CN107629085A - A kind of post-processing approach of DECPP crude product - Google Patents
A kind of post-processing approach of DECPP crude product Download PDFInfo
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- CN107629085A CN107629085A CN201710847711.6A CN201710847711A CN107629085A CN 107629085 A CN107629085 A CN 107629085A CN 201710847711 A CN201710847711 A CN 201710847711A CN 107629085 A CN107629085 A CN 107629085A
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Abstract
The present invention relates to a kind of post-processing approach of DECPP crude product.Specific method is to add methanol into the crude product alcoholysis reaction occurs, secondary crude product alcoholysis in the crude product is formed to the byproduct for being dissolved in water, the crude product containing by-product is obtained, then the DECPP finished product of high-purity is obtained through alkali cleaning, washing, vacuum distillation.After the method processing of the present invention; the content of secondary crude product is reduced within 10PPM by 400 original 500PPM in crude product; through placing 5 days; daily finished product acid number increase is few; its protection period extends; it when obtained product is used for into the interior material such as automobile or furniture, can effectively drop low fogging, obtain the favor of consumers in general.
Description
Technical field
The invention belongs to fine chemical product purification technique field, and in particular to a kind of diethylene glycol chloropropyl phosphate is low
The post-processing approach of polymers crude product.
Background technology
DECPP is generally used for automotive interior material etc., due in automobile back temperature liter
Gao Shi, condensation phenomenon easily is produced in vehicle glass, makes vehicle glass smudgy, while unfavorable shadow is produced to health
Ring.But DECPP (vehicle economy CPP prepared by prior art）In all contain a certain amount of pair
Crude product, the accessory substance are easily atomized, and have impact on the quality of product, more shorten the storage life of product, therefore prepare low secondary crude product
DECPP be the purpose of the present invention.
The patents such as US3968187, US3976619, US4242288, JP48-96649A, JP8259577 describe diethyl two
Alcohol and phosphorus oxychloride reaction generation diethylene glycol are double（Phosphoryl chloride phosphorus oxychloride）Oligomer, then generate diethylene glycol with reacting ethylene oxide
It is double（Two-（Chloroethyl）Phosphate）Oligomer, these patents can produce this when not referring to and preparing DECPP with the method
Secondary crude product.
The B patents of CN 103408583 describe a kind of synthetic method of DECPP, mainly
The Dichloroethyl ether in product is reduced, this patent can produce above-mentioned secondary thick when not referring to and preparing DECPP with the method
Product, the structural formula such as formula of above-mentioned secondary crude product（Ⅰ）It is shown：
。
The content of the invention
The problem of existing for prior art, it is an object of the invention to design to provide a kind of diethylene glycol chloropropyl phosphoric acid
The post-processing approach of ester oligomer crude product, the pair in DECPP can be effectively removed by this method
Product.
The post-processing approach of described a kind of DECPP crude product, it is characterised in that thick to this
Methanol is added in product alcoholysis reaction occurs, the secondary crude product alcoholysis in the crude product is formed to the byproduct for being dissolved in water, obtained containing pair
The crude product of product, then the DECPP finished product of high-purity is obtained through alkali cleaning, washing, vacuum distillation,
The structural formula such as formula of the secondary crude product and byproduct（Ⅰ）And formula（Ⅱ）It is shown：
。
The post-processing approach of the DECPP crude product, it is characterised in that comprise the following steps
：
1）Methanol is added to DECPP crude product, is warming up to 30-55 DEG C, stirs 20-40 minutes, formula
（Ⅰ）Alcoholysis reaction production occurs for shown secondary crude product（Ⅱ）Shown byproduct, obtain the reaction solution containing byproduct；
2）To step 1）Sig water is added in obtained reaction solution, it is that 20-40 minutes are stirred at 50-60 DEG C to control temperature, then quiet
Put layering, branch vibration layer, organic layer is standby；
3）To step 2）Deionized water washing is added in obtained organic layer, controls and 20-40 minutes is stirred at 50-60 DEG C of temperature,
Stratification again, branch vibration layer, organic layer are standby；
4）By step 3）Obtained organic layer be evaporated under reduced pressure slough water and methanol to obtain finished product diethylene glycol chloropropyl phosphate low
Polymers finished product.
The post-processing approach of the DECPP crude product, it is characterised in that step 1）Middle diethyl
The mass ratio that feeds intake of glycol chloropropyl phosphoric acid ester oligomer crude product and methanol is 1:0.02-0.05.
The post-processing approach of the DECPP crude product, it is characterised in that step 2）In it is dilute
Alkali lye be 1-3% sig water, preferred concentration 1%.
The post-processing approach of the DECPP crude product, it is characterised in that step 2）In it is dilute
Alkali lye is 1% sodium carbonate liquor.
The post-processing approach of the DECPP crude product, it is characterised in that step 3）In water
Untill being washed till neutrality.
The post-processing approach of the DECPP crude product, it is characterised in that diethylene glycol chlorine third
Secondary content in crude product is 400-500ppm in base phosphoric acid ester oligomer crude product.
The post-processing approach of the DECPP crude product, it is characterised in that diethylene glycol chlorine third
Secondary content in crude product is less than 10ppm in base phosphoric acid ester oligomer crude product.
Due to eight circular ring structures in secondary crude product be present, the surface tension of eight annulus makes it be insoluble in water, is not easy to be hydrolyzed, but
It is that this secondary crude product is soluble in methanol, and alcoholysis reaction occurs for easy and methanol, generates byproduct soluble in water, the present invention is for being somebody's turn to do
Secondary crude product is easy to methanol and the characteristics of easily by alcoholysis, alcoholysis reaction occurs by adding methanol into the crude product, by the crude product
Secondary crude product alcoholysis formed and be dissolved in the byproduct of water, obtain the crude product containing by-product, then through alkali cleaning, wash, be evaporated under reduced pressure to
To the DECPP finished product of high-purity.The present invention is by using the above method, by eight circular ring structures
Secondary crude product make its open loop through processing, form the byproduct for being readily soluble in water, make DECPP thick
The content of secondary crude product is dropped to less than 10 PPM by original 400-500ppm in product, and through placing 5 days, daily finished product acid number increases
Add seldom, and secondary crude product is essentially unchanged in comparing embodiment, its acid number substantially increases, and atomization parameter of the invention is significantly high
In comparing embodiment, because than relatively for embodiment, after the method processing by the present invention, drastically increasing finished product
Quality, extend storage life, when obtained product is used for into the interior material such as automobile or furniture, can effectively drop low fogging, obtain
To the favor of consumers in general.
Embodiment
Below by way of following embodiments, comparing embodiment, the present invention is further illustrated, they are not to be construed as to the present invention
The limitation of protection domain.
The post-processing approach of the DECPP crude product of the present invention, comprises the following steps：
1）To DECPP crude product（Secondary content in crude product is 400-500ppm in the crude product）Add first
Alcohol, 30-55 DEG C is warming up to, stirs 20-40 minutes, formula（Ⅰ）Alcoholysis reaction production occurs for shown secondary crude product（Ⅱ）Shown
Byproduct, obtain the mass ratio that feeds intake of the reaction solution containing byproduct, DECPP crude product and methanol
For 1:0.02-0.05；
2）To step 1）Sig water is added in obtained reaction solution, it is that 20-40 minutes are stirred at 50-60 DEG C to control temperature, then quiet
Layering is put, branch vibration layer, organic layer is standby, and sig water is 1-3% sig water, preferred concentration 1%, is adopted in the embodiment of the present invention
Sig water is 1% sodium carbonate liquor；
3）To step 2）It is multiple that deionized water washing is added in obtained organic layer, untill being washed till reaction solution as neutrality, is washed every time
Control and stirred at 50-60 DEG C of temperature 20-40 minutes when washing, then stratification, branch vibration layer, organic layer are standby；
4）By step 3）Obtained organic layer be evaporated under reduced pressure slough water and methanol to obtain finished product diethylene glycol chloropropyl phosphate low
Polymers finished product, secondary content in crude product is less than 10ppm in finished product；The structural formula such as formula of the secondary crude product and byproduct（Ⅰ）And formula（Ⅱ）
It is shown：
。
Present invention analysis and test method explanation：
The assay of secondary crude product in DECPP crude product：Detected using gas chromatography (GC)；
The acid value measuring of DECPP：Using acid-base neutralization potentiometric titration；
DECPP storage life test method explanation：Take 100g diethylene glycol chloropropyl phosphates low
Polymers is added in beaker, is placed in baking oven and is warming up to 60 DEG C, higher every 24 hours sampling and testing its acid numbers, acid number, it was demonstrated that
Its storage life is shorter, and quality is relatively poor.
The preparation method of DECPP crude product of the present invention presses already known processes：Equipped with temperature
Meter, constant pressure funnel, mechanical agitator, reflux condenser and drying tube four-hole bottle in add POCl3, catalyst, it is cold
But to 10-15 DEG C, diethylene glycol is dripped off, after question response terminates, removes unreacted POCl3, is warming up to 50-55 DEG C, is added dropwise
Expoxy propane to PH 5-6, complete by insulation to reaction, obtains DECPP crude product, secondary crude product in crude product
Content is 492ppm；
Embodiment 1-4
500g crude products are taken, methanol 10g, 15g, 20g, 25g are sequentially added at 40 DEG C and carries out alcoholysis reaction, is stirred 30 minutes respectively
30 minutes are stood afterwards, obtains organic layer；500ml 1% sodium carbonate liquor is added in organic layer, stirs and is warming up to 55 DEG C, stir
30 minutes are stood after mixing 30 minutes, branch vibration layer, obtains organic layer；500ml deionized waters are added in organic layer to stir and heat up
To 55 DEG C, stirring stands 30 minutes after 30 minutes, branch vibration layer, repeats once above-mentioned water-washing step, PH is washed into
Property, branch vibration layer obtains organic layer, and by organic layer in vacuo dehydration and methanol, it is oligomeric to obtain diethylene glycol chloropropyl phosphate for filtering
Thing finished product.
Comparing embodiment
Take 500g crude products, add 500ml 1% sodium carbonate liquor, stir and be warming up to 55 DEG C, stirring stands 30 after 30 minutes
Minute, branch vibration layer, obtain organic layer；Add 500ml deionized waters in organic layer to stir and be warming up to 55 DEG C, 30 points of stirring
30 minutes are stood after clock, branch vibration layer, above-mentioned water-washing step is repeated once, PH is washed and obtains organic to neutrality, branch vibration layer
Layer, organic layer in vacuo is dehydrated, and is filtered, is obtained DECPP finished product.
The content of secondary crude product in the finished product that 1-4 of the embodiment of the present invention and comparing embodiment are obtained（GC is analyzed）, acid number（Through
Cross the analysis of acid-base neutralization potentiometric titration）, atomization（Detected using atomization measure instrument with the methods of PV 3015）And storage life test
（Survey the acid number of different time）As a result it is as shown in table 1.
The Comparative result table of the embodiment of table 1 and comparing embodiment
As known from Table 1, after processed by the invention, the content of secondary crude product is dropped to by original 400-500ppm and is less than in crude product
10 PPM, through placing 5 days, daily finished product acid number increase is few, and secondary crude product is essentially unchanged in comparing embodiment, and its acid number is obvious
Increase, atomization parameter of the invention is much higher than comparing embodiment, because than relatively for embodiment, by this hair
After bright method processing, the quality of finished product is drastically increased, extends storage life, obtained product is used for automobile or furniture
It during Deng interior material, can effectively drop low fogging, obtain the favor of consumers in general.
Claims (8)
1. a kind of post-processing approach of DECPP crude product, it is characterised in that added into the crude product
Alcoholysis reaction occurs for methanol, and the secondary crude product alcoholysis in the crude product is formed to the byproduct for being dissolved in water, obtained containing the thick of by-product
Product, then the DECPP finished product of high-purity is obtained through alkali cleaning, washing, vacuum distillation, it is described secondary thick
The structural formula of product and byproduct such as formula（Ⅰ）And formula（Ⅱ）It is shown：
。
2. the post-processing approach of DECPP crude product according to claim 1, it is characterised in that
Comprise the following steps：
1）Methanol is added to DECPP crude product, is warming up to 30-55 DEG C, stirs 20-40 minutes, formula
（Ⅰ）Alcoholysis reaction production occurs for shown secondary crude product（Ⅱ）Shown byproduct, obtain reaction solution containing byproduct；
2）To step 1）Sig water is added in obtained reaction solution, it is that 20-40 minutes are stirred at 50-60 DEG C to control temperature, then quiet
Put layering, branch vibration layer, organic layer is standby；
3）To step 2）Deionized water washing is added in obtained organic layer, controls and 20-40 minutes is stirred at 50-60 DEG C of temperature,
Stratification again, branch vibration layer, organic layer are standby；
4）By step 3）Obtained organic layer be evaporated under reduced pressure slough water and methanol to obtain finished product diethylene glycol chloropropyl phosphate low
Polymers finished product.
3. the post-processing approach of DECPP crude product according to claim 2, it is characterised in that
Step 1）The mass ratio that feeds intake of middle DECPP crude product and methanol is 1:0.02-0.05.
4. the post-processing approach of DECPP crude product according to claim 2, it is characterised in that
Step 2）In sig water be 1-3% sig water, preferred concentration 1%.
5. the post-processing approach of DECPP crude product according to claim 2, it is characterised in that
Step 2）In sig water be 1% sodium carbonate liquor.
6. the post-processing approach of DECPP crude product according to claim 2, it is characterised in that
Step 3）In be washed to neutrality untill.
7. the post-processing approach of DECPP crude product according to claim 2, it is characterised in that
Secondary content in crude product is 400-500ppm in DECPP crude product.
8. the post-processing approach of DECPP crude product according to claim 2, it is characterised in that
Secondary content in crude product is less than 10ppm in DECPP crude product.
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|---|---|---|---|
| CN201710847711.6A CN107629085B (en) | 2017-09-19 | 2017-09-19 | Post-treatment method of diethylene glycol chloropropyl phosphate oligomer crude product |
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| CN201710847711.6A CN107629085B (en) | 2017-09-19 | 2017-09-19 | Post-treatment method of diethylene glycol chloropropyl phosphate oligomer crude product |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968187A (en) * | 1972-12-26 | 1976-07-06 | Monsanto Company | Flame retardant haloalkyl esters of glycols |
| JP2010235553A (en) * | 2009-03-31 | 2010-10-21 | Kuraray Medical Inc | Phosphate ester compound and polymerizable composition containing the same |
| CN102010586A (en) * | 2010-11-29 | 2011-04-13 | 浙江万盛化工有限公司 | Phosphate flame retardant for urethane foams and synthesis method of phosphate flame retardant |
| CN103408583A (en) * | 2013-07-30 | 2013-11-27 | 浙江万盛股份有限公司 | DECPP preparation method |
-
2017
- 2017-09-19 CN CN201710847711.6A patent/CN107629085B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968187A (en) * | 1972-12-26 | 1976-07-06 | Monsanto Company | Flame retardant haloalkyl esters of glycols |
| JP2010235553A (en) * | 2009-03-31 | 2010-10-21 | Kuraray Medical Inc | Phosphate ester compound and polymerizable composition containing the same |
| CN102010586A (en) * | 2010-11-29 | 2011-04-13 | 浙江万盛化工有限公司 | Phosphate flame retardant for urethane foams and synthesis method of phosphate flame retardant |
| CN103408583A (en) * | 2013-07-30 | 2013-11-27 | 浙江万盛股份有限公司 | DECPP preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 姚成 等: "四-(2-氯乙基)乙撑二磷酸酯和二乙二醇双[二-(2-氯乙基)]磷酸本的合成与应用", 《江苏化工》 * |
| 李培国 等: "低聚磷酸酯阻燃剂合成的研究", 《现代化工》 * |
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