CN1022106C - Preparation process of phosphotriaromatic ester - Google Patents
Preparation process of phosphotriaromatic ester Download PDFInfo
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- CN1022106C CN1022106C CN 89106790 CN89106790A CN1022106C CN 1022106 C CN1022106 C CN 1022106C CN 89106790 CN89106790 CN 89106790 CN 89106790 A CN89106790 A CN 89106790A CN 1022106 C CN1022106 C CN 1022106C
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Abstract
The present invention relates to a preparation process of phosphoric tri-aromatic ester in organic synthesis. In the process, phenol or a homologous compound of phenol and phosphorus oxychloride are severely stirred in the existence of a 20% NaOH water solution and a small amount of toluene, and materials are fed in two steps or multiple steps; after a reaction at the temperature of 25 DEG C, the reaction continues with the temperature increased by 50 to 60 DEG C; and through the technology of decompression, dehydration and the like, nearly 90% of phosphoric tri-aromatic ester with the quality sufficient for use in film is finally obtained.
Description
The invention belongs to the preparation technology of the relevant tri aromatic ester of phosphic acid in the organic synthesis.
Tri aromatic ester of phosphic acid (typical in triphenylphosphate, front three phenyl ester, three diformazan phenyl esters etc.) is a class important chemical product, is extensively used as softening agent, fire retardant, lubricant, functional fluid etc.Phenol or its homologue and phosphorus oxychloride (POCl are generally adopted in the production of this series products
3) technology of in the presence of high temperature and catalyzer, carrying out esterification.This technological process has than distinct disadvantage, as temperature of reaction up to 150-300 ℃, reaction times reached more than 8 hours, and yield is only at 70-80% and need under the excessive situation of phenol, because of emitting the generation that HCl and pyroreaction easily cause the reaction product variable color or cause by product in the reaction process, event needs the refining side of distillation to get qualified product, and simultaneously, the HCl that reaction is emitted easily causes the corrosion of equipment.
W.ter Horst and W.Autenrieth once proposed by phenol or its homologue and POCl in patent (U.S.P1,837,176) and report (Chem.Ber., 30,2369(1933)) respectively
3At (the former is also in the presence of a small amount of organic solvent) corresponding phosphoric acid ester of prepared in reaction in the presence of the NaOH aqueous solution, can make to be reflected at than carrying out under the mild conditions, but yield is all lower, only reaches 60-75%, so be unsuitable for industrial-scale production.The reason that reaction yield is not high is POCl
3Easily by the part or all of hydrolysis of the NaOH aqueous solution, hydrolysate can not further generate phosphoric acid ester with the phenols reaction under the reaction conditions of being taked.
H.Selbeck in 1979 etc. apply for a patent (U.S.P4,267,127) improvement have been done in above-mentioned reaction, and mainly the once adding with reaction mass changes secondary or repeatedly adding into, makes phenol or its homologue and POCl
3In the presence of the 20%NaOH aqueous solution and small amount of toluene, in quick stirring and keep under the 18-25 ℃ of temperature and react, that continues reacted under 25 ℃ 30 minutes again, after toluene, water and the steaming of unreacted phenols remove in the organic phase, residuum it is said and the phosphoric acid ester yield can be brought up to more than 90% without any refining promptly as product.Yet this patent author has ignored the detection to quality product, in fact, can not guarantee quality product by the described synthetic method of this patent, contains a large amount acidic substance in the products therefrom and (is obvious acidity, n as phosphoric acid phenol ester product
45 DBe generally 1.5540-1.5550, and with prolonging storage period, darken, acidity is strong more, n
45 DMore decline) do not meet industrial reagent standard; As making product reach the reagent index by refining means, then the product actual recovery of the described method of this patent mostly is about 70% most.We think that this result is reflected at because of this patent is described also to fail under the used condition fully to carry out and product causes without refining.
The object of the invention be to provide one can really overcome the old technology shortcoming, product yield is higher and new preparation process that quality is good.
Technology of the present invention mainly is made up of following process: make phenol or its homologue and POCl
3In the presence of the 20%NaOH aqueous solution and small amount of toluene, vigorous stirring and keeping under 18-28 ℃, in two steps or multistep add reaction mass and react, reaction solution continues reaction after 30 minutes in 25 ℃, improve temperature again to 50-60 ℃ of reaction 30 minutes, organic phase steamed down in decompression dewater, behind toluene and unreacted phenol and a small amount of by product, the NaOH aqueous solution and distilled water with 5-0.1% washs residuum down in 60 ℃ respectively, at last in 100 ℃ of following decompression dehydrations, then finally obtain the high-quality phosphoric acid aromatic ester of-90% yield, as triphenylphosphate product, n
45 DReach 1.5563, every index all reaches film and uses the level level.
The present invention confirms, takes to make reaction solution to continue reaction 30 minutes and with the measure of alkali liquid washing crude product, for guaranteeing that sufficient reacting carries out, improve product yield and guarantee that quality product is indispensable in 50-60 ℃ in the described technology.The action principle of these measures is that the former can make the intermediate product that contains chlorine or dichloro phosphoric acid phenol ester in the reaction fully transform, and reacts fully and carries out; The latter can make crude product be removed any acidic impurities, thereby guarantees that whole technology obtains best product with high yield high quality.
Technology of the present invention can apply to the preparation of a series of products, as triphenylphosphate, front three phenyl ester, three diformazan phenyl esters, tri-isopropyl benzene ester and three aromatic ester of the mixed type between them etc.
The optimum range of adoptable reaction mass proportioning and reaction conditions is in the technology of the present invention:
In the reaction, every mol phenolic compound uses the preferably normal phosphorus halide of 1-1.2 mol (using 1-1.2 molar Phosphorus Oxychloride as per 3 molar phenolic compounds) of 1-1.3 mol equivalent.
In the reaction, every normal phosphorus halide uses the preferably normal sodium hydroxide of 1-1.2 of 1-1.4 equivalent, and its concentration of aqueous solution is preferably in the preferable 10-30% of the being weight concentration of the 5-50% scope.
The 30-1500% that the usage quantity of toluene is preferably calculated based on phosphorus halide weight is more preferably in the 50-1000% weight range.
Reaction mass reacts with two steps or multistep adding.As the phenolic compound that makes full dose earlier with 30-95%(50-90% preferably) the NaOH solution and the Phosphorus Oxychloride solution reaction of expense, then with remaining 5-70%(10-50% preferably) NaOH solution and Phosphorus Oxychloride solution in second step, add (this is a two-step reaction) in regular turn, or residual content is divided into several shares alternately adds (this is polystep reaction), in most cases, two-step reaction is enough to reach-90% high yield, for the purpose of economy, the reaction be no more than usually five the step carry out.In reaction process, the pH value of solution value preferably remains in the 7.5-13.5 scope, and this can guarantee that successful reaction carries out and avoid emitting HCl causing equipment corrosion.
Temperature of reaction when adding material can be preferably in the 20-30 ℃ of scope and carry out in 0 ℃ of-40 ℃ of scope.The reaction required time is very short, in most cases reacts through 5-60 minute promptly to accuse and finishes.
The characteristics of the inventive method be reaction mass room temperature keep the reaction 30 minutes after, then bring up to 50-80 ℃, preferably at 50-60 ℃, reacted again 30 fens; After removing organic phase under reduced pressure water, toluene, a small amount of unreacted phenols and a small amount of by product, to residuum execute again (the NaOH strength of solution is at 0.1-5% with alkali cleaning, be preferably in the 0.5-1% weight concentration scope), purification step such as washing, decompression dehydration, obtain higher yields (90%) thus, the phosphoric acid aromatic ester product of better quality.
Processing method provided by the invention is produced former technology with phosphoric acid ester and has been compared following characteristics: 1. temperature of reaction low (20-30 ℃), reaction times short (1-2 hour), reaction conditions gentleness, extensive, available industrial goods raw material; 2, reaction is simple, and by product is few, and is easily separated refining, and the quality product height uses the level level as the very easy film that reaches of tri aromatic ester of phosphic acid product; 3. can exempt product distillation purification step, save energy and time; 4. yield can improve about 10% and need not emphasize that phenol is excessive; 5. exempt HCl and emit, avoid equipment corrosion.
Embodiment provided by the invention is as follows:
Embodiment 1:
Is furnished with dropping funnel one, add 282.3 gram (3 mol) phenol and 512 gram 20%NaOH(2.56 mol in the there-necked flask of electronic stirring and thermometer) solution and 100 gram toluene, under vigorous stirring and good cooling, in 30 minutes, be added dropwise to 123 gram POCl
3(0.8 mol) solution in 300 gram toluene is kept temperature of reaction therebetween at 18-25 ℃, again with 128 gram 20%NaOH(0.64 mol) solution and 30.6 gram POCl
3(0.2 mol) solution in 100 gram toluene successively added in 5 minutes, make reaction solution continue to stir 30 minutes in 25 ℃, then bring up to 50-60 ℃ of reaction 30 minutes again, more than in each step reaction reacting phase keep alkalescence always, tell organic layer, give a baby a bath on the third day after its birth with distilled water and time can reach neutrality, decompression steams water, toluene, a small amount of unreacted phenol from organic phase down, and continue to steam except that a small amount of by product (5mmHg post), end for 220 ℃ up to bottle Nei Wenduda, residue oily transparency 298 grams (thick yield 91.3%, n in the bottle
45 D1.5561), with crude product with 300ml1%NaOH solution in 60 ℃ of down washings 1 hour, again with 60 ℃ of 300ml0.5%NaOH solution washing half an hour down, washed 10 minutes with under 60 ℃ of the 300ml distilled water at every turn, reach neutrality through three times; Decompression (5mmHg) dehydration is final that water white transparency (cold after coagulation) product 294 restrains yield 90.0%, n down in 100 ℃ again
45 D1.5563 all other indexs all meet or exceed film and use level level (seeing Table 1).
Embodiment 2:
In device described in the embodiment 1, add 324.3 gram (3 mol) M-and P-cresols (m: p=45: 55) and 528 gram 20%NaOH(2.64 mol) solution and 100 gram toluene, under vigorous stirring and good cooling, in 30 minutes, be added dropwise to 123 and restrain POCl
3(0.8 mol) solution in 300 gram toluene is kept temperature of reaction therebetween at 20-28 ℃, again with 132 gram 20%NaOH(0.66 mol) solution and 30.6 gram POCl
3(0.2 mol) solution in 100 gram toluene successively added in 5 minutes, made reaction solution continue to stir 30 minutes in 25 ℃, then brought up to 50-60 ℃ again.Reacted 30 minutes, more than in each step reaction reacting phase all keep alkalescence.Tell organic layer, give a baby a bath on the third day after its birth with distilled water and time can reach neutrality, decompression down (5mmHg post) steam from organic phase dewater, toluene, a small amount of unreacted phenol, and continue to steam except that a small amount of by product, end for 230 ℃ up to bottle Nei Wenduda, residuum in the bottle was washed 1 hour down in 60 ℃ with 300ml1%NaOH solution, wash half an hour down for 60 ℃ with 300ml10.5%NaOH solution, washed 10 minutes with under 60 ℃ of the 300ml distilled water at every turn, reach neutrality through three times; Again in 100 ℃ of (5mmHg) dehydrations of reducing pressure down, the final transparent oily product of little Huang that gets, 328.5 grams, yield 89.2%, n
20 D1.5580 quality meets industrial first grade index (seeing Table 1).
The character of the part tri aromatic ester of phosphic acid that table 1 makes with technology of the present invention
Product yield refractive index appearance luster zero pour acid number free phenol flash-point
% （Pt-Co） ℃ mgKOH/g % ℃
n
45 D
Triphenylphosphate 90.0 1.5563 white crystals 20 48.5 0.012 0.071
(white crystals≤80 47-49≤0.10≤0.10) ※
n
45 D
Tritolyl Phosphate 89.2 1.5580 little butter shapes 200 0.024 0.017 239
(little butter shape≤250≤0.15≤0.20 〉=220) ※ ※
※ is that the triphenylphosphate cinefilm uses the level performance index
※ ※ is the performance index of Tritolyl Phosphate industry first grade
Table 2 has been listed and has been implemented the mixed phenolic ester of tricresyl phosphate that 3-6 makes to be similar to embodiment 1,2 described methods, tricresyl phosphate isopropyl benzene ester, phosphoric acid benzene toluene mixed ester, the result of phosphoric acid benzene isopropyl benzene mixed ester.
Other tri aromatic ester of phosphic acid example of table 2
Embodiment phenolic compound phosphoric acid aromatic ester material proportion yield quality
Second step of the first step
(adjacent METHAPHOSPHORIC ACID three is mixed phenolic ester 3 mol mixture cresols 0.64 molecule NaOH 84 √ to 3 mixture cresols
Phenol: 2.6 mol NaOH20%, 0.2 mol POCl xylenol)
3
1: 1 0.8 mol POCl
3/ 100 gram toluene
/ 500 gram toluene
The different 3 mol isopropyl benzene phenol of 4 m-isopropyl benzene phenol tricresyl phosphates 0.62 mol NaOH 90 √
Propyl benzene ester 2.48 mol NaOH20% 0.2 mol POCl
3
0.8 mol POCl
3/ 100 gram toluene
/ 500 gram toluene
5 phenol cresylol di(2-ethylhexyl)phosphate phenol, 2 mol phenol, 1 gram, 0.64 mol NaOH, 89 √
(m: p=45: cresylol ester molecule cresylol 2.56 0.2 mol POCl
3
55) mol NaOH20%, 0.8 gram/100 gram toluene
Molecule POCl
3
/ 500 gram toluene
6 phenol di(2-ethylhexyl)phosphate phenol, 2 mol phenol, 1 gram, 0.64 mol, 88 √
M-isopropyl benzene phenol list isopropyl benzene ester molecule isopropyl benzene phenol NaOH0.2 mol
2.56 mol NaOH POCl
3
0.8 mol POCl
3/ 100 gram toluene
/ 500 gram toluene
√ represents that quality product meets reagent product index.
Claims (1)
1, a kind of technology for preparing tri aromatic ester of phosphic acid, be by phenol or its homologue and phosphorus oxychloride in the presence of the 20%NaOH aqueous solution and small amount of toluene, keep 18-28 ℃ after the vigorous stirring, in two steps or multistep add reaction mass, continue reaction down after 30 minutes at 25 ℃, with toluene in the organic phase, after water and unreacted phenols steam and remove, promptly get product, feature of the present invention is, continue reaction 30 minutes down at 25 ℃, improve temperature 50-60 ℃ again, continue reaction 30 minutes, and then organic phase under reduced pressure steamed dewater, toluene, a small amount of unreacted phenol and a small amount of by product, again under 60 ℃ respectively with the NaOH solution washing of 0.1-5%, the washing residuum is at last at 100 ℃ of following decompression dehydrations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106790 CN1022106C (en) | 1989-08-29 | 1989-08-29 | Preparation process of phosphotriaromatic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106790 CN1022106C (en) | 1989-08-29 | 1989-08-29 | Preparation process of phosphotriaromatic ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1049848A CN1049848A (en) | 1991-03-13 |
| CN1022106C true CN1022106C (en) | 1993-09-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89106790 Expired - Fee Related CN1022106C (en) | 1989-08-29 | 1989-08-29 | Preparation process of phosphotriaromatic ester |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344421B (en) * | 2011-07-28 | 2014-03-26 | 南京师范大学 | Preparation method for phenoxy ester in water phase |
| CN102558226A (en) * | 2011-12-15 | 2012-07-11 | 上海馨晟试化工科技有限公司 | Method for preparing aviation tricresyl phosphate additive |
| RU2667059C1 (en) * | 2018-03-26 | 2018-09-14 | Общество с ограниченной ответственностью "Научно-производственное предприятие КВАЛИТЕТ" ООО "НПП КВАЛИТЕТ" | Method for producing fire-resistant liquid |
-
1989
- 1989-08-29 CN CN 89106790 patent/CN1022106C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1049848A (en) | 1991-03-13 |
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