl chloride that reaction produces, underpressure distillation obtains corresponding phosphorous acid ester again, and in still high boiling product such as residual phosphorous acid.
Phosphorus trichloride technological reaction speed is fast, reaction is violent, only needs low temperature to react.But phosphorus trichloride is volatile, toxicity is big, and operating environment is poor, and key is that by product is many, for reducing side reaction, often need add solvent.Also have by products such as hydrogenchloride, chloroparaffin, phosphorous acid even add solvent, so the difficult purification of product, and the purposes of by product is limited.
Summary of the invention
Problem to be solved by this invention is: solve the technical problems such as defective that exist in the above-mentioned phosphorous acid ester production; And a kind of method of utilizing dividing wall tower reaction rectification technique to prepare phosphorous acid ester is provided; Utilize industrial phosphorous acid for raw material substitution phosphorus trichloride and excessive alcohol reaction, produce corresponding phosphorous acid ester.
The technical scheme that the present invention taked is:
A kind of method of utilizing dividing wall tower reaction rectification technique to prepare phosphorous acid ester comprises the steps:
Step 1 is chosen phosphorous acid and reactant alcohol, and/or the band aqua, and wherein the dosage of reactant alcohol is 2～9 times of the reaction required amount;
Step 2; Raw material in the step 1 is added in the subsidiary reaction kettle that the dividing wall type rectifying tower arranged reacts; The jacketed type stainless steel cauldron that reaction kettle selects for use band to stir utilizes high temperature heat conductive oil or steam to heat to reaction kettle stirring simultaneously, and temperature of reaction is 80～160 ℃; The overhead condenser of dividing wall type rectifying tower should in time feed water coolant; The water that reaction generates and reactant alcohol form minimum binary azeotrope or with reactant alcohol and be with aqua to form the ternary minimum azeotropic mixture jointly to be distillated by the cat head of dividing wall type rectifying tower, get into quantizer after the distillate condensation, oil phase passes back into a side that communicates with reaction kettle; Aqueous-phase reflux is gone into opposite side, with regard to whole dividing wall type rectifying tower, takes the total reflux mode;
Step 3; After for some time is carried out in reaction in the step 2, the water side reboiler bottom extension water of attaching troops to a unit from the dividing wall type rectifying tower, when the amount of aqueous phase water when answering aquifer yield; Reduce or stop oil phase and reflux, and progressively adjust temperature of reaction according to the product analysis test result; Need steam partial reaction thing alcohol this moment; The thick product storage tank of cat head that gets into the dividing wall type rectifying tower as oil phase is to get batch use ready; When the amount of aqueous phase water reaches when answering aquifer yield, stop to reflux, distillation or underpressure distillation steam excessive reactant alcohol or reactant alcohol and band aqua; When the cat head of dividing wall type rectifying tower does not have overhead product or the bottom product analytical study of dividing wall type rectifying tower when qualified, stop heating, the resultant of emitting at the bottom of the tower of dividing wall type rectifying tower is the phosphorous acid ester product.
In the above-mentioned steps 3, as producing tris phosphite, answering aquifer yield is the water about phosphorous acid and reactant alcohol contained humidity and 3 times of amount of substances of phosphorous acid total amount amount of substance; As produce the phosphorous acid diester, answering aquifer yield is the water of phosphorous acid and reactant alcohol contained humidity and 2 times of amount of substances of phosphorous acid total amount amount of substance; Above-mentionedly also in the lump liquid holdup contained humidity in the tower is taken into account when answering aquifer yield to calculate.
In the above-mentioned steps 1, reactant alcohol is selected from ethanol, propyl alcohol, propyl carbinol or the trimethyl carbinol; The band aqua is selected from benzene or hexanaphthene.
In the above-mentioned steps 1, the dosage of reactant alcohol (in amount of substance) is 4～6 times of phosphorous acid amount, the final phosphorous acid diester that obtains in the above-mentioned steps 3.
In the above-mentioned steps 1, the dosage of reactant alcohol (in amount of substance) is 6～9 times of phosphorous acid amount, the final tris phosphite that obtains in the above-mentioned steps 3.
In the above-mentioned steps 2, reaction temperature in earlier stage is 80～120 ℃, and the temperature in reaction later stage rises to 110～160 ℃ gradually.
Useful technique effect of the present invention is:
The present invention is a raw material with phosphorous acid and corresponding alcohol; For accelerating speed of reaction; Add excessive many times alcohol on the one hand, in time remove reaction product water on the other hand, simultaneously along with reaction process can also improve constantly temperature of reaction to improve speed of reaction to break the restriction of molecular balance.Utilize the dividing wall type rectifying tower to adopt the azeotropic distillation technology to remove the water that dereaction generates.Can form biphase such as the propyl carbinol that part dissolves each other after azeotrope and the azeotrope condensation for reactant alcohol and water; Need not to add the band aqua; Can not form when reactant alcohol that azeotrope maybe can form azeotrope but be equal phase time after the condensation, need to add band aqua such as ethanol, the trimethyl carbinols etc. such as benzene, hexanaphthene.
Begin reaction when reactant adds the reaction kettle post-heating, the anti-substrate concentration of initial reaction stage is big, and speed of reaction is fast; But the very easy balance that reaches; For the water conservancy of removing the dereaction generation leaves reactive system with water by dividing wall type rectifying tower band with the binary minimum azeotropic mixture of reactant alcohol and water formation or the ternary minimum azeotropic mixture that should form of reactant alcohol and the formation of water band aqua, behind overhead condensation, get into quantizer; In quantizer, be divided into profit two phases; Oil phase reflux to get into a side that is connected with reaction kettle, through carry heat up in a steamer azeotrope after, alcohol and band aqua flow into reaction kettle to be continued to participate in reacting; Water layer passes back into and the isolated side of reaction kettle; Draw liquid phase at this side bottom and get into the reboiler of establishing in addition, the termite or the steam heating of being come out by reacting kettle jacketing produce aqueous phase side in the vapour phase entering tower, when reaction for some time; After whole tower is more stable; After the concentration of detection water was up to standard, the part water was with progressively extraction of liquid state, until answering aquifer yield.
When reaction proceeds to the later stage, for reaching higher transformation efficiency and shortening the reaction times and need improve temperature of reaction, the amount of aqueous phase water need reduce or stop oil phase and reflux, and progressively improve temperature of reaction according to the product analysis test result near answering aquifer yield at this moment.Need steam partial reaction thing alcohol this moment, get into the thick product storage tank of cat head to get batch use ready as oil phase.When the amount of aqueous phase water reaches when answering aquifer yield, stop to reflux, the band aqua that distillation or underpressure distillation steam excessive reactant alcohol and possibly need to add obtains the corresponding phosphorous acid ester product of purified.
Can further draw by above-mentioned; The present invention utilizes dividing wall tower reaction rectification technique, is the raw material substitution phosphorus trichloride with industrial phosphorous acid, and takes excessive reactant alcohol; Reaction can be carried out under 80～170 ℃ the higher temperature conditions; Speed of reaction is fast, when obtaining high purity product, has also fundamentally reduced the by product of reaction.
Embodiment
Specify in the face of a kind of method of utilizing dividing wall tower reaction rectification technique to prepare phosphorous acid ester of the present invention down:
Reaction raw materials and dosage:
The phosphorous acid amount of substance: 1 part (respectively by pure quality kg, or pure article amount of substance mol meter);
Reactant alcohol such as ethanol, propyl alcohol, propyl carbinol or the trimethyl carbinol etc.: than reaction required amount (in amount of substance) excessive 2～9 times; As produce tris phosphite, and the dosage of reactant alcohol is 6～9 times that add-on (in amount of substance) should be the phosphorous acid amount, if as producing the phosphorous acid diester, the add-on of reactant alcohol (in amount of substance) should be 4～6 times of phosphorous acid amount.
Add band aquas such as benzene, hexanaphthene when partial reaction such as reactant alcohol are ethanol, propyl alcohol, the trimethyl carbinol etc.: the ratio of band aqua is answered aquifer yield calculating by theory in forming in azeotropic.
Conversion unit:
Be the subsidiary reaction kettle that the dividing wall type rectifying tower is arranged, the jacketed type stainless steel cauldron that reaction kettle selects for use band to stir.The dividing wall type rectifying tower is positioned at reaction kettle top one side; Reaction kettle is the tower still of rectifying tower simultaneously, and the partition tower can be a packing tower, also can be tray column; Its constructional feature is can be by two telescopic partition towers that concentric circular tower is formed of size, and the circle that is also cut off by baffle plate lacks shape partition tower.But part does not have partition near cat head, and the steam of two portions generation gets into overhead condenser together at interval, and cat head is established quantizer and coarse raw materials storage tank in addition.Overhead vapours is after condensation, layering, and oil phase and water pass back into the both sides of partition respectively.Pure water or diluted alcohol aqueous solution are drawn in the bottom of one side of aqueous-phase reflux, and the reboiler heating vaporization part moisture of being established by other produces vapour phase, and part is with the liquid phase extraction.
The preparation process:
(1) with phosphorous acid, corresponding reactant alcohol, the band aqua that possibly need to add is by in the corresponding ratio adding reaction kettle.
(2) start stirring, utilize high temperature heat conductive oil or steam to heat simultaneously, and control corresponding temperature of reaction, but for preventing that phosphorous acid from decomposing, temperature of reaction must not be higher than 170 ℃ promptly in 80～160 ℃ of preferred range to reaction kettle.Overhead condenser should in time feed water coolant; Water that reaction produces and reactant itself form minimum binary azeotrope or water and reactant alcohol such as ethanol, the trimethyl carbinol etc. and are with aqua to form the ternary minimum azeotropic mixture jointly like propyl carbinol and distillated by dividing wall type rectifying tower cat head; Get into quantizer after the distillate condensation; Oil phase passes back into a side that communicates with reaction kettle, and aqueous-phase reflux is gone into opposite side.Reflux type is total reflux with regard to whole tower.
(3) after reaction for some time, the extension water from water side reboiler bottom, when the amount of aqueous phase water when answering aquifer yield, reduce or stop oil phase and reflux, and progressively adjust temperature of reaction according to the product analysis test result.Need steam partial reaction thing alcohol this moment, gets into the thick product storage tank of cat head as oil phase and batch use to get ready, when the amount of aqueous phase water reaches when answering aquifer yield, stops to reflux the band aqua that distillation or underpressure distillation steam excessive reactant alcohol and possibly need to add.As to produce the moisture that tris phosphite should take out of be the water about phosphorous acid and pure contained humidity and 3 times of amount of substances of phosphorous acid total amount amount of substance; The moisture that production phosphorous acid diester should be taken out of is the water of phosphorous acid and pure contained humidity and 2 times of amount of substances of phosphorous acid total amount amount of substance, simultaneously liquid holdup contained humidity in the considered tower.
When (4) cat head does not have overhead product or bottom product analytical study when qualified, stop heating, emit resultant at the bottom of the tower to be purified phosphorous acid ester product.
Above-mentioned reaction raw materials and dosage, the temperature of reaction condition with and the mode of resultant in can taking to give an example as follows:
Embodiment 1
The preparation of tributyl phosphate, early stage, temperature of reaction was 120 ℃, the later stage is warming up to 160 ℃ gradually
The amount umber of reaction raw materials and tie substance thereof is following:
1. phosphorous acid 82
2. propyl carbinol 660
Embodiment 2
The preparation of dibutyl phosphite, early stage, temperature of reaction was 120 ℃, the later stage is warming up to 150 ℃ gradually
The amount umber of reaction raw materials and tie substance thereof is following:
1. phosphorous acid 82
2. propyl carbinol 300
Embodiment 3
The preparation of diethyl phosphite, early stage, temperature of reaction was 80 ℃, the later stage is warming up to 110 ℃ gradually
The amount umber of reaction raw materials and tie substance thereof is following:
1. phosphorous acid 82
2. ethanol 280
3. benzene 80
Embodiment 4
The preparation of phosphorous acid di tert butyl carbonate, early stage, temperature of reaction was 90 ℃, and the later stage is warming up to 120 ℃ gradually
The amount umber of reaction raw materials and tie substance thereof is following:
1. phosphorous acid 41
2. the trimethyl carbinol 150
4. hexanaphthene 80
The method of inspection
The present invention obtains product or middle sampling analysis all can adopt vapor-phase chromatography or high-efficient liquid phase chromatogram technique analysis.
Claims (6)
1. method of utilizing dividing wall tower reaction rectification technique to prepare phosphorous acid ester, characteristic is to comprise the steps:
Step 1 is chosen phosphorous acid and reactant alcohol, and perhaps with reactant alcohol and band aqua, wherein the dosage of reactant alcohol is counted 4～9 times of phosphorous acid amount with amount of substance;
Step 2; Raw material in the step 1 is added in the subsidiary reaction kettle that the dividing wall type rectifying tower arranged reacts; The jacketed type stainless steel cauldron that reaction kettle selects for use band to stir utilizes high temperature heat conductive oil or steam to heat to reaction kettle stirring simultaneously, and temperature of reaction is 80～160 ℃; The overhead condenser of dividing wall type rectifying tower should in time feed water coolant; The water that reaction generates and reactant alcohol form minimum binary azeotrope or with reactant alcohol and be with aqua to form the ternary minimum azeotropic mixture jointly to be distillated by the cat head of dividing wall type rectifying tower, get into quantizer after the distillate condensation, oil phase passes back into a side that communicates with reaction kettle; Aqueous-phase reflux is gone into opposite side, with regard to whole dividing wall type rectifying tower, takes the total reflux mode;
Step 3; After for some time is carried out in reaction in the step 2, the water side reboiler bottom extension water of attaching troops to a unit from the dividing wall type rectifying tower, when the amount of aqueous phase water when answering aquifer yield; Reduce or stop oil phase and reflux, and progressively adjust temperature of reaction according to the product analysis test result; Need steam partial reaction thing alcohol this moment; The thick product storage tank of cat head that gets into the dividing wall type rectifying tower as oil phase is to get batch use ready; When the amount of aqueous phase water reaches when answering aquifer yield, stop to reflux, distillation or underpressure distillation steam excessive reactant alcohol or reactant alcohol and band aqua; When the cat head of dividing wall type rectifying tower does not have overhead product or the bottom product analytical study of dividing wall type rectifying tower when qualified, stop heating, the resultant of emitting at the bottom of the tower of dividing wall type rectifying tower is the phosphorous acid ester product.
2. the method for utilizing dividing wall tower reaction rectification technique to prepare phosphorous acid ester according to claim 1; It is characterized in that: in the said step 3; As produce tris phosphite, answering aquifer yield is the water of phosphorous acid and reactant alcohol contained humidity and 3 times of amount of substances of phosphorous acid total amount amount of substance; As produce the phosphorous acid diester, answering aquifer yield is the water of phosphorous acid and reactant alcohol contained humidity and 2 times of amount of substances of phosphorous acid total amount amount of substance; Above-mentionedly also in the lump liquid holdup contained humidity in the tower is taken into account when answering aquifer yield to calculate.
3. the method for utilizing dividing wall tower reaction rectification technique to prepare phosphorous acid ester according to claim 1 is characterized in that: in the said step 1, reactant alcohol is selected from ethanol, propyl alcohol, propyl carbinol or the trimethyl carbinol; The band aqua is selected from benzene or hexanaphthene.
4. the method for utilizing dividing wall tower reaction rectification technique to prepare phosphorous acid ester according to claim 1; It is characterized in that: in the said step 1; The dosage of reactant alcohol is counted 4～6 times of phosphorous acid amount with amount of substance, the final phosphorous acid diester that obtains in the above-mentioned steps 3.
5. the method for utilizing dividing wall tower reaction rectification technique to prepare phosphorous acid ester according to claim 1; It is characterized in that: in the said step 1; The dosage of reactant alcohol is counted 9 times of phosphorous acid amount with amount of substance, the final tris phosphite that obtains in the above-mentioned steps 3.
6. the method for utilizing dividing wall tower reaction rectification technique to prepare phosphorous acid ester according to claim 1 is characterized in that: in the said step 2, reaction temperature in earlier stage is 80～120 ℃, and the temperature in reaction later stage rises to 110～160 ℃ gradually.
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| EP2581378A1 (en) | 2011-10-13 | 2013-04-17 | Straitmark Holding AG | Method for the esterification of P-O components |
| CN107383086A (en) * | 2017-06-14 | 2017-11-24 | 浙江嘉华化工有限公司 | A kind of diethyl phosphite refining process |
| CN108003188A (en) * | 2017-12-25 | 2018-05-08 | 长春吉大天元化学技术股份有限公司 | A kind of new purification process of alkyl phosphoric acid esters compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493575A (en) * | 2002-10-28 | 2004-05-05 | 刘德亮 | Method of preparing phosphite ester |
| CN101250199A (en) * | 2008-03-20 | 2008-08-27 | 太仓市茜泾化工有限公司 | Method for preparing diisopropyl phosphite |
| CN101624400A (en) * | 2009-08-07 | 2010-01-13 | 湖北三才堂化工科技有限公司 | Production method of triethyl phosphite |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493575A (en) * | 2002-10-28 | 2004-05-05 | 刘德亮 | Method of preparing phosphite ester |
| CN101250199A (en) * | 2008-03-20 | 2008-08-27 | 太仓市茜泾化工有限公司 | Method for preparing diisopropyl phosphite |
| CN101624400A (en) * | 2009-08-07 | 2010-01-13 | 湖北三才堂化工科技有限公司 | Production method of triethyl phosphite |
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