CN103224529A - Preparation method of triphenyl phosphite - Google Patents
Preparation method of triphenyl phosphite Download PDFInfo
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- CN103224529A CN103224529A CN201310120595XA CN201310120595A CN103224529A CN 103224529 A CN103224529 A CN 103224529A CN 201310120595X A CN201310120595X A CN 201310120595XA CN 201310120595 A CN201310120595 A CN 201310120595A CN 103224529 A CN103224529 A CN 103224529A
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Abstract
The present invention relates to a preparation method of triphenyl phosphite, which includes the following steps of (1) plunging the molten phenol into the reaction kettle; stirring when the material temperature is below 45DEG C, adding the phosphorus trichloride for 4.5 to 5.5 hours with the kettle temperature of between 20 and 30DEG C and the pressure of between 50 and 90mmHg, continuing stirring for 1 hour; (2) heating up to 120DEG C after stirring, naturally draining acid for 3 hours, cooling to 95-100DEG C, starting negative-pressure draining acid for 5 to 7 hours, increasing the negative pressure to 650mmHg, sampling to obtain the qualified crude ester with acid value of no more than 4mgKOH/g; (3) heating the qualified crude ester to reduce the pressure, separating by distillation, collecting the finished product with acid value of 0.8mgKOH/g and light-colored transparent appearance to obtain the triphenyl phosphite. The preparation method provided by the invention simplifies the process, and has simple method easy to operate, available raw materials and low costs. In addition, the yield rate of triphenyl phosphite obtained by the method is up to 87% or more, and the resultant products have stable quality and good effect for use, which various technical indicators reach the standard.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to triphenyl phosphite, especially a kind of preparation method of triphenyl phosphite.
Background technology
Triphenyl phosphite, molecular formula is: (C
6H
5O)
3P, molecular weight are 310.29, and its structural formula is as follows:
Triphenyl phosphite is colourless or little yellow oily liquid, when being lower than below 16 ℃, is colourless or little yellow monoclinic crystal, and little have the phenol stink, and irritating smell is arranged, and has corrodibility, water insoluble, can be dissolved in organic solvents such as ethanol ether chloroform.
Triphenyl phosphite can be used as the oxidation inhibitor and the stablizer of many polymkeric substance, with many phenolic antioxidants good synergism is arranged, and also can make the auxiliary antioxidant of polyvinyl chloride, polypropylene, polystyrene, ABS resin etc.Triphenyl phosphite is an auxiliary antioxidant, and has a light stabilising effect, mainly be applicable to polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyester, the ABS resin, epoxy resin, the antioxidant stabilizer of synthetic rubber etc., be used for polrvinyl chloride product and make sequestrant, when being main stabilizer with the metal, cooperate this product can reduce the harm of metal chloride, the transparency that keeps goods, and inhibition colour-change, it also is a kind of good chemical intermediate, with halogenated flame retardant and usefulness, can bring into play the fire retardant antioxidant effect, and have light stability concurrently, can be used as synthetic alkyd resin and polyester, this product is mainly the raw material of resin, also can produce the pesticide intermediate trimethyl phosphite.
Triphenyl phosphite is celluosic resin, Vinylite, natural rubber, elastomeric flame retardant resistance extender plasticizer; Evaporation rate is low, has the good transparency, flexibility, and obdurability also has certain flame retardant resistance; Be the plasticising and the physics softening agent of nitrocotton, cellulose acetate (sheet base), Resins, epoxy, synthetic plastics, polyvinyl chloride, nitrile rubber; And the uninflammability surrogate of camphor in the viscose fiber; Be suitable for film, synthetic glass, engineering plastics etc.
At present, also have the preparation method of many triphenyl phosphites in the prior art, these methods also respectively have their advantage, but also exist deficiencies such as preparation method's reactions steps is many, route is long, efficient is low, energy consumption is high, etching apparatus, environmental pollution.
By retrieval, do not find the patent publication us relevant with present patent application.
Summary of the invention
This application aims is to overcome the deficiencies in the prior art, the preparation method of the triphenyl phosphite that provide a kind of and provide that a kind of method is simple, easy handling, pollution is little.
The present invention realizes that the technical scheme of purpose is:
A kind of preparation method of triphenyl phosphite, step is as follows:
(1) fused phenol is dropped in the reactor; Below the material temperature drop to 45 ℃, begin to stir, drip phosphorus trichloride, temperature of reaction kettle remains on 20-30 ℃, and pressure-controlling is at 50-90mmHg, and the dropping time was controlled at 4.5-5.5 hour, dropwises the back and stirs 1 hour;
Wherein, phenol: the mass ratio of phosphorus trichloride is 1190 ~ 1210:540 ~ 560;
(2) stirring is warming up to 120 ℃ after finishing, and natural acid discharge 3 hours is cooled to 95-100 ℃ then and starts negative pressure acid discharge 5-7 hour, and negative pressure is increased to 650mmHg, with sampling acid number≤4mgK
OH/ g is qualified thick ester;
(3) qualified thick ester intensification carrying out underpressure distillation is separated, low-boiling-point substance, middle fraction, finished product are collected respectively, the gained acid number is at 0.8 mg
KOHDuring/g, the as clear as crystal finished product of outward appearance light color is triphenyl phosphite.
And phenol among the described step ⑴: the mass ratio of phosphorus trichloride is 1200:550.
And the isolating condition of underpressure distillation is among the described step ⑶:
Vacuum degree control is greater than 0.0987MPa; The fraction temperature of low-boiling-point substance is controlled at 140 ℃; The fraction temperature of middle fraction is controlled at 200 ℃; The fraction temperature of finished product is controlled at 280 ℃.
Advantage of the present invention and beneficial effect are:
1, preparation method of the present invention has simplified building-up process, and method is simple, easy handling, and raw material is easy to get, and cost is low.And the yield of the triphenyl phosphite that makes by this method can reach more than 87% ℃, the steady quality of product, and every technical indicator all reaches within the standard, and the product result of use is good.
2, adopt among the preparation method of the present invention dropping temperature and flow velocity the control semi-automation, can alleviate producers' labour intensity than remote manipulation, increased security, protect that the staff's is healthy.
3, preparation method of the present invention makes in the production process of triphenyl phosphite, stir and rotate sealing fully, the run, drip, leak of equipment have reduced many or have not had substantially in the workshop, poison flavor as chlorine, the pollution of air, sewage makes that the air ambient in workshop is good, and also is beneficial to the healthy of staff.
Embodiment
The invention will be further described below by specific embodiment, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
Employed reagent among the present invention if no special instructions, is commercially available conventional reagent; Employed method if no special instructions, is the ordinary method in present technique field.
A kind of preparation method of triphenyl phosphite, overall preparation thinking is as follows:
With 1200 kilograms of fused phenol, in the suction reactor; Start to stir, below the material temperature drop to 45 ℃, begin to stir, beginning slowly drips phosphorus trichloride, and temperature of reaction kettle remains on 20-30 ℃, and the dropping time was controlled at 4.5-5.5 hour, stirred 1 hour behind the Dropwise 5 50Kg; In the process that drips phosphorus trichloride, the normal pressure acid dump system is controlled at 50-90mmHg, and regulate rate of addition at any time according to temperature, slowly be warming up to 120 ℃ then, natural acid discharge 3 hours is lowered the temperature 95-100 ℃ then, start negative pressure acid discharge 5-7 hour, negative pressure strengthens pre-650mmHg, and about 8-10 hour, sampling acid number≤4mgK
OH/ g is that a qualified will China and a back are extracted into thick ester in the still kettle with negative pressure, distills then.Vacuum degree control is collected front-end volatiles, middle cut and finished product greater than 0.0987MPa by temperature.
(1) ratio of components:
Phenol: phosphorus trichloride=1200:550(kilogram)
(2) control condition
1. synthesis procedure
A. material temperature＜40 ℃ is thrown phosphorus trichloride.
B. normal pressure acid discharge:
A kind of preparation method of triphenyl phosphite, concrete steps are as follows:
1, esterification step
(1) start squirt pump, suitable for reading with the stifled good surge tank of plug, open negative pressure joint door on the retort, connect the material loading pipeline.
When (2) negative pressure is greater than 300mmHg in the retort,, be pumped in the retort 1200 kilograms of fused phenol.
(3) open exhaust joint door, close negative pressure joint door; Open thief hole, drop into the catalyzer for preparing, close thief hole.
(4) start to stir, chuck is given water for cooling, below liquid temperature drop to 45 ℃, 550 kilograms of phosphorus trichlorides is splashed in the retort.
(5) open surge tank plug suitable for reading, close squirt pump; Open a jar last emptying,, close emptying to a jar interior normal pressure.
(6) open the nature acid dump system, hydrochloric acid absorption tower is given water coolant.
(7) stirred 1 hour, the retort chuck heats up to steam heating,
(8) with speed per hour 4-5 ℃/time, be warming up to 120 ℃, balance 1 hour.
(9) cool to naturally below 95 ℃, start squirt pump, suitable for reading with the stifled good surge tank of plug, open and shut negative pressure joint door; Close normal pressure, acid discharge joint door and acid dump system; Negative pressure on the jar〉400mmHg.7 hours.
(10) after the balance, close negative pressure joint door, thief hole is opened in emptying, sample examination.
(11) acid number≤4 mg
KOH/ g, it is qualified to be.
2, distillation process
(1) starts vacuum pump, open material loading joint door, will synthesize in suction pot of thick ester, close charging joint door.
(2) heat up with the charcoal stove of lighting, open pipe bundle condenser water coolant joint door in right amount, carry out underpressure distillation.
(3) joint door on the water collecting tank is opened, vacuum tightness is observed visor more than 0.0987Mpa, and when liquid temperature during near 140 ℃, effluent is a low-boiling-point substance,
(4) when more than the liquid temperature rise to 200 ℃, flow occurs, and rises to 200 ℃, and flow changes from small to big, and this fraction is middle fraction, fraction jar in being collected in, (close joint door on the low-boiling-point substance holding tank in advance, in opening on the fraction holding tank joint door).
(5) the liquid temperature raises gradually, observes feed liquid by slightly muddy to limpid transparent from visor, during temperature to the 280 ℃ left and right sides, according to the feed liquid outward appearance, surveys its acid number.
(6) when acid number at 0.8 mg
KOHDuring/g the left and right sides, outward appearance light color is as clear as crystal, can open joint door on the finished product holding tank, joint door on the fraction holding tank in closing simultaneously.
(7) in collecting the finished product process, about liquid temperature rise to 280 ℃, vacuum tightness keeps stable more than 0.0987Mpa, and observes the variation of finished product outward appearance and acid number at any time.
(8) deepen or acid number when increasing when color and luster, fraction is collected in changing over to, and distillation finishes, cooling, thorough fire, termination of pumping.
(9) low-boiling-point substance is put into standby bucket and is stored backsight situation analysis use temporarily.
(10) all or part of according to circumstances thick ester of cooking of incorporating into of fraction steams the deduction product or handles single the steaming in.
The detected result of the preparation-obtained triphenyl phosphite of aforesaid method:
The standard of triphenyl phosphite sees Table 1, and the index of correlation detected result of the triphenyl phosphite that preparation method of the present invention prepares meets every standard listed in the table 1, and product is qualified.
The specification of quality standard of table 1 triphenyl phosphite
| Project | Index |
| Colourity (Pt-Co) #?≤ | 80 |
| Acid number mg KOH/g?≤ | 0.50 |
| Density | 1.180-1.185 |
| Refractive index | 1.586-1.590 |
Claims (3)
1. the preparation method of a triphenyl phosphite, it is characterized in that: step is as follows:
(1) fused phenol is dropped in the reactor; Below the material temperature drop to 45 ℃, begin to stir, drip phosphorus trichloride, temperature of reaction kettle remains on 20-30 ℃, and pressure-controlling is at 50-90mmHg, and the dropping time was controlled at 4.5-5.5 hour, dropwises the back and stirs 1 hour;
Wherein, phenol: the mass ratio of phosphorus trichloride is 1190 ~ 1210:540 ~ 560;
(2) stirring is warming up to 120 ℃ after finishing, and natural acid discharge 3 hours is cooled to 95-100 ℃ then and starts negative pressure acid discharge 5-7 hour, and negative pressure is increased to 650mmHg, with sampling acid number≤4mgK
OH/ g is qualified thick ester;
(3) qualified thick ester intensification carrying out underpressure distillation is separated, low-boiling-point substance, middle fraction, finished product are collected respectively, the gained acid number is at 0.8 mg
KOHDuring/g, the as clear as crystal finished product of outward appearance light color is triphenyl phosphite.
2. the preparation method of triphenyl phosphite according to claim 1, it is characterized in that: phenol among the described step ⑴: the mass ratio of phosphorus trichloride is 1200:550.
3. the preparation method of triphenyl phosphite according to claim 1, it is characterized in that: the isolating condition of underpressure distillation is among the described step ⑶:
Vacuum degree control is greater than 0.0987MPa; The fraction temperature of low-boiling-point substance is controlled at 140 ℃; The fraction temperature of middle fraction is controlled at 200 ℃; The fraction temperature of finished product is controlled at 280 ℃.
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| CN201310120595XA CN103224529A (en) | 2013-04-09 | 2013-04-09 | Preparation method of triphenyl phosphite |
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| CN201310120595XA CN103224529A (en) | 2013-04-09 | 2013-04-09 | Preparation method of triphenyl phosphite |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724370A (en) * | 2013-12-31 | 2014-04-16 | 中国天辰工程有限公司 | Method for preparing phosphite ester compounds through reactive rectification coupling |
| CN103739622A (en) * | 2014-01-06 | 2014-04-23 | 重庆中平紫光科技发展有限公司 | Method for synthesizing phosphorous acid triaryl ester by using two-step method |
| CN103801400A (en) * | 2014-03-07 | 2014-05-21 | 中国天辰工程有限公司 | Process for synthesizing mono-phosphite metal coordination catalyst by coupling reactive distillation and magnetically-stabilized bed |
| CN106279266A (en) * | 2016-07-14 | 2017-01-04 | 山东省临沂市三丰化工有限公司 | A kind of preparation method of liquid phosphite kind antioxidant |
| CN107759631A (en) * | 2017-09-18 | 2018-03-06 | 江苏常青树新材料科技有限公司 | A kind of environment protecting and power-saving type triphenyl phosphite preparation method |
| CN108059641A (en) * | 2017-09-19 | 2018-05-22 | 江苏常青树新材料科技有限公司 | A kind of one isooctyl preparation method of novel high-efficiency environment friendly phosphorous acid hexichol |
| CN112221456A (en) * | 2020-10-29 | 2021-01-15 | 昌和化学新材料(江苏）有限公司 | Low-acid-value triphenyl phosphite production process and device |
| EP4407016A1 (en) | 2023-01-30 | 2024-07-31 | Afton Chemical Corporation | Lubricating composition for vehicle transmissions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003100072A2 (en) * | 2002-05-23 | 2003-12-04 | Basf Aktiengesellschaft | Method for the production of sulphur-containing fine chemicals by fermentation |
| CN1493575A (en) * | 2002-10-28 | 2004-05-05 | 刘德亮 | Method of preparing phosphite ester |
| CN102344421A (en) * | 2011-07-28 | 2012-02-08 | 南京师范大学 | Preparation method for phenoxy ester in water phase |
-
2013
- 2013-04-09 CN CN201310120595XA patent/CN103224529A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003100072A2 (en) * | 2002-05-23 | 2003-12-04 | Basf Aktiengesellschaft | Method for the production of sulphur-containing fine chemicals by fermentation |
| CN1493575A (en) * | 2002-10-28 | 2004-05-05 | 刘德亮 | Method of preparing phosphite ester |
| CN102344421A (en) * | 2011-07-28 | 2012-02-08 | 南京师范大学 | Preparation method for phenoxy ester in water phase |
Non-Patent Citations (1)
| Title |
|---|
| JAVIER HERNA´NDEZ ET AL.: "Substituent effects on the 31PNMR chemical shifts of arylphosphorothionates", 《TETRAHEDRON》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724370A (en) * | 2013-12-31 | 2014-04-16 | 中国天辰工程有限公司 | Method for preparing phosphite ester compounds through reactive rectification coupling |
| CN103739622A (en) * | 2014-01-06 | 2014-04-23 | 重庆中平紫光科技发展有限公司 | Method for synthesizing phosphorous acid triaryl ester by using two-step method |
| CN103801400A (en) * | 2014-03-07 | 2014-05-21 | 中国天辰工程有限公司 | Process for synthesizing mono-phosphite metal coordination catalyst by coupling reactive distillation and magnetically-stabilized bed |
| CN103801400B (en) * | 2014-03-07 | 2015-12-02 | 中国天辰工程有限公司 | A kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling |
| CN106279266A (en) * | 2016-07-14 | 2017-01-04 | 山东省临沂市三丰化工有限公司 | A kind of preparation method of liquid phosphite kind antioxidant |
| CN107759631A (en) * | 2017-09-18 | 2018-03-06 | 江苏常青树新材料科技有限公司 | A kind of environment protecting and power-saving type triphenyl phosphite preparation method |
| CN108059641A (en) * | 2017-09-19 | 2018-05-22 | 江苏常青树新材料科技有限公司 | A kind of one isooctyl preparation method of novel high-efficiency environment friendly phosphorous acid hexichol |
| CN112221456A (en) * | 2020-10-29 | 2021-01-15 | 昌和化学新材料(江苏）有限公司 | Low-acid-value triphenyl phosphite production process and device |
| CN112221456B (en) * | 2020-10-29 | 2023-09-05 | 昌和化学新材料(江苏）有限公司 | Process and device for producing triphenyl phosphite with low acid value |
| EP4407016A1 (en) | 2023-01-30 | 2024-07-31 | Afton Chemical Corporation | Lubricating composition for vehicle transmissions |
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