CN100357301C - N,N'-di (diphenyl phosphate) piperazines flame retardants and process for preparing same - Google Patents
N,N'-di (diphenyl phosphate) piperazines flame retardants and process for preparing same Download PDFInfo
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- CN100357301C CN100357301C CNB2005100516995A CN200510051699A CN100357301C CN 100357301 C CN100357301 C CN 100357301C CN B2005100516995 A CNB2005100516995 A CN B2005100516995A CN 200510051699 A CN200510051699 A CN 200510051699A CN 100357301 C CN100357301 C CN 100357301C
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- piperazine
- diphenyl phosphate
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- phosphorus oxychloride
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Abstract
The present invention relates to an N, N-bi-(diphenyl phosphate) piperazine flame retardant and a preparing method thereof. The method comprises the steps that phosphorus oxychloride reacts with phenol to generate chloro diphenyl phosphate; chloro diphenyl phosphate then reacts with piperazine in a water solution containing inorganic carbonate to synthesize N, N-bi-(diphenyl phosphate) piperazine. The present invention has the most obvious characteristic that an organic solvent is replaced by water in the reaction in the second step so that the water is used as a medium; organic amine is replaced by inorganic carbonate so that the inorganic carbonate is used as an absorbent of hydrogen chloride gas; the yield reaches 80 %.
Description
Technical field
The present invention relates to a kind of N, N '-two (diphenyl phosphate) piperazines flame retardants.
The invention still further relates to the preparation method of above-mentioned fire retardant, by the synthetic and chlorinated diphenyl phosphate and the piperazine reaction generation N of chlorinated diphenyl phosphate, two steps of N '-two (diphenyl phosphate) piperazine are formed.The characteristics of this method are that second step was reflected in the aqueous solution that contains mineral alkali and carries out, and have avoided the use of a large amount of organic solvents and the multistep separation and purification operation of product, have eco-friendly characteristics.
Background technology
Phosphate compounds is widely used as various fire retardants, wherein based on the diphenyl phosphate compounds of piperazine be exactly the important phosphorus nitrogen of a class be inflammable resin fire retardant.
About N, the existing relevant bibliographical information of the synthetic method of N '-two (diphenyl phosphate) piperazine compounds is seen J.Chem.Soc. (C) 1971,3614 and J.Chem.Eng.Data 1988,33,221.The former be about diphenyl phosphate and Piperazine anhydrous in the presence of triethylamine, reaction makes N in tetracol phenixin, N '-two (diphenyl phosphate) piperazine, reaction yield has only 30%, and has used the very big tetracol phenixin of toxicity; The latter has reported that chloro di(2-ethylhexyl)phosphate (2, the 6-xylyl) ester and Piperazine anhydrous react synthetic N in the presence of triethylamine and organic solvent, N '-two [di(2-ethylhexyl)phosphate (2, the 6-xylyl) ester] piperazine, and yield is about 68%.United States Patent (USP) (US 6,569,929) has been reported chloro di(2-ethylhexyl)phosphate (2 recently, the 6-xylyl) ester and Piperazine anhydrous prepare N in the presence of triethylamine and a large amount of methylene dichloride, N '-two [di(2-ethylhexyl)phosphate (2, the 6-xylyl) ester] piperazine, the highest yield reaches more than 90%.However, still there are some shortcomings of original organic solvent method in this technology, the one, reaction must need to carry out in a large amount of organic solvents, give the recovery of solvent bring difficulty with and caused the potential threat to environment; The 2nd, need to use a large amount of organic bases triethylamines to absorb the hydrogen chloride gas of generation, increased the product separation purification process.
Along with of the increase of poly-resin industry to nitrogen phosphorus flame retardant demand, be necessary that the exploitation system is simple, easy and simple to handle, the new synthetic process of this compounds with low cost.
Summary of the invention
The object of the present invention is to provide a kind of N, N '-two (diphenyl phosphate) piperazines flame retardants.
Another object of the present invention is to provide the preparation method of the above-mentioned fire retardant of preparation.
For achieving the above object, N provided by the invention, N '-two (diphenyl phosphate) piperazines flame retardants, its structural formula is as follows:
The method of the above-mentioned fire retardant of preparation provided by the invention is to realize by two-step reaction, at first synthesize chlorinated diphenyl phosphate (shown in 1 in suc as formula 1) by phosphorus oxychloride and phenol under Lewis acid effect, chlorinated diphenyl phosphate reacts in the aqueous solution in the presence of inorganic carbonate with piperazine and obtains purpose compound (shown in 2 in suc as formula 2):
Specifically, the present invention prepares the method for above-mentioned fire retardant and is:
A) phosphorus oxychloride and phenol are with mol ratio 1: 1-2 mixes, and adds the 0.8-5g Lewis acid by every mole of phosphorus oxychloride again, in 90-200 ℃ of reaction 0.5-10 hour, collects the cut of 160-180 ℃/1-5mmHg.
B) compound concentration is the aqueous solution of 0.2-1.0mol/500ml yellow soda ash or salt of wormwood, and with the product of step a and piperazine in molar ratio 1: 0.5-1 is dissolved in the alkali aqueous solution, in 0-100 ℃ of reaction 0.1-5 hour, is washed to neutrality, after the drying target product.
For achieving the above object, Lewis acid of the present invention is aluminum trichloride (anhydrous), chlorates such as Magnesium Chloride Anhydrous.
To achieve these goals, phosphorus oxychloride and phenol bulk reaction make diphenyl phosphate, and the amount of phosphorus oxychloride and phenol are suitable even excessive, excessively help the carrying out that react, but the big excessive operation that will increase the separation and purification product.Described phenol is phenol or 2, the 6-xylenol.
To achieve these goals, for the very high or solid-state diphenyl phosphate of boiling point, phosphorus oxychloride and phenol reaction can interpolation organic solvent is beneficial to the carrying out that react, and solvent is a dimethylbenzene, aromatic hydrocarbons or its mixtures such as trimethylbenzene.Add-on adds 15-20g by every mole of phosphorus oxychloride.
To achieve these goals, phosphorus oxychloride and phenol are reflected at 90-200 ℃ to carry out, and the reaction times is 0.5-10 hour; Extent of reaction is determined by TLC (tlc) or GLC (gas-liquid chromatography) that specifically if the reaction times is not enough, substrate phenol does not just fully transform, and the reaction times is long, is easy to generate the by product phosphotriester.
To achieve these goals, chlorinated diphenyl phosphate and piperazine react in the aqueous solution; For the hydrogenchloride that absorption reaction produces, need to add the balance of alkali with maintenance system.Used alkali is inorganic carbonates such as yellow soda ash, salt of wormwood.
To achieve these goals, the used piperazine of the present invention can be Piperazine anhydrous, three water piperazines, six or five piperazines or contains the aqueous solution of piperazine, but the purity of all piperazines should be less than 95%.
To achieve these goals, chlorinated diphenyl phosphate for liquid, the aqueous solution that can directly be added drop-wise to piperazine reacts, for being the solid chlorinated diphenyl phosphate under the room temperature, preferably use and be with the feeding device of heating so that its fusing back dropping, perhaps add proper amount of solvent dissolving back and react in being added drop-wise to the aqueous solution of piperazine, solvent can steam when dropwise reaction, steams after also can dropwise reaction finishing again.
To achieve these goals, used chlorinated diphenyl phosphate is 0.5-1 with the ratio of the molar weight of piperazine, and piperazine is excessive slightly to help the carrying out that react, but can not be excessive a lot, otherwise easily generates single substitution compound.
To achieve these goals, being reflected between 0-100 ℃ of chlorinated diphenyl phosphate and piperazine carried out, and suitably heating helps inorganic carbonate and the solvability of piperazine in water, is preferably 20-60 ℃.To achieve these goals, the reaction times of chlorinated diphenyl phosphate and piperazine is 0.1-5 hour, is preferably 1-3 hour.
The present invention has the following advantages:
1. the reaction of second step substitutes organic solvent as reaction medium with water, has avoided VOC (volatile organic compounds) to pollute, and has eco-friendly characteristics;
2. replace organic bases such as triethylamine as the hydrogen chloride gas absorption agent in the second step reaction with inorganic carbonate, not only reduce cost but also simplified operation;
3. the raw material piperazine scope of application is very wide, can be for Piperazine anhydrous, contain the crystal water piperazine or contain the aqueous solution of piperazine, and the conventional organic solvents method is necessary for Piperazine anhydrous;
4. the second step reaction conditions gentleness is carried out in the thermotonus of room temperature to 60 ℃;
5. second step reaction technique is simple, and is easy to operate, reaction finish the back only need through filtration, washing and drying get final product product, saved the operations such as solvent distillation, product extracting and recrystallization in the organic solvent technology;
6. the yield of this technology is higher.
Embodiment
Help to understand the present invention by following embodiment, but content of the present invention do not limit therewith, wherein each embodiment is made up of two-step reaction: synthetic (formula 1) and the N of a chlorine phosphoric acid ester, and synthetic (formula 2) of N '-two (diphenyl phosphate) piperazine:
Embodiment 1
In a 1000mL four-hole bottle (prolong of mechanical stirring, thermometer, connection HCl gas absorbing device and reinforced), add phosphorus oxychloride (1.0mol) and aluminum trichloride (anhydrous) (0.84g), be warming up to 90 ℃ gradually, add phenol (2.0mol) in batches, emit a large amount of HCl gas simultaneously, reaction is 1 hour about 105 ℃, till no HCl gas is emitted, get filbert solution, steam not reacted raw material earlier, front-end volatiles are removed in underpressure distillation again, collect the cut of 172 ℃/5mmHg, get the 507g chlorinated diphenyl phosphate, yield is 75.5%;
Add anhydrous sodium carbonate (0.81mol) and water (360mL) in the 3000mL four-hole bottle, add Piperazine anhydrous (0.41mol) after the stirring and dissolving, stir and begin to drip chlorinated diphenyl phosphate (0.81mol) after 20 minutes, separate out the solid of white simultaneously, dropwised in about 2 hours, continue reaction 2 hours under the room temperature, suction filtration, filter cake wash with water to neutrality, at last with cold normal hexane washing, the moisture in the product is removed in vacuum-drying, gets white products 217.4g, and yield is 97.8%.
Embodiment 2
After phenol (11mol) all joined phosphorus oxychloride (5.5mol) and aluminum trichloride (anhydrous) (4.62g) in batches, 95 ℃ of reactions 0.5 hour, yield was 71.2%; The reaction of second step is with embodiment 1.
Embodiment 3
The first step reaction is with embodiment 1; Substitute anhydrous sodium carbonate with Anhydrous potassium carbonate in the reaction of second step, yield is 78.3%.
Embodiment 4
The first step reaction is with embodiment 1; Substitute Piperazine anhydrous with three water piperazines in the reaction of second step, yield is 81.5%.
Embodiment 5
The first step reaction is with embodiment 1; Substitute Piperazine anhydrous with six or five piperazines in the reaction of second step, yield is 73.6%.
Embodiment 6
The first step reaction is with embodiment 1; The piperazine aqueous solution with 30% in the reaction of second step substitutes Piperazine anhydrous, 0 ℃ of temperature of reaction, and yield is 64.7%.
Embodiment 7
The first step reaction is with embodiment 1; Earlier the aqueous solution is heated to 50 ℃ in the reaction of second step with dissolving yellow soda ash and piperazine, all the other are with embodiment 1, and yield is 89.0%.
Embodiment 8
In a 2000mL four-hole bottle, add 2,6-xylenol (6.0mol), Magnesium Chloride Anhydrous (6.72g) and dimethylbenzene (60g), be heated to 115 ℃ and be stirred to 2, after the 6-xylenol all melts, begin to drip phosphorus oxychloride (3.26mol), needed dropwise in 4 hours approximately, continue back flow reaction, TLC or GLC follow the tracks of reaction simultaneously, need reaction in 10 hours to finish approximately, get brown solution, steam solvent and not reacted phosphorus oxychloride earlier, front-end volatiles are removed in underpressure distillation again, collect the cut 671.5g of 165 ℃/1mmHg, yield is 63.4%;
In the four-hole boiling flask of a 500mL, add Piperazine anhydrous (0.1mol), anhydrous sodium carbonate (0.2mol) and water (500mL), be heated to 100 ℃ of stirrings and make piperazine and yellow soda ash dissolving, stir and drip chloro di(2-ethylhexyl)phosphate (2 down, the 6-xylyl) dichloromethane solution (50mL) of ester (0.1mol), dropwise the back and continue reaction 1 hour, and then steam methylene dichloride, white solid is separated out in cooling, and suction filtration washes with water to neutrality, at last with cold normal hexane washing, the infrared lamp drying gets white products 43.0g, and yield is 64.9%.
Embodiment 9
The first step reaction is with embodiment 8; When making solvent with the substituted ether methylene dichloride in the second step reaction, the 47.0g product, yield is 70.9%.
Embodiment 10
In a 2000mL four-hole bottle, add 2,6-xylenol (6.0mol), Magnesium Chloride Anhydrous (6.72g) and dimethylbenzene (60g), be heated to 115 ℃ and be stirred to 2, after the 6-xylenol all melts, begin to drip phosphorus oxychloride (3.26mol), needed dropwise in 4 hours approximately, continue back flow reaction, TLC or GLC follow the tracks of reaction simultaneously, need reaction in 10 hours to finish approximately, get brown solution, steam solvent and not reacted phosphorus oxychloride earlier, front-end volatiles are removed in underpressure distillation again, collect the cut 671.5g of 165 ℃/1mmHg, yield is 63.4%;
In the four-hole boiling flask of a 500mL, load onto mechanical stirring, thermometer, constant pressure funnel and water distilling apparatus, add Piperazine anhydrous (0.1mol), anhydrous sodium carbonate (0.2mol) and water (500mL), be heated to 60 ℃ of stirrings and make piperazine and yellow soda ash dissolving, stir and drip chloro di(2-ethylhexyl)phosphate (2 down, the 6-xylyl) diethyl ether solution (50mL) of ester (0.1mol) is separated out white precipitate at once, steams ether simultaneously, dropwise the back and continue reaction 1 hour, cooling, suction filtration washes with water to neutrality, at last with cold normal hexane washing, the infrared lamp drying gets white products 51.0, and yield is 76.9%.
Embodiment 11
In a 2000mL four-hole bottle, add 2,6-xylenol (4.0mol), Magnesium Chloride Anhydrous (10.8g) and phosphorus oxychloride (2.1mol), be heated to 200 ℃, there is HCl gas to emit, TLC or GLC follow the tracks of reaction simultaneously, need reaction in 5 hours to finish approximately, get brown solution, steam solvent and not reacted phosphorus oxychloride earlier, front-end volatiles are removed in underpressure distillation again, collect the cut 575g of 165 ℃/1mmHg, be solidified as white solid under the room temperature immediately, yield is 88.5%, the GC normalization method is analyzed, and purity is 97%;
Second step reacted with embodiment 10,0.1 hour reaction times.
Claims (6)
1. one kind prepares N, the method of N '-two (diphenyl phosphate) piperazines flame retardants, react under the Lewis acid effect by phosphorus oxychloride and phenol earlier and generate chlorinated diphenyl phosphate, chlorinated diphenyl phosphate reacts synthetic N with piperazine again in containing the inorganic carbonate salt brine solution, N '-two (diphenyl phosphate) piperazine, concrete steps are:
A) phosphorus oxychloride and phenol are with mol ratio 1: 1-2 mixes, and adds the 0.8-5g Lewis acid by every mole of phosphorus oxychloride again, in 90-200 ℃ of reaction 0.5-10 hour, collects the cut of 160-180 ℃/1-5mmHg; Described phenol is phenol or 2, the 6-xylenol;
B) compound concentration is the aqueous solution of 0.2-1.0mol/500ml yellow soda ash or salt of wormwood, with the product of step a and piperazine in molar ratio 1: 0.5-1 is dissolved in the aqueous solution of aforementioned yellow soda ash or salt of wormwood, in 0-100 ℃ of reaction 0.1-5 hour, be washed to neutrality, get target product after the drying;
The structural formula of this target product is as follows:
In the formula, R
1Be hydrogen or C
1～C
6Alkane, R
2Be hydrogen or C
1～C
6Alkane.
2. according to the preparation method of claim 1, it is characterized in that, add the dimethylbenzene of 15-20g or/and trimethylbenzene by every mole of phosphorus oxychloride among the step a.
3. according to the preparation method of claim 1, it is characterized in that described Lewis acid is aluminum trichloride (anhydrous) or Magnesium Chloride Anhydrous.
4. according to the preparation method of claim 1, it is characterized in that described piperazine is Piperazine anhydrous, three water piperazines, six or five piperazines or the aqueous solution that contains piperazine.
5. according to the preparation method of claim 1, it is characterized in that temperature of reaction is 20-60 ℃ among the step b.
6. according to the preparation method of claim 1, it is characterized in that the reaction times is 1-3 hour among the step b.
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| CNB2005100516995A CN100357301C (en) | 2005-03-01 | 2005-03-01 | N,N'-di (diphenyl phosphate) piperazines flame retardants and process for preparing same |
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| CNB2005100516995A CN100357301C (en) | 2005-03-01 | 2005-03-01 | N,N'-di (diphenyl phosphate) piperazines flame retardants and process for preparing same |
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| KR20140097367A (en) * | 2011-11-15 | 2014-08-06 | 바스프 에스이 | P-piperazine compounds as flame retardants |
| CN102558228B (en) * | 2011-12-19 | 2013-10-16 | 和夏化学(太仓)有限公司 | Process for preparing diphenyl diphenoxy phosphoryl aniline compound |
| CN106588986A (en) * | 2016-10-28 | 2017-04-26 | 深圳瑞隆新能源科技有限公司 | High-safety lithium ion battery diaphragm fire retardant, and preparation method and application thereof |
| CN106995535A (en) * | 2017-04-18 | 2017-08-01 | 三峡大学 | A kind of preparation method and applications of the bis phosphoric acid phenyl ester phosphorus nitrogen synergistic fire retardant of the phosphonitrile containing ring three |
| CN107652324B (en) * | 2017-09-22 | 2019-09-24 | 东北林业大学 | Three-source-in-one expansion type fire retardant and its synthetic method and application |
| CN109942824B (en) * | 2019-04-18 | 2021-07-09 | 黑龙江科技大学 | A kind of nitrogen-containing phosphonate flame retardant and its synthesis method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH10175985A (en) * | 1996-12-17 | 1998-06-30 | Tosoh Corp | Nitrogen-containing organic phosphoric acid compound and flame-retardant resin composition containing the same |
| WO2003035965A1 (en) * | 2001-10-19 | 2003-05-01 | Daikyo Chemical Co., Ltd. | Flameproofing agent for polyester-based textile product and method of flameproofing |
| US6569929B2 (en) * | 1999-01-22 | 2003-05-27 | General Electric Company | Method to prepare phosphoramides, and resin compositions containing them |
-
2005
- 2005-03-01 CN CNB2005100516995A patent/CN100357301C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10175985A (en) * | 1996-12-17 | 1998-06-30 | Tosoh Corp | Nitrogen-containing organic phosphoric acid compound and flame-retardant resin composition containing the same |
| US6569929B2 (en) * | 1999-01-22 | 2003-05-27 | General Electric Company | Method to prepare phosphoramides, and resin compositions containing them |
| WO2003035965A1 (en) * | 2001-10-19 | 2003-05-01 | Daikyo Chemical Co., Ltd. | Flameproofing agent for polyester-based textile product and method of flameproofing |
Non-Patent Citations (3)
| Title |
|---|
| Preparation of sterically hindered phosphoramidates.. Talley,John J.J. Chem. Eng. Data,Vol.33 No.2. 1988 * |
| 有机磷阻燃剂研究进展 王新龙，韩平.精细石油化工进展，第3卷第6期 2002 * |
| 非卤膨胀型阻燃剂研究发展 张传梅.河南化工，第3卷 1999 * |
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