CN102002068A - After-treatment method of crude tris-(2-isopropyl chloride) phosphate - Google Patents
After-treatment method of crude tris-(2-isopropyl chloride) phosphate Download PDFInfo
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- CN102002068A CN102002068A CN 201010562551 CN201010562551A CN102002068A CN 102002068 A CN102002068 A CN 102002068A CN 201010562551 CN201010562551 CN 201010562551 CN 201010562551 A CN201010562551 A CN 201010562551A CN 102002068 A CN102002068 A CN 102002068A
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- acid ester
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Abstract
The invention relates to an after-treatment method of crude tris-(2-isopropyl chloride) phosphate, in particular to a treatment method which can effectively remove the stinky 2-methyl-pentanal in the tris-(2-isopropyl chloride) phosphate. The method is characterized by comprising the steps of: introducing a certain amount of ozone in the crude tris-(2-isopropyl chloride) phosphate obtained by reaction; directly oxidizing the insoluble 2-methyl-pentanal generated by reaction into acidic materials such as 2- methyl-valeric acid and the like soluble in an alkaline solution; and conveniently removing the acidic materials in the subsequent washing process to ensure that the obtained tris-(2-isopropyl chloride) phosphate does not contain the 2-methyl-pentanal which stinks. The method of the invention reduces the content of the stinky 2-methyl-pentanal in the tris-(2-isopropyl chloride) phosphate from about 200-300ppm to less than 5ppm; and when the product is applied to the interior materials of automobiles or furniture and the like, the stink is eliminated, and therefore, the product is in the favor of consumers.
Description
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Technical field
The invention belongs to fine chemical product purification techniques field, be specifically related to a kind of post-treating method of effectively removing repugnant substance 2-methyl alkene valeral in three-(2-chloro isopropyl) the phosphoric acid ester crude products.
Background technology
At present, three
-The preparation method of (2-chloro isopropyl) phosphoric acid ester is to react synthetic by phosphorus oxychloride and propylene oxide under lewis acid catalysis.Obtain three-(2-chloro isopropyl) phosphoric acid ester crude products after phosphorus oxychloride and propylene oxide reaction are finished, crude product is finished product after pickling, alkali cleaning, washing, distillation remove water.Yet in three-(2-chloro isopropyl) phosphoric acid ester production processes, produced simultaneously and had malodorous material 2-methyl alkene valeral, it and three-(2-chloro isopropyl) phosphoric acid ester have good intermiscibility, water-soluble hardly, though therefore through pickling, alkali cleaning, washing and distillation, its content is generally still about 200-3OOppm.Thereby stink is bigger, and when it is used for other goods, can pollute other goods, sends denseer stink, has a strong impact on other Products Quality.When especially being used for interior materials such as automobile or furniture when goods, the existence of stink has a strong impact on its normal use.At patent US2610978, US3100220, US 2008227997, DE-A1921504, introduced the method that adopts synthetic three-(2-chloro isopropyl) phosphoric acid ester of different catalyzer among EP 0398095 A2, but all not mentioned 2-methyl alkene valeral content method that how to reduce.Patent CN 101007952 has proposed to reduce the method for aldehyde material, this method be by at three-(2-chloro isopropyl) phosphoric acid ester crude products after pickling, alkali cleaning, add oxammonium hydrochloride solution, utilize it and aldehyde reaction, generate water-soluble oxime compounds, and then reduce aldehyde through washing, distilling.The main drawback of this method is: 1) the oxammonium hydrochloride aqueous solution is immiscible with three-(2-chloro isopropyl) phosphoric acid ester, therefore need the long reaction times, and the slow hydrolysis of meeting in water of three-(2-chloro isopropyl) phosphoric acid ester, thereby meeting finally influence the yield of product.The affiliation that adds of oxammonium hydrochloride finally enters Waste Water Treatment, thereby increases environmental protection pressure.The adding of oxammonium hydrochloride has simultaneously increased production cost simultaneously.2) if use the oxammonium hydrochloride alcoholic solution, although can shorten the reaction times, reduce the decomposition of product, can further increase environmental protection pressure and production cost.Thereby this method is not feasible in industrial production.
Summary of the invention
At the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of post-treating method of effectively removing repugnant substance 2-methyl alkene valeral in three-(2-chloro isopropyl) the phosphoric acid ester crude products.
The post-treating method of described a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products, it is characterized in that in three-(2-chloro isopropyl) phosphoric acid ester crude products, feeding ozone, carry out oxidizing reaction, malodor impurities 2-methyl alkene valeral in the crude product is oxidized to the acidic substance 2-methyl allyl acetic acid that is dissolved in alkaline aqueous solution, again through pickling, alkali cleaning, underpressure distillation obtain low smell three-(2-chloro isopropyl) phosphoric acid ester finished product.
The post-treating method of described a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products is characterized in that concrete processing step is as follows:
1) get a certain amount of three-(2-chloro isopropyl) phosphoric acid ester crude product 500g, input has in bottle 1000ml four-necked bottle of spirit body access tube, stirs and is warming up to 20-100 ℃, and logical ozone gas mixture generation oxidizing reaction 10-90 minute obtains reaction solution;
2) add 500ml2% dilute hydrochloric acid in the reaction solution that step 1) obtains, 55 ℃ of controlled temperature stir half an hour, leave standstill layering half an hour again, discard water layer, and organic layer is standby;
3) to step 2) add 500ml 1% sig water in the organic layer that obtains, 55 ℃ of controlled temperature stir half an hour, leave standstill layering half an hour again, discard water layer, and organic layer is standby;
4) organic layer that obtains to step 3), with 1000ml deionized water wash twice, behind the branch vibration layer, underpressure distillation dewater low smell three-(2-chloro isopropyl) phosphoric acid ester finished product.
The post-treating method of described a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products is characterized in that the ozone gas mixture described in the step 1) is ozone-containing air or oxygen ozoniferous, and the concentration of described ozone is 10-50mg/L.
The post-treating method of described a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products, it is characterized in that ozone consumption in the step 1) with respect to the 100ppm of three-(2-chloro isopropyl) phosphoric acid ester crude product amounts to 10000ppm.
The post-treating method of described a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products, it is characterized in that ozone consumption in the step 1) with respect to three-(2-chloro isopropyl) phosphoric acid ester crude product amounts 1000ppm to 5000ppm.
The post-treating method of described a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products is characterized in that the ozone oxidation temperature described in the step 1) is 30-50 ℃.
The post-treating method of described a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products is characterized in that the ozone oxidation time described in the step 1) is 15-30 minute.
The post-treating method of described a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products is characterized in that the ozone oxidation time described in the step 1) is 30 minutes.
The post-treating method of described a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products, the underpressure distillation condition described in the step 4) that it is characterized in that is temperature 70-120 ℃, vacuum is 500-1000mmHg, the low smell three that obtains-(2-chloro isopropyl) phosphoric acid ester.
The post-treating method of the present invention three-(2-chloro isopropyl) phosphoric acid ester crude product, owing to adopt the crude product that reaction is obtained, directly through ozone Oxidation Treatment, 2-methyl alkene valeral is oxidized to and is dissolved in the alkaline aqueous solution acidic substance, in subsequent laundering process, conveniently remove then, thereby make three-(2-chloro isopropyl) the phosphoric acid ester products that hang down smell.Drop to less than 5ppm about utilizing 2-methyl alkene valeral content that the inventive method can make tool foul smell in three-(2-chloro isopropyl) phosphoric acid ester by original 200-300ppm, when being used for interior materials such as automobile or furniture at this product, eliminate stink, obtained consumers in general's favor.
Embodiment
Below by following embodiment, comparing embodiment, further specify the present invention, they should not be considered limiting the scope of the invention.
The preparation of crude product: the preparation of three-(2-chloro isopropyl) phosphoric acid ester crude products: in phosphorus oxychloride, add aluminum trichloride catalyst by processes well known; after under nitrogen protection, being stirred to catalyst dissolution; drip propylene oxide at 50-80 ℃; keep 60-70 ℃ of temperature of reaction; after dripping propylene oxide; continue 80 ℃ of reactions of insulation 1.5 hours, get three-(2-chloro isopropyl) phosphoric acid ester crude products, the content of 2-methyl alkene valeral is 495.6ppm in the stratographic analysis crude product.
Embodiment 1 gets above-mentioned three-(2-chloro isopropyl) the phosphoric acid ester crude product 500g that make, input has in 1000 liters the four-necked bottle of bottle spirit body access tube, stirring is warmed up to 40 ℃, evenly feeding concentration with 15 fens clock times is that 30mg/L contains ozone-air 20L, adds 500ml then, 2% dilute hydrochloric acid, 55 ℃ of controlled temperature, stir half an hour, leave standstill layering half an hour again, tell the sour water layer.Use the same manner, with the washing of 500 ml, 1% diluted alkaline once, wash at twice with 1000 ml deionized waters, behind the branch vibration layer, organic layer is at 70-120 ℃, under the vacuum tightness 500mmHg-1000 mmHg condition vacuum distilling dewater low smell three-(2-chloro isopropyl) phosphoric acid ester finished product, the content of 2-methyl alkene valeral is 4.5ppm in the stratographic analysis product.
Embodiment 2 gets above-mentioned three-(2-chloro isopropyl) the phosphoric acid ester crude product 500g that make, input has in 1000 liters the four-necked bottle of bottle spirit body access tube, stirring is warmed up to 20 ℃, evenly feeding concentration with 90 fens clock times is that 10mg/L contains ozone-air 50L, adds 500ml then, 2% dilute hydrochloric acid, 55 ℃ of controlled temperature, stir half an hour, leave standstill layering half an hour again, tell the sour water layer.Use the same manner, with the washing of 500 ml, 1% diluted alkaline once, wash at twice with the 1000ml deionized water, behind the branch vibration layer, vacuum distilling dewater low smell three-(2-chloro isopropyl) phosphoric acid ester finished product, the content of 2-methyl alkene valeral is 3.8ppm in the stratographic analysis product.
Embodiment 3 gets above-mentioned three-(2-chloro isopropyl) the phosphoric acid ester crude product 500g that make, input has in 1000 liters the four-necked bottle of bottle spirit body access tube, stirring is warmed up to 100 ℃, evenly feeding concentration with 10 fens clock times is that 50mg/L contains ozone-air 30L, adds 500ml then, 2% dilute hydrochloric acid, 55 ℃ of controlled temperature, stir half an hour, leave standstill layering half an hour again, tell the sour water layer.Use the same manner, with the washing of 500 ml, 1% diluted alkaline once, wash at twice with the 1000ml deionized water, behind the branch vibration layer, vacuum distilling dewater low smell three-(2-chloro isopropyl) phosphoric acid ester finished product, the content of 2-methyl alkene valeral is 1.1ppm in the stratographic analysis product.
Embodiment 4 gets above-mentioned three-(2-chloro isopropyl) the phosphoric acid ester crude product 500g that make, input has in 1000 liters the four-necked bottle of bottle spirit body access tube, stirring is warmed up to 100 ℃, evenly feeding concentration with 10 fens clock times is that 50mg/L contains ozone-air 30L, adds 500ml then, 2% dilute hydrochloric acid, 55 ℃ of controlled temperature, stir half an hour, leave standstill layering half an hour again, tell the sour water layer.Use the same manner, with 500 ml, 1% diluted alkaline washing once, wash at twice with the 1000ml deionized water, behind the branch vibration layer, vacuum distilling dewater low smell three-(2-chloro isopropyl) phosphoric acid ester finished product.Implementation method such as embodiment 1, evenly feeding concentration is that 30mg/L contains ozone-air 50L, the content of 2-methyl alkene valeral is 0.8ppm in the stratographic analysis product.
Embodiment 5 gets above-mentioned three-(2-chloro isopropyl) the phosphoric acid ester crude product 500g that make, input has in 1000 liters the four-necked bottle of bottle spirit body access tube, stirring is warmed up to 30 ℃, evenly feeding concentration with 30 fens clock times is that 30mg/L contains ozone-air 30L, adds 500ml then, 2% dilute hydrochloric acid, 55 ℃ of controlled temperature, stir half an hour, leave standstill layering half an hour again, tell the sour water layer.Use the same manner, with 500 ml, 1% diluted alkaline washing once, wash at twice with the 1000ml deionized water, behind the branch vibration layer, vacuum distilling dewater low smell three-(2-chloro isopropyl) phosphoric acid ester finished product.Implementation method such as embodiment 1, evenly feeding concentration is that 30mg/L contains ozone-air 50L, the content of 2-methyl alkene valeral is 0.4ppm in the stratographic analysis product.
Embodiment 6 gets above-mentioned three-(2-chloro isopropyl) the phosphoric acid ester crude product 500g that make, input has in 1000 liters the four-necked bottle of bottle spirit body access tube, stirring is warmed up to 50 ℃, evenly feeding concentration with 15 fens clock times is that 30mg/L contains ozone-air 40L, adds 500ml then, 2% dilute hydrochloric acid, 55 ℃ of controlled temperature, stir half an hour, leave standstill layering half an hour again, tell the sour water layer.Use the same manner, with 500 ml, 1% diluted alkaline washing once, wash at twice with the 1000ml deionized water, behind the branch vibration layer, vacuum distilling dewater low smell three-(2-chloro isopropyl) phosphoric acid ester finished product.Implementation method such as embodiment 1, evenly feeding concentration is that 30mg/L contains ozone-air 50L, the content of 2-methyl alkene valeral is 0.2ppm in the stratographic analysis product.
Embodiment 7 implementation methods such as embodiment 1, under 80 ℃, it is that 30mg/L contains ozone-air 50L that 30 fens clock times evenly feed concentration, the content of 2-methyl alkene valeral is 0.4ppm in the stratographic analysis product.
Embodiment 8 implementation methods such as embodiment 1, under 60 ℃, evenly feeding concentration with 45 fens clock times is that 30mg/L contains ozone-air 100L, the content of 2-methyl alkene valeral is 0.3ppm in the stratographic analysis product.
Embodiment 9 implementation methods are as 1, and under 70 ℃, evenly feeding concentration with 30 fens clock times is that 40mg/L contains ozone-air 100L, and the content of 2-methyl alkene valeral is 0.3ppm in the stratographic analysis product.
Comparing embodiment:
Get three-(2-chloro isopropyl) the phosphoric acid ester crude product 500g that make, add 500ml, 2% dilute hydrochloric acid, 55 ℃ of controlled temperature stir half an hour, leave standstill layering half an hour again, tell the sour water layer.Use the same manner, with 500 ml, 1% diluted alkaline washing once, wash at twice with 1000 ml deionized waters, behind the branch vibration layer, vacuum distilling dewater three-(2-chloro isopropyl) phosphoric acid ester finished products, the content of 2-methyl alkene valeral is 223.3ppm in the stratographic analysis product.
Claims (9)
1. the post-treating method of one kind three-(2-chloro isopropyl) phosphoric acid ester crude product, it is characterized in that in three-(2-chloro isopropyl) phosphoric acid ester crude products, feeding ozone, carry out oxidizing reaction, malodor impurities 2-methyl alkene valeral in the crude product is oxidized to the acidic substance 2-methyl allyl acetic acid that is dissolved in alkaline aqueous solution, again through pickling, alkali cleaning, underpressure distillation obtain low smell three (2-chloro isopropyl) phosphoric acid ester finished product.
2. the post-treating method of a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products according to claim 1 is characterized in that concrete processing step is as follows:
1) get a certain amount of three-(2-chloro isopropyl) phosphoric acid ester crude product 500g, input has in bottle 1000ml four-necked bottle of spirit body access tube, stirs and is warming up to 20-100 ℃, and logical ozone gas mixture generation oxidizing reaction 10-90 minute obtains reaction solution;
2) add 500ml2% dilute hydrochloric acid in the reaction solution that step 1) obtains, 55 ℃ of controlled temperature stir half an hour, leave standstill layering half an hour again, discard water layer, and organic layer is standby;
3) to step 2) add 500ml 1% sig water in the organic layer that obtains, 55 ℃ of controlled temperature stir half an hour, leave standstill layering half an hour again, discard water layer, and organic layer is standby;
4) organic layer that obtains to step 3), with 1000ml deionized water wash twice, behind the branch vibration layer, underpressure distillation dewater low smell three (2-chloro isopropyl) phosphoric acid ester finished product.
3. the post-treating method of a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products according to claim 2 is characterized in that the ozone gas mixture described in the step 1) is ozone-containing air or oxygen ozoniferous, and the concentration of described ozone is 10-50mg/L.
4. the post-treating method of a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products according to claim 2, it is characterized in that ozone consumption in the step 1) with respect to the 100ppm of three-(2-chloro isopropyl) phosphoric acid ester crude product amounts to 10000ppm.
5. the post-treating method of a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products according to claim 2, it is characterized in that ozone consumption in the step 1) with respect to three-(2-chloro isopropyl) phosphoric acid ester crude product amounts 1000ppm to 5000ppm.
6. the post-treating method of a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products according to claim 2 is characterized in that the ozone oxidation temperature described in the step 1) is 30-50 ℃.
7. the post-treating method of a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products according to claim 2 is characterized in that the ozone oxidation time described in the step 1) is 15-30 minute.
8. the post-treating method of a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products according to claim 2 is characterized in that the ozone oxidation time described in the step 1) is 30 minutes.
9. the post-treating method of a kind of three-(2-chloro isopropyl) phosphoric acid ester crude products according to claim 2, the underpressure distillation condition described in the step 4) that it is characterized in that is a temperature 70-120 degree, vacuum is greater than 500mmHg.
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Cited By (4)
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| WO2014166086A1 (en) * | 2013-04-07 | 2014-10-16 | 深圳新宙邦科技股份有限公司 | Method for preparing tri(hexafluoroisopropyl)phosphate |
| CN108948422A (en) * | 2018-07-25 | 2018-12-07 | 浙江万盛股份有限公司 | A kind of composite flame-retardant agent and its preparation method and application, a kind of polyurethane foam |
| CN112209964A (en) * | 2020-10-20 | 2021-01-12 | 浙江万盛股份有限公司 | Preparation method of TCPP (trichloropropylphosphate) flame retardant |
| CN112898335A (en) * | 2021-01-22 | 2021-06-04 | 山东万盛新材料有限公司 | Preparation method of low-odor phosphate ester TCPP |
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| CN101775031A (en) * | 2009-12-22 | 2010-07-14 | 江苏雅克科技股份有限公司 | Method for preparing TCPP (Tris(Chloroisopropyl)Phosphate) flame retardant |
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| CN101007952A (en) * | 2006-01-26 | 2007-08-01 | 江苏雅克化工有限公司 | TCPP fire retarding agent preparation method |
| CN101240425A (en) * | 2008-03-18 | 2008-08-13 | 太原理工大学 | Technique for preparing 2,2-dihydroxymethylpropionic acid by electrochemistry method |
| CN101775031A (en) * | 2009-12-22 | 2010-07-14 | 江苏雅克科技股份有限公司 | Method for preparing TCPP (Tris(Chloroisopropyl)Phosphate) flame retardant |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014166086A1 (en) * | 2013-04-07 | 2014-10-16 | 深圳新宙邦科技股份有限公司 | Method for preparing tri(hexafluoroisopropyl)phosphate |
| CN108948422A (en) * | 2018-07-25 | 2018-12-07 | 浙江万盛股份有限公司 | A kind of composite flame-retardant agent and its preparation method and application, a kind of polyurethane foam |
| CN108948422B (en) * | 2018-07-25 | 2020-04-07 | 浙江万盛股份有限公司 | Composite flame retardant, preparation method and application thereof, and polyurethane foam |
| CN112209964A (en) * | 2020-10-20 | 2021-01-12 | 浙江万盛股份有限公司 | Preparation method of TCPP (trichloropropylphosphate) flame retardant |
| CN112209964B (en) * | 2020-10-20 | 2023-04-07 | 浙江万盛股份有限公司 | Preparation method of TCPP (trichloropropylphosphate) flame retardant |
| CN112898335A (en) * | 2021-01-22 | 2021-06-04 | 山东万盛新材料有限公司 | Preparation method of low-odor phosphate ester TCPP |
| CN112898335B (en) * | 2021-01-22 | 2022-09-20 | 山东万盛新材料有限公司 | Preparation method of low-odor phosphate ester TCPP |
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