CN101696224B - Method for synthesizing di(isooctyl) phosphate - Google Patents
Method for synthesizing di(isooctyl) phosphate Download PDFInfo
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Abstract
The invention discloses a method for synthesizing di(isooctyl) phosphate, which aims to solve the problem of low purity and yield of a finished product in the traditional production method. The method comprises the following steps of: A. esterification reaction: adding phosphorus oxychloride into a three-opening bottle with magnetic stirring, starting to stir, dropwise adding isooctanol at 0-15 DEG C, discharging a plurality of heat and generating HCl gas, wherein the process of dropwise adding needs 2.0-5.0 hours, and the molar ratio of the phosphorus oxychloride and the isooctanol is 1.0:3.0-1.0:3.5; B. hydrolysis reaction process: adding a phase transfer catalyst which is 0.2-0.5 percent of the mass of the phosphorus oxychloride and a sodium hydroxide solution which is 1.5-2.5 times of the mass of the phosphorus oxychloride into a reaction system; standing, demixing, removing a water layer and washing an organic phase once by using water; and C. acidification process: adding 10 percent of sulfuric acid which is 4-5 times of phosphorus oxychloride into the organic phase obtained in the step B. Compared with the prior art, the yield and the purity are improved, the yield is larger than and equal to 95, and the purity is larger than and equal to 96.
Description
The technical field the technical field of the invention is the synthetic of di (isooctyl) phosphate (p204).
Background technology di (isooctyl) phosphate structure be for
Former synthetic method is a kind of to be that 2-hexyl hexanol (is called for short isooctyl alcohol, i-C
8H
17O
2) with the phosphorus oxychloride esterification after, the synthesis technique that in the presence of alkali NaOH, reacts, this technology also is the method that domestic industryization all adopts.Reaction equation is as follows:
Esterification
2i-C
8H
17OH+POCl
3→(C
8H
17O)
2POCl+2HCl
The alkaline hydrolysis reaction
(C
8H
17O)
2POCl+NaOH→(C
8H
17O)
2POONa+NaCl
Acidification reaction
2(C
8H
17O)
2POONa+H
2SO
4→2(C
8H
17O)
2PO(OH)+Na
2SO
4
Though this synthesis technique flow process is fairly simple, but because of there being a plurality of molecular balances in the reaction process, reaction product has the different monooctyl ester of mono phosphoric acid ester, di (isooctyl) phosphate, multiple material such as triisooctyl phosphate will allow di (isooctyl) phosphate is primary product as far as possible in this reaction system, is difficult to control in reaction process, the purity of the finished product is not high, and yield is not high yet.
Summary of the invention the purpose of this invention is to provide a kind of synthetic method of di (isooctyl) phosphate, and is not high with the purity that solves existing production method the finished product, the problem that yield is not high.
The present invention includes the following step:
A, esterification
The phosphorus oxychloride adding is had in the there-necked flask of magnetic agitation, start stirring, begin to drip isooctyl alcohol at 0～15 ℃, have heat release in a large number, and have HCl gas to produce, and the dropping process needs 2.0～5.0 hours, and phosphorus oxychloride: isooctyl alcohol (mol ratio) is 1.0: 3.0～1.0: 3.5.
React 0.5～1.5h after dripping at normal temperatures, begin to vacuumize, ascending, in 0.5～1.5h, increase vacuum tightness to 0.0850MPa～0.0855MP; Slowly begin to be warming up to 50～65 ℃, this process needs 0.5～1.5h, insulation reaction 2.0～3.0h again, and less than 1% (massfraction), stopped reaction, the hydrogenchloride water of generation absorb and are recycled into dilute hydrochloric acid solution through gas chromatographic detection phosphorus oxychloride content;
B, hydrolysis reaction
0.2～0.5% phase-transfer catalyst and 1.5～2.5 times of amounts of the phosphorus oxychloride quality sodium hydroxide solution (the sodium hydroxide solution mass percent is 40～60%) that add the phosphorus oxychloride quality to reaction system, heat up in 90～130 ℃, reaction 1～2h, after gas chromatographic analysis reaches standard (three ester contents are less than 1% massfraction), standing demix, branch vibration layer, organic phase wash with water once;
Phase-transfer catalyst is a kind of in quaternary ammonium salt, quaternary alkylphosphonium salt or the polyether.
Quaternary ammonium salt is a kind of in benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, benzyl triethyl ammonium bromide, benzyl tributyl ammonium chloride or the Tetrabutyl amonium bromide.Quaternary alkylphosphonium salt is a kind of in tetraphenyl methyl bromo-phosphonium, Tetraphenylphosphonium Bromide, BPP, the benzyl tri-phenyl-phosphorus bromide.Polyether is polyoxyethylene glycol series (its molecular weight M=500～2000) or crown ether series, is selected from a kind of in hexaoxacyclooctadecane-6-6,15-crown ether-5, dibenzo-18-crown-6 (DB18C6) or the 12-crown ether-4.
C, acidization
The organic phase that the B step is obtained adds 10% sulfuric acid of 4～5 times of amounts of phosphorus oxychloride quality, behind 40～60 ℃ of reaction 1～2.0h, leaves standstill branch and anhydrates, wash with water more once, excessive isooctyl alcohol is removed in the organic phase underpressure distillation, and cooling discharging promptly gets the di (isooctyl) phosphate product.
The present invention utilizes the mechanism of alkyl phosphate catalytic hydrolysis, strengthen isooctyl alcohol and phosphorus oxychloride reaction feed ratio, allow reaction generate di (isooctyl) phosphate and triisooctyl phosphate as much as possible, (this product water dissolubility is very strong to generate the different monooctyl ester of mono phosphoric acid ester less to the greatest extent, in water, run off easily, and in reaction, should not reclaim separation); Because the iso-octyl steric hindrance is higher, so triisooctyl phosphate less stable, add catalyzer in hydrolytic process, utilize the unstable of triisooctyl phosphate that it is hydrolyzed into the desired di (isooctyl) phosphate of reaction control again, hydrolysis obtains also this reaction desired raw material just of by product isooctyl alcohol, can recycling, thus the product yield and the purity of original technology improved, and production cost is further reduced.
Its reaction principle is as follows:
Esterification
3i-C
8H
17OH+POCl
3→(C
8H
17O)
3PO+3HCl
The reaction of catalysis alkaline hydrolysis
Acidification reaction
2(C
8H
17O)
2PO(ONa)+H
2SO
4→2(C
8H
17O)
2PO(OH)+Na
2SO
4
The invention solves in original technological reaction process and have a plurality of molecular balances, reaction product has the different monooctyl ester of mono phosphoric acid ester, di (isooctyl) phosphate, multiple material such as triisooctyl phosphate, allow di (isooctyl) phosphate is primary product as far as possible in this reaction system, in reaction process, be difficult to the problem of control; Because the different monooctyl ester of mono phosphoric acid ester that generates in the novel process seldom, it is less to run off in processes such as washing purifying, has therefore improved the yield of product; In hydrolytic process, triisooctyl phosphate is utilized the method for catalytic hydrolysis, greatly reduce in the product its content and generated our desired product di (isooctyl) phosphate, well solved the purity problem of product again.
Experimental result
Determining of 1 feed ratio
In the esterification of phosphorus oxychloride and isooctyl alcohol, there are a plurality of esterification balanced reactions, have only the isooctyl alcohol of increasing and phosphorus oxychloride reaction feed ratio, make the first step esterification generate a large amount of triisooctyl phosphates and small amounts of phosphoric acid di-isooctyl as much as possible, the content of the different monooctyl ester of mono phosphoric acid ester is low as far as possible, and (this product is not easily separated, influence product yield and purity), and the triisooctyl phosphate poor heat stability, at high temperature, alkaline condition, can resolve into di (isooctyl) phosphate (P204) and isooctyl alcohol under the effect of catalyzer, so feed ratio is very crucial, isooctyl alcohol is excessive, but excessive many inconvenience that can cause isooctyl alcohol to reclaim too much.
Determine that esterification reaction temperature is 55 ℃, change the feed ratio of phosphorus oxychloride and isooctyl alcohol, carry out esterification, control phosphorus oxychloride content less than 1% through vapor detection, the gas phase analysis product quality is used in catalysis alkaline hydrolysis, acidifying, underpressure distillation then again, calculates product yield (in the phosphorus oxychloride that consumes), investigated its influence, the results are shown in Table 1 product quality.
The feed ratio of table 1 phosphorus oxychloride and isooctyl alcohol is to the influence of product quality
| Phosphorus oxychloride: isooctyl alcohol (mol ratio) | Different monooctyl ester/the % of mono phosphoric acid ester | Di (isooctyl) phosphate/% | Triisooctyl phosphate/% | Yield/% |
| 1.0∶2.1 | 18.3 | 80.8 | 0.9 | 82.1 |
| 1.0∶2.5 | 9.0 | 90.2 | 0.8 | 90.3 |
| 1.0∶3.0 | 3.5 | 96.1 | 0.4 | 96.0 |
| 1.0∶3.2 | 3.2 | 96.5 | 0.3 | 96.2 |
| 1.0∶3.5 | 2.8 | 96.6 | 0.6 | 96.4 |
As shown in Table 1, increase along with the isooctyl alcohol consumption, the content of di (isooctyl) phosphate and yield all increase to some extent, but increase to 3.0 when above, content and yield change little, consider production cost and economic benefit, phosphorus oxychloride: isooctyl alcohol (mol ratio) be 1.0: 3.0～1.0: 3.5 the most reasonable.
Determining of 2 esterification conditions
The dropping mode: found through experiments dropping phosphorus oxychloride or isooctyl alcohol does not have much differences, but considers phosphorus oxychloride (POCl
3) volatility is big and toxicity is stronger, so the dropping isooctyl alcohol is more reasonable.
Temperature of reaction during dropping: the dropping process has a large amount of heat release, if temperature is higher than 15 ℃, because a large amount of HCl gas generates, under vacuum condition, can take away a certain amount of phosphorus oxychloride and isooctyl alcohol.So determine that dropping temperature is less than 15 ℃.
The condition of vacuum tightness and temperature: temperature is too high, the volatility of system is increased, and the color and luster of product is increased the weight of.And condition of high vacuum degree helps the carrying out that react, so earlier in the normal temperature gas clean-up, slowly be warming up to 55 ℃ again, in entire reaction course, maintain a small amount of bubble and is produced as suitable.
Determining of 3 catalysis alkaline hydrolysis reacting middle catalyst consumptions and reaction times
This reaction is the emphasis and the key of this research, directly uses the reaction of NaOH hydrolysis for high steric hindrance alkyl phosphate, because its is water-soluble relatively poor, and steric hindrance is bigger, so its hydrolysis reaction is not ideal.The isooctyl alcohol that this institute uses just in time belongs to this type of.After adding catalyzer, find that it is very helpful to this reaction, not only accelerated the speed of reaction, and the balance of this hydrolysis reaction is also shifted to favourable aspect.But its add-on and hydrolysis time are very important.Catalytic amount is too many, the too fast bad control of hydrolysis reaction; Time is too short, and hydrolysis is incomplete; The overlong time di (isooctyl) phosphate also can be hydrolyzed into the different monooctyl ester of mono phosphoric acid ester.By experiment catalyst levels and reaction times are determined, be the results are shown in Table 2.
Table 2 catalyst levels and reaction times are to the influence of product content
| Catalyzer/% | Reaction times/h | Different monooctyl ester/the % of mono phosphoric acid ester | Di (isooctyl) phosphate/% | Triisooctyl phosphate/% |
| Do not add | 2.0 | 2.5 | 38.7 | 58.6 |
| 0.1 | 1.0 | 2.6 | 89.0 | 8.1 |
| 0.1 | 2.0 | 2.6 | 96.0 | 1.0 |
| 0.2 | 2.0 | 2.7 | 96.5 | 0.4 |
| 0.3 | 2.0 | 3.0 | 96.5 | 0.3 |
As shown in Table 2, catalyst levels is that 0.1～0.5% (in the phosphorus oxychloride quality) is optimum amount in catalytic hydrolysis reaction, and the reaction times is 1.0～2.0h.
Sulfuric acid consumption, temperature of reaction and reaction times determines in 4 acidification reactions
Temperature crosses that low acidifying is incomplete, and the product viscosity is bigger, and vacuum distillation process is easy to generate side reaction, influences product purity; Temperature is too high, also can cause the decomposition of di (isooctyl) phosphate. and by experiment sulfuric acid consumption, temperature of reaction and reaction times are determined, be the results are shown in Table 3.
Table 3 sulfuric acid consumption, temperature of reaction and reaction times are to the influence of product quality
| H 2SO 4/g | Temperature of reaction/℃ | Reaction times/h | Phenomenon |
| 40.0 | 25 | 2.0 | The product system viscosity is bigger |
| 35.0 | 55 | 2.0 | The product system viscosity is bigger |
| 40.0 | 40 | 2.0 | Product is qualified |
| 40.0 | 60 | 1.0 | Product is qualified |
| 40.0 | 50 | 1.5 | Product is qualified |
As shown in Table 3, H
2SO
4Be to be diluted to 10% about 40 grams, i.e. 10% sulfuric acid of 4～5 times of amounts of phosphorus oxychloride quality, behind 40～60 ℃ of reaction 1～2.0h, acidification reaction just can carry out obtaining qualified product fully.
The analysis of di (isooctyl) phosphate
1 qualitative analysis
Referring to Fig. 2 is the infrared spectrum of sample that the present invention does (purity is 96.5%).With Fig. 1 be standard with commercially available purity 97% di (isooctyl) phosphate (chemical pure), the contrast of this experiment products obtained therefrom infrared spectrum and standard model spectrogram finds that infrared signature is identical.
2 quantitative analyses
The quantitative analysis of product is according to acid phosphatase ester quat pyrolysis method.Easy and the Tetramethylammonium hydroxide reaction generation quaternary ammonium salt of acid phosphoric acid ester, the pyrolysis at a certain temperature of this quaternary ammonium salt generates corresponding methyl esters, carries out quantitative analysis with gas-chromatography GC again.Get the 0.1g acid phosphoric acid ester and place in the 5mL graduated centrifuge tube, add the 0.5mL anhydrous methanol, vibration drips 35% Tetramethylammonium hydroxide methanol solution to alkalescence, and the quaternary ammonium salt direct injection that makes is carried out gas chromatographic analysis.
Description of drawings
Fig. 1 is 97% standard infrared analysis spectrogram for commercially available purity;
Fig. 2 is the infrared spectrum of sample that the present invention does.
Embodiment
Phosphorus oxychloride 82 gram (0.534mol) addings are had in the there-necked flask of magnetic agitation, start stirring, at 10 ℃, begin to drip isooctyl alcohol 222 grams (1.70mol), phosphorus oxychloride: isooctyl alcohol (mol ratio) is 1: 3.2, and whole dropping needs 2 hours; React 1.5h after dripping at normal temperatures, begin to vacuumize, ascending, in 0.5h, increase vacuum tightness to 0.0850MPa; Slowly begin to be warming up to 50 ℃, this process needs 0.5h; Insulation reaction 3.0h again, less than 1% (massfraction), stopped reaction, the hydrogenchloride water of generation absorb and are recycled into dilute hydrochloric acid solution through gas chromatographic detection phosphorus oxychloride content.
Add 0.16 gram phase-transfer catalyst benzyltriethylammoinium chloride to reaction system, mass percent is 40% sodium hydroxide solution 205 grams, heat up in 90 ℃, reacted 2 hours, after gas chromatographic analysis reaches standard (three ester contents are less than 1% massfraction), standing demix, branch vibration layer, organic phase washes with water once.
Add 410 grams, 10% sulfuric acid again,, leave standstill branch and anhydrate, wash with water more once 40 ℃ of reactions 2 hours; This process is an acidization.Excessive isooctyl alcohol is removed in the organic phase underpressure distillation, and cooling discharging promptly gets product (p204).
The difference of embodiment 2 and embodiment 1 is that phase-transfer catalyst selects benzyl trimethyl ammonium chloride for use.
The difference of embodiment 3 and embodiment 1 is that phase-transfer catalyst selects benzyl triethyl ammonium bromide for use.
The difference of embodiment 4 and embodiment 1 is that phase-transfer catalyst selects benzyl tributyl ammonium chloride for use.
The difference of embodiment 5 and embodiment 1 is that phase-transfer catalyst selects Tetrabutyl amonium bromide for use.
The yield of embodiment 1-5 and purity see following table 4 for details.
Table 4 quaternary ammonium salt catalyst kind, consumption are to the influence of product yield, purity
| Embodiment | Catalyst type | Catalyst levels (g) | Product p204 quality (g) | Purity % | Productive |
| Embodiment | |||||
| 1 | Benzyltriethylammoinium chloride | 0.16 | ?168 | ?96.5 | ?95.8 |
| Embodiment 2 | Benzyl trimethyl ammonium chloride | 0.16 | ?169 | ?96.6 | ?95.8 |
| |
Benzyl triethyl ammonium bromide | 0.16 | ?167 | ?96.4 | ?95.4 |
| Embodiment 4 | Benzyl tributyl ammonium chloride | 0.16 | ?168 | ?96.4 | ?95.8 |
| |
Tetrabutyl amonium bromide | 0.16 | ?167 | ?96.3 | ?95.4 |
Embodiment 6
Phosphorus oxychloride 82 gram (0.534mol) addings are had in the there-necked flask of magnetic agitation, start stirring, at 0 ℃, begin to drip isooctyl alcohol 209 grams (1.60mol), phosphorus oxychloride: isooctyl alcohol (mol ratio) is 1: 3.0, and whole dropping needs 2h; React 0.5h after dripping at normal temperatures and begin to vacuumize, ascending, in 1.5h, increase vacuum tightness to 0.0855MPa; Slowly begin to be warming up to 50 ℃, this process needs 1.5h, insulation reaction 3.0h again, and less than 1% (massfraction), stopped reaction, the hydrogenchloride water of generation absorb and are recycled into dilute hydrochloric acid solution through gas chromatographic detection phosphorus oxychloride content.
Add 0.16 gram phase-transfer catalyst tetraphenyl methyl bromo-phosphonium to reaction system, mass percent is 60% sodium hydroxide solution, 123 grams, heat up in 130 ℃, reacted 1 hour, after gas chromatographic analysis reaches standard (three ester contents are less than 1% massfraction), standing demix, branch vibration layer, organic phase washes with water once.
Add 328 grams, 10% sulfuric acid again,, leave standstill branch and anhydrate, wash with water more once 50 ℃ of reactions 1.5 hours; This process is an acidization.Excessive isooctyl alcohol is removed in the organic phase underpressure distillation, and cooling discharging promptly gets product (p204).
The difference of embodiment 7 and embodiment 6 is that phase-transfer catalyst selects Tetraphenylphosphonium Bromide for use.
The difference of embodiment 8 and embodiment 6 is that phase-transfer catalyst selects BPP for use.
The difference of embodiment 9 and embodiment 6 is that phase-transfer catalyst selects the benzyl tri-phenyl-phosphorus bromide for use.
The yield of embodiment 6-9 and purity see following table 5 for details.
Table 5 quaternary alkylphosphonium salt catalyst series kind, consumption are to the influence of product yield, purity
| Embodiment | Catalyst type | Catalyst levels (g) | Product p204 quality (g) | Purity % | Productive rate % |
| Embodiment 6 | Tetraphenyl methyl bromo-phosphonium | 0.25 | ?167 | ?96.2 | ?95.4 |
| |
Tetraphenylphosphonium Bromide | 0.25 | ?166 | ?96.1 | ?95.0 |
| Embodiment 8 | BPP | 0.25 | ?166 | ?96.3 | ?95.0 |
| |
The benzyl tri-phenyl-phosphorus bromide | 0.25 | ?167 | ?96.2 | ?95.4 |
Phosphorus oxychloride 82 gram (0.534mol) addings are had in the there-necked flask of magnetic agitation, start stirring, at 15 ℃, begin to drip isooctyl alcohol 243 grams (1.869mol), phosphorus oxychloride: isooctyl alcohol (mol ratio) is 1: 3.5, and whole dropping needs 5 hours; React 1.5h after dripping at normal temperatures and begin to vacuumize, ascending, in 0.5h, increase vacuum tightness to 0.0850MPa; Slowly open and be warming up to 50 ℃, this process needs 0.5h; Insulation reaction 3.0h again, less than 1% (massfraction), stopped reaction, the hydrogenchloride water of generation absorb and are recycled into dilute hydrochloric acid solution through gas chromatographic detection phosphorus oxychloride content.
Add 0.32 gram phase-transfer catalyst hexaoxacyclooctadecane-6-6 to reaction system, mass percent is 40% sodium hydroxide solution, 205 grams, heat up in 90 ℃, reacted 2 hours, after gas chromatographic analysis reaches standard (three ester contents are less than 1% massfraction), standing demix, branch vibration layer, organic phase washes with water once.
Add 370 grams, 10% sulfuric acid again,, leave standstill branch and anhydrate, wash with water more once 60 ℃ of reactions 1 hour; This process is an acidization.Excessive isooctyl alcohol is removed in the organic phase underpressure distillation, and cooling discharging promptly gets product (p204).
The difference of embodiment 11 and embodiment 10 is that phase-transfer catalyst selects 15-crown ether-5 for use.
The difference of embodiment 11 and embodiment 10 is that phase-transfer catalyst selects dibenzo-18-crown-6 (DB18C6) for use.
The difference of embodiment 11 and embodiment 10 is that phase-transfer catalyst selects 12-crown ether-4 for use.
The yield of embodiment 10-13 and purity see following table 6 for details.
Table 6 crown ether catalyst series kind, consumption are to the influence of product yield, purity
| Embodiment | Catalyst type | Catalyst levels (g) | Product p204 quality (g) | Purity % | Productive |
| Embodiment | |||||
| 10 | Hexaoxacyclooctadecane-6-6 | 0.32 | ?168 | ?96.6 | ?95.8 |
| Embodiment 11 | 15-crown ether-5 | 0.32 | ?167 | ?96.7 | ?95.4 |
| Embodiment 12 | Dibenzo-18-crown-6 (DB18C6) | 0.32 | ?166 | ?96.3 | ?95.0 |
| Embodiment 13 | 12-crown ether-4 | 0.32 | ?168 | ?96.2 | ?95.8 |
Embodiment 14
In phosphorus oxychloride 82 grams (0.534mol), 5 ℃ begin to drip the isooctyl alcohol adding and have in the there-necked flask of magnetic agitation, start stirring, begin to drip isooctyl alcohol 240 grams (1.77mol) at 5 ℃, have heat release in a large number, and have HCl gas to produce, and the dropping process needs 2 hours, and phosphorus oxychloride: isooctyl alcohol (mol ratio) is 1.0: 3.4.
React 1.5h after dripping at normal temperatures, begin to vacuumize, ascending, in 0.5h, increase vacuum tightness to 0.0850MPa; Slowly begin to be warming up to 65 ℃, this process needs 1.5h, insulation reaction 2.0h again, and less than 1% (massfraction), stopped reaction, the hydrogenchloride water of generation absorb and are recycled into dilute hydrochloric acid solution through gas chromatographic detection phosphorus oxychloride content.
Add 0.42 gram phase-transfer catalyst polyoxyethylene glycol M=600 to reaction system, mass percent is 50% sodium hydroxide solution, 165 grams, heat up in 110 ℃, reacted 1.5 hours, after gas chromatographic analysis reaches standard (three ester contents are less than 1% massfraction), standing demix, branch vibration layer, organic phase washes with water once.
Add 370 grams, 10% sulfuric acid again,, leave standstill branch and anhydrate, wash with water more once 55 ℃ of reactions 1.5 hours; This process is an acidization.Excessive isooctyl alcohol is removed in the organic phase underpressure distillation, and cooling discharging promptly gets product (p204).
The difference of embodiment 15 and embodiment 14 is that phase-transfer catalyst selects polyoxyethylene glycol M=800 for use.
The difference of embodiment 16 and embodiment 14 is that phase-transfer catalyst selects polyoxyethylene glycol M=1000 for use.
The difference of embodiment 17 and embodiment 14 is that phase-transfer catalyst selects polyoxyethylene glycol M=1500 for use.
The yield of embodiment 15-17 and purity see following table 7 for details.
Table 7 polyoxyethylene glycol catalyst series kind, consumption are to the influence of product yield, purity
| Embodiment | Catalyst type | Catalyst levels (g) | Product p204 quality (g) | Purity % | Productive rate % |
| Embodiment 14 | Polyoxyethylene glycol M=600 | ?0.42 | ?168 | ?96.3 | ?95.8 |
| |
Polyoxyethylene glycol M=800 | ?0.42 | ?167 | ?96.3 | ?95.4 |
| Embodiment 16 | Polyoxyethylene glycol M=1000 | ?0.42 | ?167 | ?96.1 | ?95.4 |
| Embodiment 17 | Polyoxyethylene glycol M=1500 | ?0.42 | ?166 | ?96.0 | ?95.0 |
Claims (1)
1. the synthetic method of a di (isooctyl) phosphate is characterized in that it comprises the following steps:
A, esterification
The phosphorus oxychloride adding is had in the there-necked flask of magnetic agitation, start stirring, begin to drip isooctyl alcohol at 0～15 ℃, have heat release in a large number, and have HCl gas to produce, and the dropping process needs 2.0～5.0 hours, and the mol ratio of phosphorus oxychloride and isooctyl alcohol is 1.0: 3.0～1.0: 3.5;
React 0.5～1.5h after dripping at normal temperatures, begin to vacuumize, ascending, in 0.5～1.5h, increase vacuum tightness to 0.0850MPa～0.0855MP; Slowly begin to be warming up to 50～65 ℃, this process needs 0.5～1.5h, insulation reaction 2.0～3.0h again, and less than 1%, stopped reaction, the hydrogenchloride water of generation absorb and are recycled into dilute hydrochloric acid solution through the massfraction content of gas chromatographic detection phosphorus oxychloride;
B, hydrolysis reaction
0.2～0.5% phase-transfer catalyst and 1.5～2.5 times of amounts of the phosphorus oxychloride quality sodium hydroxide solution that add the phosphorus oxychloride quality to reaction system, the sodium hydroxide solution mass percent is 40～60%, heat up in 90～130 ℃, reaction 1～2h, after gas chromatographic analysis reached standard, promptly three ester massfraction content were less than 1%, standing demix, branch vibration layer, organic phase wash with water once;
C, acidization
The organic phase that the B step is obtained adds 10% sulfuric acid of 4～5 times of amounts of phosphorus oxychloride quality, behind 40～60 ℃ of reaction 1～2.0h, leaves standstill branch and anhydrates, wash with water more once, excessive isooctyl alcohol is removed in the organic phase underpressure distillation, and cooling discharging promptly gets the di (isooctyl) phosphate product;
Phase-transfer catalyst among the described step B is a kind of in quaternary ammonium salt, quaternary alkylphosphonium salt or the polyether; Described quaternary ammonium salt is a kind of in benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, benzyl triethyl ammonium bromide, benzyl tributyl ammonium chloride or the Tetrabutyl amonium bromide; Described quaternary alkylphosphonium salt is a kind of in tetraphenyl methyl bromo-phosphonium, Tetraphenylphosphonium Bromide, BPP, the benzyl tri-phenyl-phosphorus bromide; Described polyether is that molecular weight is 500～2000 polyoxyethylene glycol series or crown ether series, is selected from a kind of in hexaoxacyclooctadecane-6-6,15-crown ether-5, dibenzo-18-crown-6 (DB18C6) or the 12-crown ether-4.
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| CN104804038B (en) * | 2014-01-23 | 2017-09-26 | 北京化工大学苏州（相城）研究院 | A kind of preparation method of phosphate |
| CN105461748A (en) * | 2015-12-11 | 2016-04-06 | 三门峡中达化工有限公司 | Method for preparing di(isooctyl) phosphate from tri-iso-octyl phosphate through phase-transfer catalytic hydrolysis |
| CN105884821A (en) * | 2016-04-29 | 2016-08-24 | 三门峡中达化工有限公司 | Process for preparing bis phosphate from tri-iso-octyl phosphate by means of phosphonium salt phase-transfer catalytic hydrolysis |
| CN105859773A (en) * | 2016-04-29 | 2016-08-17 | 三门峡中达化工有限公司 | Technology for preparing di-2-ethylhexyl phosphoric acid through quaternary phosphonium salt phase transfer, catalysis and hydrolysis |
| CN107999126A (en) * | 2017-11-27 | 2018-05-08 | 湖北富邦科技股份有限公司 | A kind of catalyst and preparation method and purposes for synthesizing phosphoric acid extraction defoamer |
| CN110066291A (en) * | 2018-08-06 | 2019-07-30 | 三门峡中达化工有限公司 | A kind of phase transfer catalysis (PTC) hydrolysis triisooctyl phosphate prepares di (isooctyl) phosphate method |
| CN109438506B (en) * | 2018-12-06 | 2020-12-15 | 山东泰和水处理科技股份有限公司 | Method for preparing tris (1, 3-dichloropropyl) phosphate |
| CN112010741A (en) * | 2019-05-29 | 2020-12-01 | 石家庄欧特佳化工有限公司 | Method for improving purity of chloroacetaldehyde dimethyl acetal by vinyl acetate method |
| CN113717222B (en) * | 2021-08-30 | 2024-06-04 | 杭州潜阳科技股份有限公司 | Preparation method of high-purity dioctyl phosphate |
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