CN104892675A - 2,2'-methylene-dis(4,6-di-tert-butylphenol)phosphate ester synthetic method - Google Patents
2,2'-methylene-dis(4,6-di-tert-butylphenol)phosphate ester synthetic method Download PDFInfo
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Abstract
The invention provides a 2,2'-methylene-dis(4,6-di-tert-butylphenol)phosphate ester synthetic method. The method is characterized in that in an inertia solvent, bisphenol and metallic sodium or sodium hydride are reacted, or in the inertia solvent which enables azeotropy with water, azeotropy of bisphenol and sodium hydroxide are carried out to remove water and obtain sodium phenolate; dropping phosphorous oxychloride in a sodium phenolate reaction system, controlling the reaction temperature to room temperature through water-bath during the dropping period, after dropping, stopping cooling, when the temperature is not increased, heating a reactant to backflow, reacting for a while, cooling, washing by water, removing an aqueous layer and an organic layer evaporation solvent, and cooling and crystallizing to obtain phosphate ester. The method has the advantages of non usage of organic acid binding agent and high yield.
Description
Technical field
The present invention relates to a kind of phosphate synthesis method, particularly one 2,2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphate synthesis method.
Background technology
Annular phosphate 2,2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphoric acid ester is the synthesis material of important polypropylene processing aid-nucleant agent N P508 and NP509 (external trade(brand)name is called NA-11 and NA-21).2, the structure of 2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphoric acid ester is as follows:
Bibliographical information mainly contains two kinds of synthetic methods: 1. make reaction medium with the inert solvent such as hexanaphthene or toluene, take triethylamine as acid binding agent, take phosphorus oxychloride as acylating agent, product yield is 45% (Wang Yizhong, the synthesis of remaining ancient cooking vessel sound .PP nucleator and application. plastics industry, 1999,27 (5): 29 ~ 31); 2. with tribromo oxygen phosphorus for acylating agent, DMF is catalyzer, and yield is 34% (Yurugen S.Preparation of pure cyclic diarylester phosphate, JP63181493,1991-08-07; Tajma Kenji, Takahashi Masayuki.Production of diaryl phosphate metal salt, JP 61210090,1986-09-18).The main shortcoming of literature procedures is that yield is low, and aftertreatment is complicated.
Phenols has acidity, and can form sodium phenolate with sodium Metal 99.5 and hydride and oxyhydroxide etc. under certain condition, the nucleophilie nucleus ability of sodium phenolate is far longer than phenol itself, so when with phosphorus oxychloride reaction, the activity of sodium phenolate is also far longer than phenol.
Therefore, a kind of phenol sodium that uses can be designed and replace 2 of phenol, 2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphoric acid ester synthesis technique, manage to improve yield, increase economic benefit.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of 2,2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphate synthesis method.
Described in this patent 2, the structure of 2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphoric acid ester is as follows:
Described in this patent 2,2 '-methylene radical-bis-(4,6-di-t-butyl) phenol (hereinafter referred to as bis-phenol) structure is:
Sodium phenolate described in this patent is 2,2 '-methylene radical-bis-(4,6-di-t-butyl) sodium phenylate (hereinafter referred to as phenol sodium), and its structure is:
In order to realize the object solved the problems of the technologies described above, present invention employs following technical scheme:
2 of this patent, 2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphate synthesis method, technological process comprises:
(1), the synthesis of phenol sodium: described phenol sodium is by inert solvent, and bis-phenol and sodium Metal 99.5 or sodium hydride react to be prepared; Or can with the inert solvent of water azeotropic, bis-phenol and sodium hydroxide azeotropic anhydrate and prepare.
(2) synthetic phosphoric acid ester: after the building-up reactions of phenol sodium terminates, drips phosphorus oxychloride to reaction system, and controlling temperature of reaction by water-bath during dropping is room temperature; Drip and finish, stop cooling, when temperature no longer raises, reacting by heating thing is to backflow, and reaction completes; Then lower the temperature, washing, branch vibration layer, organic layer evaporating solvent, decrease temperature crystalline obtains phosphoric acid ester.
In the synthesis technique of described phenol sodium, the ratio of inert solvent and bis-phenol can select every gram of bis-phenol to add inert solvent 2 ~ 100ml; Preferably every gram of bis-phenol adds inert solvent 5 ~ 20ml; More preferably every gram of bis-phenol adds inert solvent 6 ~ 10ml.
The synthesis technique of described phenol sodium can be add a certain amount of bis-phenol, stirring and dissolving in inert solvent, and water-bath cooling keeps room temperature, adds a certain amount of sodium or sodium hydride in batches, obtains phenol sodium; The synthesis technique of phenol sodium also can adopt azeotropic to anhydrate method, namely can with the inert solvent of water azeotropic in add a certain amount of bis-phenol and sodium hydroxide, heating makes boiling, is separated with solvent azeotropic water out, treat that point water reaches theoretical amount, obtain phenol sodium by water trap.
Above process can schematically as follows:
Described inert solvent is benzene, toluene or hexanaphthene.
The mol ratio of described bis-phenol and sodium Metal 99.5 (or sodium hydride, sodium hydroxide) is preferably 1:2.1.
Described phosphorus oxychloride and the mol ratio of bis-phenol are preferably 1.1:1.
These technical schemes, comprise different inert solvents, the different synthesis techniques of phenol sodium and the technique of synthetic phosphoric acid ester, and the mol ratio of the mol ratio of different phosphorus oxychloride and bis-phenol, bis-phenol and sodium Metal 99.5 (or sodium hydride, sodium hydroxide) also can combine mutually or combine, thus reach better technique effect.
By adopting technique scheme, the present invention has following beneficial effect:
Present method has compared with literature method and does not use organic acid binding agent and yield advantages of higher.
Embodiment
Embodiment 1
The synthesis of phenol sodium: add 12.7g bis-phenol (0.03mol) and 80mL benzene in the 250mL four-hole bottle that mechanical stirring, thermometer and prolong are housed, stirring makes molten.Keep room temperature with water-bath, add 1.45g sodium Metal 99.5 (0.063mol) in batches, after stopping releasing hydrogen gas, continue to stir 30min, obtain phenol sodium.
Synthetic phosphoric acid ester: install dropping funnel on the reaction unit preparing phenol sodium, drips 5.06g phosphorus oxychloride (0.033mol) from dropping funnel.Maintain the temperature at room temperature with water-bath during dropping, dropwise post-heating backflow 1h, be cooled to about 40 DEG C, add 100mL water, stir 30min, branch vibration layer, decompression removes the solvent of about half, drops to room temperature, leaves standstill crystallization 3h, decompress filter, filtration cakes torrefaction, obtains clear crystal, dry product, quality 13.8g, yield is 94.5%, and liquid-phase chromatographic analysis purity is 95.3%.
Embodiment 2
Process is with embodiment 1, but the building-up process solvent of phenol sodium changes 80mL toluene into, and other conditions are constant, obtain product 14.1g, and yield is 96.6%, and liquid-phase chromatographic analysis purity is 95.2%.
Embodiment 3
Process is with embodiment 1, but the building-up process solvent of phenol sodium changes 100mL hexanaphthene into, and other conditions are constant, obtain product 13.5g, and yield is 92.5%, and liquid-phase chromatographic analysis purity is 96.1%.
Embodiment 4
Process is with embodiment 1, but the building-up process 1.45g sodium Metal 99.5 of phenol sodium changes 1.51g sodium hydride (0.063mol) into, and other conditions are constant, obtain product 13.8g, and yield is 94.5%, and liquid-phase chromatographic analysis purity is 96.2%.
Embodiment 5
Process is with embodiment 4, but the building-up process solvent of phenol sodium changes 80mL toluene into, and other conditions are constant, obtain product 14.2g, and yield is 97.3%, and liquid-phase chromatographic analysis purity is 95.8%.
Embodiment 6
Process is with embodiment 4, but the building-up process solvent of phenol sodium is 100mL hexanaphthene, and other conditions are constant, obtain product 13.6g, and yield is 93.2%, and liquid-phase chromatographic analysis purity is 95.5%.
Embodiment 7
The synthesis of phenol sodium: add 12.7g bis-phenol (0.03mol) and 80mL benzene in the 250mL four-hole bottle that mechanical stirring, thermometer, water trap and prolong are housed, stirring makes molten.Add 2.52g sodium hydroxide (0.063mol) solid, be heated to backflow, collect azeotropic water out, about need 4h in water trap, point water reaches theoretical amount, obtains phenol sodium.
Other conditions of synthetic phosphoric acid ester are constant, and finally obtain product 13.0g, yield is 89.0%, and liquid-phase chromatographic analysis purity is 94.5%.
Embodiment 8
Process is with embodiment 7, but the building-up process solvent of phenol sodium changes 80mL toluene into, and other conditions are constant, obtain product 13.3g, and yield is 91.1%, and liquid-phase chromatographic analysis purity is 96.3%.
Embodiment 9
Process is with embodiment 7, but the building-up process solvent of phenol sodium changes 100mL hexanaphthene into, and other conditions are constant, obtain product 12.5g, and yield is 85.6%, and liquid-phase chromatographic analysis purity is 92.1%.
Claims (5)
1. one kind 2,2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphate synthesis method, is characterized in that technological process comprises:
(1), the synthesis of phenol sodium: phenol sodium is by inert solvent, and bis-phenol and sodium Metal 99.5 or sodium hydride react to be prepared; Or can with the inert solvent of water azeotropic, bis-phenol and sodium hydroxide azeotropic anhydrate and prepare;
(2) synthetic phosphoric acid ester: after the building-up reactions of phenol sodium terminates, drips phosphorus oxychloride to reaction system, and controlling temperature of reaction by water-bath during dropping is room temperature; Drip and finish, stop cooling, when temperature no longer raises, reacting by heating thing is to backflow, and reaction completes; Then lower the temperature, washing, branch vibration layer, organic layer evaporating solvent, decrease temperature crystalline obtains phosphoric acid ester.
2. according to claim 12,2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphate synthesis method, it is characterized in that: the synthesis technique of described phenol sodium adds bis-phenol in inert solvent, stirring and dissolving, water-bath cooling keeps room temperature, adds sodium or sodium hydride in batches, obtains phenol sodium; Or can with the inert solvent of water azeotropic in add bis-phenol and sodium hydroxide, heating make boiling, separated with solvent azeotropic water out by water trap, treat that point water reaches theoretical amount, obtain phenol sodium.
3. according to claim 12,2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphate synthesis method, is characterized in that: described inert solvent is benzene, toluene or hexanaphthene.
4. according to claim 12,2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphate synthesis method, is characterized in that: described bis-phenol and sodium Metal 99.5, sodium hydride, any one mol ratio of sodium hydroxide are 1:2.1.
5. according to claim 12,2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) phosphate synthesis method, is characterized in that: described phosphorus oxychloride and the mol ratio of bis-phenol are 1.1:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588978A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Phosphate ester fire retardant based on biomass and preparation method thereof |
| CN110684049A (en) * | 2019-10-16 | 2020-01-14 | 山西省化工研究所（有限公司） | One-pot preparation method of bisphenol phosphate hydroxyl aluminum salt nucleating agent |
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2015
- 2015-05-07 CN CN201510227765.3A patent/CN104892675A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588978A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Phosphate ester fire retardant based on biomass and preparation method thereof |
| CN110684049A (en) * | 2019-10-16 | 2020-01-14 | 山西省化工研究所（有限公司） | One-pot preparation method of bisphenol phosphate hydroxyl aluminum salt nucleating agent |
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