Five-membered ring phosphite compound, and preparation method and application thereof

A kind of cyclic phosphite, compound technology

Pending Publication Date: 2020-06-02
EVERGRANDE NEW ENERGY TECH SHENZHEN CO LTD
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AI-Extracted Technical Summary

Problems solved by technology

[0005] The purpose of the present invention is to provide a five-membered cyclic phosphite compound, which aims to solve the problem that the existing non-aqueous electrolyte phosp...
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Method used

In some embodiments, the general structural formula of five-membered ring phosphite compounds is: In another embodiment, the general structural formula of five-membered ring phosphite compounds is: wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17 and R18 are independently selected from: hydrogen, alkyl, alkenyl, alkynyl, alkoxy Alkynyloxy, alkenyloxy, silyl, siloxane, arylsilyl, arylsiloxy, haloalkyl, phenyl, biphenyl, naphthyl, pyridyl, thienyl, halo Phenyl, halogenated biphenyl, phenol, alkyl-containing phenol, alkenyl-containing phenol, alkynyl-containing phenol, nitrile-containing phenol, monohalogenated phenol, polyhalogenated phenol One of. In the above-mentioned embodiments of the present invention, the five-membered ring phosphite compounds all contain two five-membered ring phosphite structures, the phosphorus content increases, the flame retardant effect is enhanced, and the two five-membered ring structures and other functional groups Working together, the five-membered ring phosphite compound has comprehensive properties such as excellent film-forming properties, high-temperature and high-pressure stability, and can effectively improve battery safety when applied to batteries.
In some embodiments, the molar ratio of described compound B and described compound C is (2~3): 1, and the compound B of this proportioning and compound C can fully guarantee mutual reaction between compound, generate following C-centered five-membered ring phosphite compounds with B-C-B structure make five-membered ring phosphite compounds contain two molecules of five-membered ring phosphite structures at the same time, and through the interaction with other functional groups, five-membered ring phosphite compounds The membered ring phosphite compound has excellent flame retardancy, high temperature and high pressure resistance, and good stability.
In some embodiments, the step of adding phosphorus trichloride reaction after compound A is dissolved in non-aqueous solvent comprises: take the reaction system that volume is not more than 10L as benchmark, after compound A is dissolved in non-aqueous solvent, in Under the condition that the temperature is -40°C-40°C, add phosphorus trichloride at a rate of 0.5-1.5 drops/second and react until no gas is generated to obtain compound B. Since the reaction is a process of exothermic gas production, the embodiment of the present invention controls the reaction rate by controlling the drop rate of phosphorus trichloride, which can not only avoid the potential safety hazard caused by too fast addition of phosphorus trichloride, excessive heat production and gas production , and can effectively control the generation of by-products. If phosphorus trichloride is added too quickly, the reaction in the system will be violent, the exothermic gas will be violent, and more by-products will be easily generated during the rapid reaction process, which will increase the difficulty of subsequent separation and purification.
Test example of the present invention has made CR2032 type button type lithium ion battery, comprises: the electrolytic solution prepared by stainless steel battery case, gasket, shrapnel, positive electrode material, negative electrode material, membrane material and test example 1; Wherein, with nickel cobalt Lithium manganese oxide (LiNi0.6Co0.2Mn0.2O2, referred to as NCM622) ternary material is the positive electrode, artificial graphite is the negative electrode, and the positive electrode material is 96% positive electrode active material + 2% PVDF binder + 2% Super S conductive carbon by mass ratio Black is mixed into positive electrode slurry. The resulting slurry is then coated on aluminum foil in a clean room with a thickness of 0.06-0.20 mm. The negative electrode material is mixed into negative electrode slurry by mass ratio of 96% active material + 2% CMC/SBR binder + 2% Super S conductive carbon black, and then the obtained slurry is coated on copper foil in a clean room with a thickness of 0.06~0.20mm. Put the coated positive and negative pole pieces in a blast drying oven and dry them at 80°C for 12 hours, punch and slice the dried pole pieces, dry them in a vacuum drying oven at 120°C for 24 hours, and then transfer them to In the glove box (the content of water and oxygen in the glove box is less than 1ppm). Weigh to calculate the mass of the active substance. Finally, a 2032 coin cell was prepared in a glove box. The production of button batteries adopts a bottom-up assembly method, that is, positive electrode shell + positive electrode + separator + negative electrode + gasket + shrapnel + negative electrode shell, to reduce the misalignment of the positive and negative pole pieces caused by the shrapnel and gasket during the rotation process.
The embodiment of the present invention 2~33 prepares ...
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Abstract

The invention belongs to the technical field of batteries, and especially relates to a five-membered ring phosphite compound. The structural general formula of the five-membered ring phosphite compound is represented by formula 1 shown in the description; and in the formula, R<1>, R<2>, R<3>, R<4>, R<5>, R<6>, R<7>, R<8>, R<9>, R<10>, R<11>, R<12>, R<13>, R<14>, R<15>, R<16>, R<17> and R<18> are independently selected from hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkynyloxy group, an enyloxy group, a silyl group, a siloxane group, aryl silicon, an arylsilyl group, an arylsiloxy group, a halogenated alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halogenated phenyl group, a halogenated biphenyl group, a phenolic group, an alkyl-containing phenolic group, an alkenyl-containing phenolic group, an alkynyl-containing phenolic group, a nitrile-containing phenolic group, a monohalogenated phenolic group and a polyhalogenated phenolic group. The five-membered ring phosphite compound provided by the invention has excellent flame retardant property, can effectively prevent electrolytes from being oxidized when being applied to the field of batteries, reduces oxygenolysis of the electrolytes on positive electrodes, and remarkably improves the comprehensive properties such as high temperature, circulation, storage and the like of the batteries.

Application Domain

Technology Topic

Phosphite esterPhosphorous acid +17

Image

  • Five-membered ring phosphite compound, and preparation method and application thereof
  • Five-membered ring phosphite compound, and preparation method and application thereof
  • Five-membered ring phosphite compound, and preparation method and application thereof

Examples

  • Experimental program(34)
  • Effect test(2)

Example Embodiment

[0047] The embodiment of the present invention also provides a method for preparing a five-membered ring phosphite compound, which includes the following steps:
[0048] S10. After dissolving compound A in a non-aqueous solvent, adding phosphorus trichloride for reaction, and separating compound B;
[0049] S20. After mixing the compound B and the compound C, they are reacted at a temperature of -40°C to 60°C to separate a five-membered ring phosphite compound;
[0050] Wherein, the reactant A is selected from: and / or The reactant C is selected from: and / or
[0051] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 And R 18 They are independently selected from: hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkynyloxy, alkenyloxy, silyl, siloxane, arylsilyl, arylsilyl, haloalkyl , Phenyl, biphenyl, naphthyl, pyridyl, thienyl, halogenated phenyl, halogenated biphenyl, phenol, alkyl-containing phenol, alkenyl-containing phenol, alkynyl-containing phenol , One of nitrile-containing phenol groups, monohalogenated phenol groups, and polyhalogenated phenol groups.
[0052] In the method for preparing five-membered ring phosphite compounds provided by the embodiments of the present invention, compound A is dissolved in a non-aqueous solvent and then phosphorus trichloride is added to react to obtain compound B; then, after compound B is mixed with compound C, The five-membered ring phosphite compound can be obtained by reacting at a temperature of -40°C to 60°C. The preparation method of the five-membered ring phosphite compound provided by the embodiment of the present invention has the advantages of low raw material cost, simple experimental steps, safe operation, novel compound structure, high product purity, easy waste disposal, low environmental pollution, low production cost, etc. Advantage. The five-membered ring phosphite compound prepared by this method, due to the synergistic effect of the two five-membered ring phosphite structures and other functional groups, makes the five-membered ring phosphite compound have excellent flame retardancy and high temperature resistance High voltage and good stability.
[0053] Specifically, in the above step S10, the compound A is dissolved in a non-aqueous solvent and then phosphorus trichloride is added to react to isolate the compound B, wherein the reactant A is selected from: and / or The reaction process is as follows:
[0054] When A is Time,
[0055] When A is Time,
[0056] In the embodiment of the present invention, a five-membered ring phosphite structure is formed through the condensation reaction between the hydroxyl group in compound A and phosphorus trichloride.
[0057] In some embodiments, the step of dissolving compound A in a non-aqueous solvent and then adding phosphorus trichloride for the reaction includes: based on a reaction system with a volume not greater than 10L, after dissolving compound A in a non-aqueous solvent, the temperature is − Under the conditions of 40°C to 40°C, phosphorus trichloride is added at a rate of 0.5 to 1.5 drops per second, and then reacted until no gas is generated, thereby obtaining compound B. Since the reaction is an exothermic and gas production process, the embodiment of the present invention controls the reaction rate by controlling the dropping rate of phosphorus trichloride, which can not only avoid the potential safety hazards caused by excessive addition of phosphorus trichloride and excessive heat and gas production. , And can effectively control the generation of by-products. If phosphorus trichloride is added too fast, the reaction in the system will be violent, exothermic gas production will be violent, and more by-products will be easily generated during the rapid reaction process, which increases the difficulty of subsequent separation and purification.

Example Embodiment

[0091] Example 1
[0092] In order to be able to compare the preparation processes of the products more intuitively in parallel comparison, the same self-made compound B (namely compound B prepared in Example 1) is used in Examples 2 to 33 of the present invention. The specific preparation process includes:
[0093] ① At room temperature, add 310g ethylene glycol (reactant A) and 350g anhydrous dichloromethane (non-aqueous solvent) into a three-necked flask with a volume of 2000mL in a fume hood, then cool to 0°C, continue stirring for 0.5h, At this time, the solution is colorless and transparent, and the three-necked bottle is connected to an external gas absorption device.
[0094] ② 700g of phosphorus trichloride dissolved in 300g of anhydrous dichloromethane was slowly added to the three-necked flask via a dropping funnel, and the dropping rate was controlled to be 1 drop/sec. With the continuous dropping of the dichloromethane solution of phosphorus trichloride, the reaction emits a lot of heat and a large amount of HCl gas is released. Keep the reaction temperature at 0°C, and continue after the dichloromethane solution of phosphorus trichloride is all dropped. The reaction system is stirred until it is colorless and transparent (2h), and then the reaction is continued to be stirred for 12 hours until no gas is generated, and then the reaction system is distilled at atmospheric pressure to remove dichloromethane to obtain a pale yellow liquid, that is, the crude compound B. The crude product of compound B was distilled under reduced pressure at 80°C to obtain 656 g of colorless and transparent liquid with a yield of 92%; the product was compound B (vinyl chlorophosphite or 2-chloro-1,3,2-phosphorus Cyclopentane).
[0095] The mass spectrum of compound B, 1 H NMR test chart and 13 C NMR test chart is attached Figure 1-3 As shown in the mass spectrum, the molecular ion peak at molecular weight 126 is the molecular ion peak, and the molecular ion peak at molecular weight 91 is the remaining (C 2 H 4 PO 2 ) Group peak, the molecular weight 98 is knocked out (CH 2 -CH 2 ) Group remaining (PO 2 Cl) group peak, the molecular weight 66 is the fragment (PCl) group peak, the molecular weight 44 is the fragment (CH 2 -CH 2 -O) group peak, fragments (CH 2 -CH 2 ) The peak of the group. 1 H NMR spectrum can be seen (CH 2 -CH 2 ) Group’s methylene peak, the chemical shift is about 4.5ppm, indicating that the methylene group is connected to the oxygen atom (-OCH 2 -CH 2 -O), 13 C NMR spectrum can see the methylene peak (CH 2 -CH 2 ), the chemical shift is about 65ppm, indicating that the methylene group is connected to the oxygen atom (-OCH 2 -CH 2 -O). In summary, it can be seen from the test results that its structure is
[0096] The HCl gas generated by the reaction is absorbed by water to obtain hydrochloric acid. The hydrochloric acid is sold as a chemical raw material, and the organic solvent used in the reaction is distilled and dried and recycled and reused.

Example Embodiment

[0097] Example 2
[0098] Compound 1 ( Preparation of bis(1,3,2-dioxaphospholane) glycol ester):
[0099] Add 400g of dichloromethane (solvent, which has the same function as the aforementioned non-aqueous solvent, can be used selectively) and 62g of ethylene glycol (reactant C) into a 1000mL three-necked flask at room temperature. The solution is colorless and transparent. The three-necked flask is connected An external gas absorption device was connected, and then 300g of compound B prepared in Example 1 was slowly added to a 1000 mL three-necked flask via a dropping funnel, the dropping rate was controlled to 1 drop/sec, and the reaction temperature was 0°C. With the dropping of compound B, A large amount of heat is released and a large amount of HCl gas is released. After all the drops are completed, the solution is colorless and transparent (compound B is dropped for 1.5 hours), then the reaction is slowly raised to room temperature and stirring is continued for 12 hours, and dichloride is removed by atmospheric distillation Methane was used to obtain a pale yellow solid, which was further crystallized by ethanol and dried under vacuum for 3 hours to obtain 223 g of a white solid with a yield of 92%. The product is compound 1 (bis(1,3,2-dioxaphospholane) ethylene glycol ester), 1 H NMR(400MHz, CDCl 3 ):δ3.72(m,12H); 13 C NMR (100MHz) δ 64.2, 64.9.
[0100] The HCl gas generated by the reaction is absorbed by water to obtain hydrochloric acid. The hydrochloric acid is sold as a chemical raw material, and the organic solvent used in the reaction is distilled and dried and recycled and reused.
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PUM

PropertyMeasurementUnit
Radius5.0 ~ 10.0mm
Thickness0.06 ~ 0.2mm
tensileMPa
Particle sizePa
strength10

Description & Claims & Application Information

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