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2-(diphenylthiophosphoryl) succinate as well as synthesis method and application thereof

A technology of diphenyl thiophosphoryl and diphenyl phosphono is applied in the field of industrial production of flame retardant 2-(diphenyl thiophosphoryl) succinate, which can solve the problem of high odor and unpleasantness. Suitable for large-scale production, difficult transportation and storage, etc.

Active Publication Date: 2022-04-12
HUBEI UNIV
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Problems solved by technology

At the same time, there are mainly two types of synthetic methods for 2-(diphenylphosphoryl)succinic acid and its derivatives: 1. Using diphenylphosphine oxide as a raw material method, diphenylphosphine oxide and maleic acid (ester) 2-(diphenylphosphoryl)succinic acid and its derivatives can be obtained by direct reaction, and its representative documents include: RU 2405789, (2010); CN103289124 (2013); CN 105218789 (2016); Polymers for Advanced Technologies, 2016, 27(7), 860-871;; Tetrahedron Letters, 2007, 48(1), 51-54; EP 665237 (1995); Synlett, 2020, 31(13), 1295-1297, the reaction can use catalyst or The heating method promotes the reaction to be complete. This type of synthesis method has a high yield and is suitable for industrial production needs; 2. Using diphenylphosphine chloride as a raw material method, the synthesis method is: diphenylphosphine chloride is converted into a P-Si intermediate After solidification, react with maleic acid ester under the condition of Rh or Pd catalyst to obtain 2-(diphenylphosphoryl) succinic acid ester, and its representative documents include Organic Letters, 2009, 11(5), 1091-1094; Tetrahedron, 2009, 65(33), 6510-6518, the synthesis method has high synthesis cost and medium yield, and is not suitable for large-scale production
On the basis of the research on 2-(diphenylphosphoryl)succinic acid and its derivatives, in order to further improve the flame retardant activity of phosphorus-containing flame retardants, this patent uses 2-(diphenylphosphoryl)succinic acid The (ester) structure was optimized and improved to 2-(diphenylphosphorothio)succinic acid (ester) (DPS-MA for short). At the same time, due to the strong odor of mercaptodiphenylphosphine, easy oxidation, high price, and difficult transportation Therefore, it is meaningful to develop a new preparation process with the advantages of simple process, low experimental odor, good product purity, and low production equipment requirements.

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  • 2-(diphenylthiophosphoryl) succinate as well as synthesis method and application thereof
  • 2-(diphenylthiophosphoryl) succinate as well as synthesis method and application thereof
  • 2-(diphenylthiophosphoryl) succinate as well as synthesis method and application thereof

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Embodiment 1

[0022]Example 1: According to the synthesis method of the document Synthetic Communications, 1980, 10(3), 175-82, 2.00 g of mercaptosuccinic acid, 20.0 mL of absolute ethanol and 3% molar equivalent of p-toluenesulfonic acid were added to a round-bottomed reaction flask Stir in medium, and react overnight under reflux in an external bath at 85°C. After most of the solvent was removed by rotary evaporation, 30 mL of ethyl acetate was added to dissolve the crude product, and then saturated sodium bicarbonate (10 mL×1) and saturated sodium chloride ( 10 mL × 2) washed until the organic phase was neutral, dried over anhydrous magnesium sulfate, filtered, and rotary evaporated to obtain 2.47 g of diethyl mercaptosuccinate with a yield of 90%, which could be directly used in the next reaction.

[0023] Under nitrogen protection, 2.00 g (9.6 mmol) of the above crude product diethyl mercaptosuccinate, 1.02 g (10.0 mmol) of triethylamine and 8.0 mL of dichloromethane were added to the r...

Embodiment 2

[0026] Add 1.78 g (10 mmol) of dimethyl mercaptosuccinate (content >98.5%), 1.05 g (10 mmol) of dry-treated triethylamine and 10 mL of dichloromethane to a 500 mL reaction under nitrogen protection In the flask, cooled in an ice bath, slowly add a mixture of 2.66 g (12.0 mmol) of diphenylphosphorus chloride and 5.0 mL of dichloromethane dropwise through a constant pressure dropping funnel, and the dropwise addition is completed within about 10 to 15 minutes, and then the temperature is raised Reaction was carried out at 60°C for 24 h, and TLC detected that the reaction of dimethyl mercaptosuccinate was complete. After the reaction was stopped, the reaction solution was quickly filtered, and the solvent was spin-dried under reduced pressure to obtain a crude product. Transfer the crude product to a sealed tube of 100 mL, dilute the product with 1.0 mL of chlorobenzene, then add 20 mg of iodine element, stir and seal under nitrogen protection, and react overnight at 140°C in an e...

Embodiment 3

[0028] Under nitrogen protection conditions, 20.0 g (97 mmol) of diethyl mercaptosuccinate (content >98.5%), 9.8 g (97 mmol) of dry-treated triethylamine and 60 mL of dichloromethane were added to a 500 mL reaction In the flask, cooled in an ice bath, slowly add a mixture of 22.4 g (101 mmol) of diphenylphosphine chloride and 20 mL of dichloromethane dropwise through a constant pressure dropping funnel, and the dropwise addition is completed within about 10 to 15 minutes, and then naturally Warming up to room temperature, reacting for 3-4 h, TLC detection of diethyl mercaptosuccinate reaction is complete, stop the reaction, quickly filter the reaction solution, and spin dry the solvent under reduced pressure to obtain the crude product. Transfer the crude product to a 100 mL sealed tube, dilute the product with 15 mL of toluene, then add 0.2 g (0.9 mmol) iodine element, stir and seal under nitrogen protection, and react overnight in an external bath at 160 ° C. After TLC detect...

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Abstract

The invention relates to 2-(diphenylthiophosphoryl) succinate as well as a synthesis method and application thereof. The synthesis method comprises the following steps: by taking triethylamine as an acid-binding agent under the protection of nitrogen atmosphere, carrying out reaction on diphenylphosphonium chloride and 2-mercaptosuccinic acid diester to prepare a 2-((diphenylphosphono) thio) succinic acid diester intermediate; and then the 2-(diphenylthiophosphoryl) succinate is prepared through a rearrangement reaction catalyzed by iodine. The 2-(diphenylthiophosphoryl) succinic acid (ester) (DPS-MA) phosphorus-containing flame retardant provided by the invention has a higher char forming speed and better flame retardant efficiency than a 2-(diphenylphosphoryl) succinic acid (ester) (DPO-MA) phosphorus-containing flame retardant.

Description

technical field [0001] The invention belongs to the chemical synthesis technology of organophosphorus flame retardants, in particular to a preparation method for industrially producing flame retardant 2-(diphenylphosphorylthio)succinate. Background technique [0002] 2-(Diphenylphosphoryl)succinic acid and its derivatives are halogen-free and environmentally friendly phosphorus-containing flame retardants. As reactive flame retardants, they can be applied to polyester, polyamide or epoxy resin materials. The material has good flame retardant properties. For example, in 2013, Chinese patent CN 103289124 (2013) reported the application of 2-(diphenylphosphoryl)succinic acid (DPO-MA for short) in PET polyester materials; in 2017, China Patents CN 106633043 (2017) and CN 106633828 (2017) reported the application of 2-(diphenylphosphoryl)succinic acid in polyamide nylon materials, document Polymers for Advanced Technologies, 2016, 27(7), 860- 871 and Chinese patent CN 110156959 ...

Claims

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Application Information

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IPC IPC(8): C07F9/53C08K5/5398C08L63/00
Inventor 李焰周烽冯世珅任君陈祖兴
Owner HUBEI UNIV
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