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CN115448947A - Halogenated phosphate containing branched chain, preparation method and application thereof - Google Patents

Halogenated phosphate containing branched chain, preparation method and application thereof Download PDF

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CN115448947A
CN115448947A CN202110645241.1A CN202110645241A CN115448947A CN 115448947 A CN115448947 A CN 115448947A CN 202110645241 A CN202110645241 A CN 202110645241A CN 115448947 A CN115448947 A CN 115448947A
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时迎华
钟海敏
田培钦
洪祖川
赵文文
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Evergrande New Energy Technology Shenzhen Co Ltd
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Abstract

本发明公开了一种含支链卤代磷酸酯及其制备方法和应用。该含支链卤代磷酸酯的分子结构式如下述通式Ⅰ所示。含支链卤代磷酸酯可以改善电解液的电化学性能,含该含支链卤代磷酸酯的电解液可以在电极材料表面形成更加稳定的界面膜,抑制阻抗增加,从而显著提升二次电池高低温、循环和存储等性能,该含支链卤代磷酸酯对抑制电池产气也有明显的作用。含支链卤代磷酸酯可以作为添加剂使用,并在电解液、二次电池中应用。

Figure DDA0003106642540000011
The invention discloses a halogenated phosphoric acid ester containing branched chains, a preparation method and application thereof. The molecular structural formula of the branched-chain halogenated phosphoric acid ester is shown in the following general formula I. The branched-chain halogenated phosphate can improve the electrochemical performance of the electrolyte, and the electrolyte containing the branched-chain halogenated phosphate can form a more stable interfacial film on the surface of the electrode material, suppressing the increase in impedance, thereby significantly improving the performance of the secondary battery. High and low temperature, cycle and storage performance, the branched-chain halogenated phosphate also has a significant effect on inhibiting battery gas production. The branched halogenated phosphoric acid ester can be used as an additive and applied in electrolyte and secondary battery.
Figure DDA0003106642540000011

Description

含支链卤代磷酸酯及其制备方法和应用Branched-chain-containing halogenated phosphoric acid ester and its preparation method and application

技术领域technical field

本发明属于电池材料技术领域,具体涉及含支链卤代磷酸酯及其制备方法,电解液添加剂、电解液和二次电池。The invention belongs to the technical field of battery materials, and in particular relates to a branched-chain halogenated phosphoric acid ester and a preparation method thereof, an electrolyte solution additive, an electrolyte solution and a secondary battery.

背景技术Background technique

锂离子电池是90年代开始发展起来的一种新型高能二次电池,锂离子电池与其他电池相比,具有能量密度高、体积小质量轻、放电速率快、自放电率低、循环寿命长、无记忆效应优点,在数码产品、动力、以及储能领域得到广泛的应用。Lithium-ion battery is a new type of high-energy secondary battery developed in the 1990s. Compared with other batteries, lithium-ion battery has high energy density, small size and light weight, fast discharge rate, low self-discharge rate, and long cycle life. It has no memory effect and is widely used in the fields of digital products, power, and energy storage.

由于诸多领域对电池的能量密度要求越来越高,快速充电越发成为趋势,电池材料必然朝着更高镍、更高电压、更大倍率方向发展。目前行业的难点主要集中在以下几个方面:Due to the increasingly high energy density requirements for batteries in many fields, fast charging has become a trend, and battery materials are bound to develop in the direction of higher nickel, higher voltage, and higher magnification. The current difficulties in the industry mainly focus on the following aspects:

1.体相结构控制:在电压较高情况下,正极由于过度脱锂,层状结构发生剧烈变化,同时伴随着相变及应力的产生,而过度的应力会使材料颗粒开裂粉化或破碎,破坏了材料的体相结构,劣化了循环性能。这一问题一定程度上可以通过元素共掺杂来抵消一定的应力,来达到抑制材料相变的目的;1. Bulk phase structure control: In the case of high voltage, the layered structure of the positive electrode changes drastically due to excessive delithiation, accompanied by phase transition and stress generation, and excessive stress will cause the material particles to crack, pulverize or break , destroying the bulk phase structure of the material and deteriorating the cycle performance. To a certain extent, this problem can be counteracted by element co-doping to offset a certain stress, so as to achieve the purpose of inhibiting the phase transition of the material;

2.界面结构的控制:主要通过引入新的界面包覆来优化界面结构,抑制过渡金属溶出,抑制界面结构变化,从而提高循环寿命;2. Interface structure control: mainly by introducing new interface coating to optimize the interface structure, inhibit the dissolution of transition metals, and inhibit the change of interface structure, thereby improving the cycle life;

3.抑制界面氧的活性:氧析出往往伴随着产气和过渡金属溶出。通过界面处理和电解液的组合使用,可以降低材料界面产气,从而达到提高材料高温状态下的稳定性,提高循环和存储性能。3. Inhibit the activity of oxygen at the interface: Oxygen precipitation is often accompanied by gas production and transition metal dissolution. Through the combined use of interface treatment and electrolyte, the gas generation at the material interface can be reduced, thereby improving the stability of the material at high temperature and improving the cycle and storage performance.

随着社会需求的不断发展,锂离子电池的使用寿命、高低温性能、安全性能、倍率性能等已不能满足动力电池发展的要求。提升动力电池性能有多种途径,其中添加剂对于电池的电化学性能起着至关重要的作用。到目前为止,人们已开发出数目众多的新型添加剂来改善电池性能。添加剂可以在电极材料表面形成固态电解质界面膜(SEI膜和CEI膜),锂二次电池的性能很大程度上取决于SEI膜,负极界面形成的SEI膜抑制了电解液在负极界面的副反应,同时还防止了电解液溶剂共嵌入到负极材料中,减轻了负极材料结构坍塌,同时还可以发挥锂离子通道的作用。With the continuous development of social needs, the service life, high and low temperature performance, safety performance, and rate performance of lithium-ion batteries can no longer meet the requirements of power battery development. There are many ways to improve the performance of power batteries, among which additives play a vital role in the electrochemical performance of batteries. So far, a large number of new additives have been developed to improve battery performance. Additives can form a solid electrolyte interface film (SEI film and CEI film) on the surface of the electrode material. The performance of lithium secondary batteries depends largely on the SEI film. The SEI film formed at the negative electrode interface inhibits the side reactions of the electrolyte at the negative electrode interface , At the same time, it also prevents the electrolyte solvent from co-intercalating into the negative electrode material, reduces the structure collapse of the negative electrode material, and can also play the role of lithium ion channel.

在锂二次电池的充放电过程中,正极活性材料在结构上坍塌或发生相变,同时金属离子从正极溶出并在负极被还原,使电池性能劣化。高温会加剧电池性能的劣化。现有研究表明电池热失控的起点来自电解质界面膜(SEI膜)的分解,随后电解质不断在正负极材料界面分解放出大量的热,导致安全问题的产生,诸多热失控因素都与电解液直接相关,即电解液是保证二次电池安全性的重要环节。During the charging and discharging process of the lithium secondary battery, the structure of the positive electrode active material collapses or undergoes a phase change, and at the same time metal ions are dissolved from the positive electrode and reduced at the negative electrode, deteriorating the performance of the battery. High temperature will aggravate the deterioration of battery performance. Existing studies have shown that the starting point of battery thermal runaway comes from the decomposition of the electrolyte interface film (SEI film), and then the electrolyte continues to decompose at the interface of positive and negative materials to release a large amount of heat, leading to safety problems. Many thermal runaway factors are directly related to the electrolyte. Related, that is, the electrolyte is an important link to ensure the safety of the secondary battery.

二次电池发展向高能量密度方向发展,正极高镍化是发展趋势,但是在研究和实际应用中发现,高能量密度二次电池在循环过程中易出现高镍材料劣化严重,产气严重以及化学稳定性低的问题。虽然目前公开报道了电解液添加剂,如包括改善电解液稳定性和抑制二次电池在循环过程中产气作用的添加剂,但是在研究和实际应用中发现,目前公开的添加剂本身的热稳定性和对电解液热稳定的改善作用不理想,导致其提高电解液稳定和抑制产气作用的相关添加剂的作用依然不理想,特别是对于高能量密度二次电池循环过程中易出现严重的产气以及化学稳定性降低等问题的改善效果不理想。从而导致高镍正极在高温储存或循环期间大量产气,导致电池鼓胀同时高温性能变差。The development of secondary batteries is developing in the direction of high energy density, and the high-nickelization of the cathode is the development trend. However, it has been found in research and practical applications that high-energy-density secondary batteries are prone to serious deterioration of high-nickel materials, serious gas production, and The problem of low chemical stability. Although electrolyte additives have been publicly reported, such as additives that improve the stability of the electrolyte and inhibit the gas production of the secondary battery during cycling, it has been found in research and practical applications that the thermal stability of the currently disclosed additives and their impact on The effect of improving the thermal stability of the electrolyte is not ideal, and the effect of related additives to improve the stability of the electrolyte and inhibit gas production is still not ideal, especially for high energy density secondary batteries that are prone to serious gas production and chemical The improvement effect of problems such as reduced stability is not satisfactory. As a result, the high-nickel positive electrode produces a large amount of gas during high-temperature storage or circulation, resulting in battery swelling and poor high-temperature performance.

鉴于以上情况,需要开发新型的添加剂,以稳定正负极材料结构并降低电池阻抗,同时保证锂二次电池在高温循环和高温存储过程中的稳定性。In view of the above situation, it is necessary to develop new additives to stabilize the structure of positive and negative electrode materials and reduce battery impedance, while ensuring the stability of lithium secondary batteries during high-temperature cycling and high-temperature storage.

发明内容Contents of the invention

本发明的目的在于克服现有技术的上述不足,提供一种含支链卤代磷酸酯及其制备方法,以解决现有添加剂热稳定性和其提高电解液高温稳定性和抑制产气作用的效果不理想的技术问题。The purpose of the present invention is to overcome the above-mentioned deficiencies of the prior art, to provide a branched-chain-containing halogenated phosphoric acid ester and a preparation method thereof, to solve the problems of existing additives in terms of thermal stability and improving the high-temperature stability of the electrolyte and inhibiting gas production. Unsatisfactory technical issues.

本发明的另一目的在于提供一种添加剂、含有该添加剂的电解液和含有电解液的二次电池,以解决现有电解液由于热稳定性不理想而导致电池如高温循环性和储存性能不理想的技术问题。Another object of the present invention is to provide an additive, an electrolyte containing the additive, and a secondary battery containing the electrolyte, so as to solve the problem of poor thermal stability of the existing electrolyte such as high temperature cycle performance and poor storage performance of the battery. Ideal for technical questions.

为了实现上述发明目的,本发明的一方面,提供了一种含支链卤代磷酸酯。本发明含支链卤代磷酸酯的分子结构式如下述通式Ⅰ所示:In order to achieve the purpose of the above invention, one aspect of the present invention provides a branched-chain halogenated phosphoric acid ester. The molecular structural formula of the present invention containing branched-chain halogenated phosphoric acid ester is shown in the following general formula I:

Figure BDA0003106642530000021
Figure BDA0003106642530000021

其中,通式Ⅰ中的R1、R2、R3独立的选自碳原子数为1~10的烷基、碳原子数为1~10的烯基、碳原子数为1~10的炔基、碳原子数为1~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、三甲基硅基、三甲基硅氧基、含卤素的烷基、苯基、联苯基、萘基、吡啶基、噻吩基、卤代苯基、卤代联苯、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、卤代苯酚基、卤代萘酚基中的一种;Among them, R 1 , R 2 , and R 3 in the general formula I are independently selected from alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 1 to 10 carbon atoms, and alkyne groups with 1 to 10 carbon atoms. Group, chain alkoxy group with 1 to 10 carbon atoms, chain alkenyloxy group with 2 to 10 carbon atoms, chain alkynyloxy group with 2 to 10 carbon atoms, and chain alkyneoxy group with 3 to 10 carbon atoms Cyclic alkoxyl with 10, cyclic alkenyloxyl with 3 to 10 carbon atoms, trimethylsilyl, trimethylsilyloxy, halogen-containing alkyl, phenyl, biphenyl, naphthyl , pyridyl, thienyl, halogenated phenyl, halogenated biphenyl, phenol, alkyl-containing phenol, alkenyl-containing phenol, alkynyl-containing phenol, nitrile-containing phenol, halogenated One of phenol group and halogenated naphthol group;

R4、R5、R6、R7分别独立的选自氢原子、卤素原子、碳原子数为6~10的芳香基团、碳原子数为6~10的卤代芳香基团中的一种基团,碳原子数为1~10的烷基、碳原子数为1~10的卤代烷基、碳原子数为1~10的烯基、碳原子数为1~10的卤代烯基、碳原子数为1~10的炔基、碳原子数为1~10的卤代炔基、碳原子数为2~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、碳原子数为3~20的三烷基硅基、碳原子数为3~20的三烷基硅氧基、含芳基硅基、含芳基硅氧基、吡啶基、噻吩基、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、卤代苯酚基、卤代萘酚基中的一种;R 4 , R 5 , R 6 , and R 7 are each independently selected from a hydrogen atom, a halogen atom, an aromatic group with 6 to 10 carbon atoms, and a halogenated aromatic group with 6 to 10 carbon atoms. A group, an alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, a haloalkenyl group with 1 to 10 carbon atoms, Alkynyl with 1 to 10 carbon atoms, haloalkynyl with 1 to 10 carbon atoms, chain alkoxy with 2 to 10 carbon atoms, chain alkenyloxy with 2 to 10 carbon atoms Group, chain alkynyloxy group with 2 to 10 carbon atoms, cyclic alkoxy group with 3 to 10 carbon atoms, cyclic alkenyloxy group with 3 to 10 carbon atoms, 3 to 10 carbon atoms 20 trialkylsilyl groups, trialkylsiloxy groups with 3 to 20 carbon atoms, aryl-containing silyl groups, aryl-containing siloxy groups, pyridyl groups, thienyl groups, phenol groups, and alkyl-containing phenol groups One of group, alkenyl-containing phenol group, alkynyl-containing phenol group, nitrile-containing phenol group, halogenated phenol group, halogenated naphthol group;

M1、M2独立的选自卤素原子;M 1 and M 2 are independently selected from halogen atoms;

x为0~10的整数。x is an integer of 0-10.

本发明含支链卤代磷酸酯所含的磷酸基团具有正极成膜功能,可以显著改善正极材料的循环稳定性和降低阻抗。含支链卤代磷酸酯所含的其他基团能够起到对磷酸基团的成膜增效作用,提高含支链卤代磷酸酯正负极界面的稳定性。所含的卤代基团和/或卤素原子赋予含支链卤代磷酸酯良好浸润性。因此,本发明含支链卤代磷酸酯能够显著改善电解液的热稳定性,提高电解液成膜性能和浸润性能,赋予电解液低阻抗特性。The phosphoric acid group contained in the branched-chain halogenated phosphoric acid ester of the present invention has the function of positive electrode film formation, which can significantly improve the cycle stability of the positive electrode material and reduce the impedance. The other groups contained in the branched-chain halogenated phosphate can play a synergistic effect on the film formation of the phosphoric acid group, and improve the stability of the positive and negative interface of the branched-chain-containing halogenated phosphate. The contained halogenated groups and/or halogen atoms endow branched-chain-containing halogenated phosphates with good wettability. Therefore, the branched chain-containing halogenated phosphoric acid ester of the present invention can significantly improve the thermal stability of the electrolyte, improve the film-forming performance and wettability of the electrolyte, and endow the electrolyte with low impedance characteristics.

进一步地,R1至R7中的至少一基团为链状基团,链状基团包括直链基团或支链基团。该些链状基团均能够调节电解质界面的膜组分和成膜能力,同时能够提高其与磷酸酯基团之间的成膜增效作用,以提升含支链卤代磷酸酯的热稳定作用。Further, at least one group among R 1 to R 7 is a chain group, and the chain group includes a straight chain group or a branched chain group. These chain groups can adjust the film composition and film-forming ability of the electrolyte interface, and at the same time can improve the film-forming synergistic effect between it and the phosphate group, so as to improve the thermal stability of the branched-chain halophosphate effect.

进一步地,R1至R7中的至少一基团为链状基团,且链状基团包含卤素原子、氧原子或不饱和键官能团中的至少一种。Further, at least one group among R 1 to R 7 is a chain group, and the chain group includes at least one of a halogen atom, an oxygen atom or an unsaturated bond functional group.

具体地,链状基团包含不饱和键官能团时,不饱和键官能团包括碳碳双键、碳碳三键、碳氮双键、碳氮三键、碳氧双键、硫氧双键、磷氧双键、酰胺、酰亚胺、磺酰胺、磺酰亚胺、磷酰胺、磷酰亚胺、羧酸酯、磺酸酯和磷酸酯中的至少一种。Specifically, when the chain group contains unsaturated bond functional groups, the unsaturated bond functional groups include carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, carbon-nitrogen triple bonds, carbon-oxygen double bonds, sulfur-oxygen double bonds, phosphorus At least one of oxygen double bonds, amides, imides, sulfonamides, sulfonimides, phosphoramides, phosphorimides, carboxylates, sulfonates and phosphates.

具体地,链状基团包含不饱和键官能团时,不饱和键官能团的位置在端基或/和者内侧。Specifically, when the chain group contains an unsaturated bond functional group, the position of the unsaturated bond functional group is inside the end group or/and.

该些链状基团能够进一步提高对磷酸基团的成膜增效作用,提高含支链卤代磷酸酯正负极界面的稳定性,提高含支链卤代磷酸酯正负极界面的稳定性。These chain groups can further improve the film-forming synergistic effect on phosphoric acid groups, improve the stability of the positive and negative interfaces containing branched-chain halophosphates, and improve the stability of the positive and negative interfaces containing branched-chain halophosphates. sex.

进一步地,R1至R7中的至少一基团为卤代基团,卤代基团为部分取代或全取代。Further, at least one group among R 1 to R 7 is a halogenated group, and the halogenated group is partially substituted or fully substituted.

进一步地,M1、M2所示的卤素原子为氟、氯、溴、碘原子中的至少一种。Further, the halogen atoms represented by M 1 and M 2 are at least one of fluorine, chlorine, bromine and iodine atoms.

该些卤代基团和M1、M2所代表卤素原子的提高了含支链卤代磷酸酯的浸润性。The halogenated groups and the halogen atoms represented by M 1 and M 2 improve the wettability of the branched-chain halogenated phosphoric acid ester.

进一步地,含支链卤代磷酸酯包括如下分子结构式Ⅰ1至结构式Ⅰ7中至少一种:Further, the branched-chain-containing halogenated phosphoric acid ester includes at least one of the following molecular structural formulas I 1 to structural formula I 7 :

Figure BDA0003106642530000022
Figure BDA0003106642530000022

Figure BDA0003106642530000031
Figure BDA0003106642530000031

其中,通式Ⅰ2至Ⅰ7中的R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R34独立的选自氢原子、卤素原子、碳原子数为6~10的芳香基团、碳原子数为6~10的卤代芳香基团、碳原子数为1~10的烷基、碳原子数为1~10的卤代烷基、碳原子数为1~10的烯基、碳原子数为1~10的卤代烯基、碳原子数为1~10的炔基、碳原子数为1~10的卤代炔基、碳原子数为2~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、碳原子数为3~20的三烷基硅基、碳原子数为3~20的三烷基硅氧基、含芳基硅基、含芳基硅氧基、吡啶基、噻吩基、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、单卤代苯酚基、多卤代苯酚基中的一种;m、n、o、p、y、z独立的为0~10的整数。Among them, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 are independently selected from hydrogen atom, halogen atom , aromatic groups with 6 to 10 carbon atoms, halogenated aromatic groups with 6 to 10 carbon atoms, alkyl groups with 1 to 10 carbon atoms, halogenated alkyl groups with 1 to 10 carbon atoms, carbon Alkenyl with 1 to 10 atoms, haloalkenyl with 1 to 10 carbon atoms, alkynyl with 1 to 10 carbon atoms, haloalkynyl with 1 to 10 carbon atoms, Chained alkoxy groups with 2 to 10 carbon atoms, chained alkenyloxy groups with 2 to 10 carbon atoms, chain alkynyloxy groups with 2 to 10 carbon atoms, and cyclic alkanes with 3 to 10 carbon atoms Oxygen, cyclic alkenyloxy with 3 to 10 carbon atoms, trialkylsilyl with 3 to 20 carbon atoms, trialkylsilyloxy with 3 to 20 carbon atoms, aryl silicon aryl group, pyridyl group, thienyl group, phenol group, alkyl group containing phenol group, alkenyl group containing phenol group, alkynyl group containing phenol group, nitrile group containing phenol group, monohalogenated phenol One of the group and the polyhalogenated phenol group; m, n, o, p, y, z are independently integers of 0-10.

具体实施例中,含支链卤代磷酸酯包含如下式1至式20所示化合物中的至少一种:In a specific embodiment, the branched-chain-containing halophosphate comprises at least one of the compounds shown in the following formulas 1 to 20:

Figure BDA0003106642530000032
Figure BDA0003106642530000032

Figure BDA0003106642530000041
Figure BDA0003106642530000041

结构式Ⅰ1至结构式Ⅰ7所示具体如式1至式20所示的含支链卤代磷酸酯具有更优异的正极成膜功能和浸润性以及低阻抗,热稳定性更优异。The branched-chain halogenated phosphoric acid esters represented by the structural formula I 1 to the structural formula I 7 specifically as shown in the formula 1 to the formula 20 have more excellent positive electrode film-forming function and wettability, low impedance, and better thermal stability.

本发明的另一方面,提供了本发明含支链卤代磷酸酯的制备方法。本发明含支链卤代磷酸酯的制备方法包括如下步骤:Another aspect of the present invention provides a method for preparing the branched-chain-containing halogenated phosphoric acid ester of the present invention. The preparation method of the present invention containing branched chain halogenated phosphoric acid ester comprises the steps:

将如下结构式ⅠA所示的反应物A与如下结构式ⅠB所示的反应物B于第一非水溶液中进行第一取代反应,生成如下结构式Ⅰ所示的含支链卤代磷酸酯产物;The reactant A shown in the following structural formula I A and the reactant B shown in the following structural formula I B are subjected to a first substitution reaction in a first non-aqueous solution to generate a branched-chain halophosphate product shown in the following structural formula I;

Figure BDA0003106642530000042
Figure BDA0003106642530000042

其中,式ⅠA和Ⅰ中的R1、R2、R3独立的选自R1、R2、R3独立的选自碳原子数为1~10的烷基、碳原子数为1~10的烯基、碳原子数为1~10的炔基、碳原子数为1~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、三甲基硅基、三甲基硅氧基、含卤素的烷基、苯基、联苯基、萘基、吡啶基、噻吩基、卤代苯基、卤代联苯、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、卤代苯酚基、卤代萘酚基中的一种;R4、R5、R6、R7分别独立的选自氢原子、卤素原子、碳原子数为6~10的芳香基团、碳原子数为6~10的卤代芳香基团、碳原子数为1~10的烷基、碳原子数为1~10的卤代烷基、碳原子数为1~10的烯基、碳原子数为1~10的卤代烯基、碳原子数为1~10的炔基、碳原子数为1~10的卤代炔基、碳原子数为2~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、碳原子数为3~20的三烷基硅基、碳原子数为3~20的三烷基硅氧基、含芳基硅基、含芳基硅氧基、吡啶基、噻吩基、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、卤代苯酚基、卤代萘酚基中的一种;M1、M2、M3独立的选自卤素原子;x为0~10的整数。Among them, R 1 , R 2 , and R 3 in Formula I A and I are independently selected from R 1 , R 2 , and R 3 are independently selected from alkyl groups with 1 to 10 carbon atoms, and alkyl groups with 1 to 10 carbon atoms. Alkenyl with 10, alkynyl with 1 to 10 carbon atoms, chain alkoxy with 1 to 10 carbon atoms, chain alkenyloxy with 2 to 10 carbon atoms, and chain alkenyl with 2 to 10 carbon atoms 10-chain alkynyloxy, cyclic alkoxy with 3 to 10 carbon atoms, cyclic alkenyloxy with 3 to 10 carbon atoms, trimethylsilyl, trimethylsilyloxy, containing Halogenated alkyl, phenyl, biphenyl, naphthyl, pyridyl, thienyl, halogenated phenyl, halogenated biphenyl, phenol, alkyl-containing phenol, alkenyl-containing phenol, alkyne-containing One of phenol group, nitrile-containing phenol group, halogenated phenol group, halogenated naphthol group; R 4 , R 5 , R 6 , R 7 are independently selected from hydrogen atom, halogen atom, carbon Aromatic groups with 6 to 10 atoms, halogenated aromatic groups with 6 to 10 carbon atoms, alkyl groups with 1 to 10 carbon atoms, halogenated alkyl groups with 1 to 10 carbon atoms, Alkenyl with 1 to 10 carbon atoms, haloalkenyl with 1 to 10 carbon atoms, alkynyl with 1 to 10 carbon atoms, haloalkynyl with 1 to 10 carbon atoms, and 2 carbon atoms Chain alkoxy with 10 to 10, chain alkenyloxy with 2 to 10 carbon atoms, chain alkynyloxy with 2 to 10 carbon atoms, cyclic alkoxy with 3 to 10 carbon atoms , cyclic alkenyloxy groups with 3 to 10 carbon atoms, trialkylsilyl groups with 3 to 20 carbon atoms, trialkylsiloxy groups with 3 to 20 carbon atoms, aryl silicon groups, Aryl-containing siloxy, pyridyl, thienyl, phenol, alkyl-containing phenol, alkenyl-containing phenol, alkynyl-containing phenol, nitrile-containing phenol, halogenated phenol, halogen One of substituted naphthol groups; M 1 , M 2 , and M 3 are independently selected from halogen atoms; x is an integer of 0-10.

本发明含支链卤代磷酸酯制备方法制备的目标产物含支链卤代磷酸酯含有磷酸酯基团等功能基团,赋予制备的含支链卤代磷酸酯具有优异成膜性能和浸润性能以及低阻抗特性,其热稳定性高。另外,含支链卤代磷酸酯制备方法通过一步反应生成目标产物,目标产物得率高,副反应少,工艺条件易控,其制备获得的含支链卤代磷酸酯的得率和性能稳定。同时,采用非水溶液作为反应溶剂,还能够降低对目标产物的纯化难度。The target product prepared by the method for preparing branched-chain-containing halogenated phosphoric acid esters of the present invention contains functional groups such as phosphoric acid ester groups, which endows the prepared branched-chain-containing halogenated phosphoric acid esters with excellent film-forming properties and wetting properties As well as low impedance characteristics, its thermal stability is high. In addition, the method for preparing the branched-chain halogenated phosphoric acid ester generates the target product through a one-step reaction, the yield of the target product is high, the side reactions are few, the process conditions are easy to control, and the yield and performance of the branched-chain-containing halogenated phosphoric acid ester prepared by the method are stable. . At the same time, using a non-aqueous solution as a reaction solvent can also reduce the difficulty of purifying the target product.

进一步地,反应物A与反应物B是按照摩尔比为1:(1~6)的比例混合于第一非水溶液中并进行第一取代反应。Further, the reactant A and the reactant B are mixed in the first non-aqueous solution according to a molar ratio of 1:(1-6), and the first substitution reaction is performed.

进一步地,反应物A与第一非水溶液的质量比为1:(1~6)。Further, the mass ratio of the reactant A to the first non-aqueous solution is 1:(1-6).

通过反应物A与反应物B的比例和浓度的调整,提高第一取代反应正向反应速率,提高第一取代反应的效率,并节约反应物用量降低合成成本。By adjusting the ratio and concentration of the reactant A and the reactant B, the forward reaction rate of the first substitution reaction is increased, the efficiency of the first substitution reaction is improved, and the amount of the reactant is saved to reduce the synthesis cost.

进一步地,第一取代反应的温度为-20~40℃。通过对取代反应的温度控制和优化,提高取代反应的效率。Further, the temperature of the first substitution reaction is -20-40°C. Through the temperature control and optimization of the substitution reaction, the efficiency of the substitution reaction is improved.

具体地,第一取代反应包括先进行前段取代反应再进行后段取代反应的步骤;其中,前段取代反应是将反应物A逐渐加入至含有反应物B的第一非水溶液中直至添加完毕后继续反应1-2小时的取代反应阶段,后段取代反应为反应物A添加完毕并继续反应1-2小时后直至取代反应结束的阶段;且前段取代反应的温度为-20~0℃;后段取代反应的温度为0~40℃。通过将取代反应设置为两阶段,提高第一取代反应的效率,降低副产物的生成,提高目标产物的得率。Specifically, the first substitution reaction includes the steps of first performing the front-stage substitution reaction and then carrying out the rear-stage substitution reaction; wherein, the front-stage substitution reaction is to gradually add the reactant A to the first non-aqueous solution containing the reactant B until the addition is completed. In the substitution reaction stage of reaction for 1-2 hours, the latter stage of the substitution reaction is the stage after the addition of reactant A is completed and the reaction continues for 1-2 hours until the end of the substitution reaction; and the temperature of the former stage of the substitution reaction is -20~0°C; The temperature of the substitution reaction is 0-40°C. By setting the substitution reaction into two stages, the efficiency of the first substitution reaction is improved, the generation of by-products is reduced, and the yield of the target product is increased.

进一步地,反应物A包括如下结构式A1至A6中的至少一种:Further, the reactant A includes at least one of the following structural formulas A1 to A6:

Figure BDA0003106642530000051
Figure BDA0003106642530000051

其中,通式A1至A6中的R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R34独立的选自氢原子、卤素原子、碳原子数为6~10的芳香基团、碳原子数为6~10的卤代芳香基团、碳原子数为1~10的烷基、碳原子数为1~10的卤代烷基、碳原子数为1~10的烯基、碳原子数为1~10的卤代烯基、碳原子数为1~10的炔基、碳原子数为1~10的卤代炔基、碳原子数为2~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、碳原子数为3~20的三烷基硅基、碳原子数为3~20的三烷基硅氧基、含芳基硅基、含芳基硅氧基、吡啶基、噻吩基、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、单卤代苯酚基、多卤代苯酚基中的一种;m、n、o、p、y、z独立的为0~10的整数。该些反应物A能够与反应物B生成上文结构式Ⅰ2至结构式Ⅰ7所示的含支链卤代磷酸酯,而且能够提高第二取代反应的效率和目标产物的得率。Among them, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 are independently selected from hydrogen atom, halogen atom , aromatic groups with 6 to 10 carbon atoms, halogenated aromatic groups with 6 to 10 carbon atoms, alkyl groups with 1 to 10 carbon atoms, halogenated alkyl groups with 1 to 10 carbon atoms, carbon Alkenyl with 1 to 10 atoms, haloalkenyl with 1 to 10 carbon atoms, alkynyl with 1 to 10 carbon atoms, haloalkynyl with 1 to 10 carbon atoms, Chained alkoxy groups with 2 to 10 carbon atoms, chained alkenyloxy groups with 2 to 10 carbon atoms, chain alkynyloxy groups with 2 to 10 carbon atoms, and cyclic alkanes with 3 to 10 carbon atoms Oxygen, cyclic alkenyloxy with 3 to 10 carbon atoms, trialkylsilyl with 3 to 20 carbon atoms, trialkylsilyloxy with 3 to 20 carbon atoms, aryl silicon aryl group, pyridyl group, thienyl group, phenol group, alkyl group containing phenol group, alkenyl group containing phenol group, alkynyl group containing phenol group, nitrile group containing phenol group, monohalogenated phenol One of the group and the polyhalogenated phenol group; m, n, o, p, y, z are independently integers of 0-10. These reactants A can form the branched-chain halogenated phosphoric acid esters shown in the above structural formula I 2 to structural formula I 7 with the reactant B, and can improve the efficiency of the second substitution reaction and the yield of the target product.

进一步地,第一非水溶液选自乙腈、丙腈、1,3-二氧戊环、四氢呋喃、2-甲基四氢呋喃、2,5-二甲基四氢呋喃、1,4-二氧六环、乙二醇二甲醚、乙二醇二乙醚、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲酰胺、六甲基磷酰三胺、六甲基亚磷酰三胺、六乙基磷酰三胺、六乙基亚磷酰三胺、二甲基亚砜、二乙基亚砜、二氯甲烷、三氯甲烷、乙醚、丙醚、甲基叔丁基醚、乙基叔丁基醚、乙酸甲酯、乙酸乙酯、丙酸乙酯、乙酸丙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、正己烷、正庚烷、环己烷、苯、甲苯、二甲苯中的至少一种。该些非水溶液能够有效溶解两反应物,而且能够有效减少副产物的生成,提高目标产物的得率。Further, the first non-aqueous solution is selected from acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, ethyl Glycol dimethyl ether, ethylene glycol diethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, formamide, hexamethylphosphoryl triamide, hexamethylphosphorous triamide Amine, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether , ethyl tert-butyl ether, methyl acetate, ethyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, n-hexane, n-heptane, cyclohexane , benzene, toluene, xylene at least one. These non-aqueous solutions can effectively dissolve the two reactants, and can effectively reduce the formation of by-products and increase the yield of the target product.

进一步地,M1、M2独立的选自氯、溴、碘原子中的任一种时,还包括如下步骤:Further, when M 1 and M 2 are independently selected from any one of chlorine, bromine, and iodine atoms, the following steps are also included:

将经第一取代反应生成的结构式Ⅰ所示的含支链卤代磷酸酯产物与氟化物于第二非水溶液中进行第二取代反应,生成如下述通式Ⅰ1所示的含支链二氟磷酸酯产物;The branched-chain halogenated phosphoric acid ester product represented by the structural formula I generated through the first substitution reaction is subjected to the second substitution reaction with fluoride in the second non-aqueous solution to generate the branched-chain-containing bisphosphonate shown in the following general formula I1. Fluorophosphate products;

Figure BDA0003106642530000052
Figure BDA0003106642530000052

通过对第一取代反应生成产物进行氟取代反应,使得生成的含支链二氟磷酸酯产物具有更加优异的浸润性,而且添加电解液中后不附带杂质元素或杂质元素少,从而提高相应电解质或电解液纯度和相应的化学性能。By performing a fluorine substitution reaction on the product generated by the first substitution reaction, the resulting branched-chain difluorophosphate product has more excellent wettability, and after being added to the electrolyte, there are no or few impurity elements, thereby improving the corresponding electrolyte. Or electrolyte purity and corresponding chemical properties.

更进一步地,结构式Ⅰ所示的含支链卤代磷酸酯产物与氟化物是按照摩尔比为1:(1~6)的比例混合于第二非水溶液中并进行第二取代反应。Furthermore, the branched-chain halogenated phosphoric acid ester product represented by structural formula I and the fluoride are mixed in the second non-aqueous solution according to a molar ratio of 1: (1-6) and undergo a second substitution reaction.

更进一步地,结构式Ⅰ所示的含支链卤代磷酸酯产物与第二非水溶液的质量比为1:(1~10)。Furthermore, the mass ratio of the branched chain-containing halogenated phosphoric acid ester product represented by the structural formula I to the second non-aqueous solution is 1: (1-10).

通过结构式Ⅰ所示的含支链卤代磷酸酯产物与氟化物的比例和浓度的调整,提高第二取代反应的效率,并节约反应物用量降低合成成本。By adjusting the ratio and concentration of the branched-chain halogenated phosphoric acid ester product shown in the structural formula I and the fluoride, the efficiency of the second substitution reaction is improved, and the amount of reactants is saved to reduce the synthesis cost.

更进一步地,第二取代反应的温度为-20~80℃。通过对取代反应的温度控制和优化,提高取代反应的效率。Furthermore, the temperature of the second substitution reaction is -20-80°C. Through the temperature control and optimization of the substitution reaction, the efficiency of the substitution reaction is improved.

更进一步地,氟化物选自氟化氢、三乙胺氟化氢、吡啶氟化氢、氟化钾、氟化钠、氟化镁、氟化锌、氟化铝、三氟化锑、五氟化锑、四氟化硫、六氟化硫中的至少一种。该些氟化物能够有效与结构式Ⅰ所示的含支链卤代磷酸酯发生取代反应,提高第二取代反应的效率和提高含支链二氟磷酸酯产物的得率。Furthermore, the fluoride is selected from hydrogen fluoride, triethylamine hydrogen fluoride, pyridine hydrogen fluoride, potassium fluoride, sodium fluoride, magnesium fluoride, zinc fluoride, aluminum fluoride, antimony trifluoride, antimony pentafluoride, tetrafluoro At least one of sulfur sulfide and sulfur hexafluoride. These fluorides can effectively undergo a substitution reaction with the branched-chain-containing halogenated phosphoric acid ester shown in the structural formula I, thereby improving the efficiency of the second substitution reaction and increasing the yield of branched-chain-containing difluorophosphate ester products.

更进一步地,第二非水溶液选自乙腈、丙腈、1,3-二氧戊环、四氢呋喃、2-甲基四氢呋喃、2,5-二甲基四氢呋喃、1,4-二氧六环、乙二醇二甲醚、乙二醇二乙醚、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲酰胺、六甲基磷酰三胺、六甲基亚磷酰三胺、六乙基磷酰三胺、六乙基亚磷酰三胺、二甲基亚砜、二乙基亚砜、二氯甲烷、三氯甲烷、乙醚、丙醚、甲基叔丁基醚、乙基叔丁基醚、乙酸甲酯、乙酸乙酯、丙酸乙酯、乙酸丙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、正己烷、正庚烷、环己烷、苯、甲苯、二甲苯中的至少一种。该些非水溶液能够有效溶解两反应物,而且能够有效减少副产物的生成,提高目标产物的得率。Furthermore, the second non-aqueous solution is selected from acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous Triamine, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl Ether, ethyl tert-butyl ether, methyl acetate, ethyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, n-hexane, n-heptane, cyclohexane at least one of alkanes, benzene, toluene, and xylene. These non-aqueous solutions can effectively dissolve the two reactants, and can effectively reduce the formation of by-products and increase the yield of the target product.

本发明的再一方面,提供了电解液添加剂。本发明电解液添加剂含有本发明含支链卤代磷酸酯或由含支链卤代磷酸酯制备方法制备的含支链卤代磷酸酯。由于电解液添加剂含有本发明含支链卤代磷酸酯,因此,电解液添加剂能够显著改善电解液的热稳定性,提高其成膜性能和浸润性能以及低阻抗特性。In yet another aspect of the present invention, an electrolyte additive is provided. The electrolyte additive of the present invention contains the branched-chain-containing halogenated phosphoric acid ester of the present invention or the branched-chain-containing halogenated phosphoric acid ester prepared by the preparation method of the branched-chain-containing halogenated phosphoric acid ester. Since the electrolyte additive contains the branched chain-containing halogenated phosphoric acid ester of the present invention, the electrolyte additive can significantly improve the thermal stability of the electrolyte, improve its film-forming performance, wetting performance and low impedance characteristics.

本发明的又一方面,提供了一种电解液。本发明电解液包括添加剂,且添加剂为本发明电解液添加剂。电解液由于含有本发明电解液添加剂,也即是含有本发明含支链卤代磷酸酯,因此,本发明电解液的成膜性能、浸润性能以及热稳定性好,可以显著提升二次电池高低温、循环和存储等性能,同时还能抑制二次电池产气以及阻抗增长,提高了二次电池安全性能和综合性能。In yet another aspect of the present invention, an electrolyte solution is provided. The electrolyte of the present invention includes an additive, and the additive is an additive of the electrolyte of the present invention. Since the electrolyte contains the electrolyte additive of the present invention, that is, contains the branched chain-containing halogenated phosphoric acid ester of the present invention, the film-forming performance, wetting performance and thermal stability of the electrolyte of the present invention are good, which can significantly improve the secondary battery. Low temperature, cycle and storage performance, and at the same time, it can inhibit the gas production and impedance growth of the secondary battery, improving the safety performance and comprehensive performance of the secondary battery.

本发明的还一方面,提供了一种二次电池。本发明二次电池包括本发明电解液。因此,二次电池在高低温下均具有良好的循环性能和存储性能,降低了二次电池产气以及阻抗增长等不良现象发生,安全性高,综合化学性能好,使用寿命更长。Still another aspect of the present invention provides a secondary battery. The secondary battery of the present invention includes the electrolytic solution of the present invention. Therefore, the secondary battery has good cycle performance and storage performance at high and low temperatures, reduces secondary battery gas production and impedance growth and other adverse phenomena, high safety, good comprehensive chemical properties, and longer service life.

具体实施方式detailed description

为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

本申请中,术语“和/或”,描述关联对象的关联关系,表示可以存在三种关系,例如,A和/或B,可以表示:单独存在A,同时存在A和B,单独存在B的情况。其中A,B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。In this application, the term "and/or" describes the association relationship of associated objects, indicating that there may be three relationships, for example, A and/or B may mean: A exists alone, A and B exist simultaneously, and B exists alone Condition. Among them, A and B can be singular or plural. The character "/" generally indicates that the contextual objects are an "or" relationship.

本申请中,“至少一个”是指一个或者多个,“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达,是指的这些项中的任意组合,包括单项(个)或复数项(个)的任意组合。例如,“a,b,或c中的至少一项(个)”,或,“a,b,和c中的至少一项(个)”,均可以表示:a,b,c,a-b(即a和b),a-c,b-c,或a-b-c,其中a,b,c分别可以是单个,也可以是多个。In this application, "at least one" means one or more, and "multiple" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one item (unit) of a, b, or c", or "at least one item (unit) of a, b, and c" can mean: a, b, c, a-b( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

应理解,在本申请的各种实施例中,上述各过程的序号的大小并不意味着执行顺序的先后,部分或全部步骤可以并行执行或先后执行,各过程的执行顺序应以其功能和内在逻辑确定,而不应对本申请实施例的实施过程构成任何限定。It should be understood that in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the order of execution, and some or all steps may be executed in parallel or sequentially, and the execution order of each process shall be based on its functions and The internal logic is determined and should not constitute any limitation to the implementation process of the embodiment of the present application.

在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的,而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”和“该”也旨在包括多数形式,除非上下文清楚地表示其他含义。Terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a" and "the" used in the embodiments of this application and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

本申请实施例说明书中所提到的相关成分的重量不仅仅可以指代各组分的具体含量,也可以表示各组分间重量的比例关系,因此,只要是按照本申请实施例说明书相关组分的含量按比例放大或缩小均在本申请实施例说明书公开的范围之内。具体地,本申请实施例说明书中的质量可以是μg、mg、g、kg等化工领域公知的质量单位。The weight of the relevant components mentioned in the description of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the various components. The scaling up or down of the content of the fraction is within the scope disclosed in the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be μg, mg, g, kg and other well-known mass units in the chemical industry.

一方面,本发明实施例提供了一种含支链卤代磷酸酯。本发明实施例含支链卤代磷酸酯的分子结构式如下述通式Ⅰ所示:On the one hand, the embodiment of the present invention provides a halogenated phosphoric acid ester containing branched chains. The molecular structural formula of the embodiment of the present invention containing branched-chain halophosphate is shown in the following general formula I:

Figure BDA0003106642530000061
Figure BDA0003106642530000061

其中,通式Ⅰ中的R1、R2、R3独立的选自碳原子数为1~10的烷基、碳原子数为1~10的烯基、碳原子数为1~10的炔基、碳原子数为1~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、三甲基硅基、三甲基硅氧基、含卤素的烷基、苯基、联苯基、萘基、吡啶基、噻吩基、卤代苯基、卤代联苯、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、卤代苯酚基、卤代萘酚基中的一种;Among them, R 1 , R 2 , and R 3 in the general formula I are independently selected from alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 1 to 10 carbon atoms, and alkyne groups with 1 to 10 carbon atoms. Group, chain alkoxy group with 1 to 10 carbon atoms, chain alkenyloxy group with 2 to 10 carbon atoms, chain alkynyloxy group with 2 to 10 carbon atoms, and chain alkyneoxy group with 3 to 10 carbon atoms Cyclic alkoxyl with 10, cyclic alkenyloxyl with 3 to 10 carbon atoms, trimethylsilyl, trimethylsilyloxy, halogen-containing alkyl, phenyl, biphenyl, naphthyl , pyridyl, thienyl, halogenated phenyl, halogenated biphenyl, phenol, alkyl-containing phenol, alkenyl-containing phenol, alkynyl-containing phenol, nitrile-containing phenol, halogenated One of phenol group and halogenated naphthol group;

通式Ⅰ中的R4、R5、R6、R7分别独立的选自氢原子、卤素原子、碳原子数为6~10的芳香基团、碳原子数为6~10的卤代芳香基团中的一种基团,碳原子数为1~10的烷基、碳原子数为1~10的卤代烷基、碳原子数为1~10的烯基、碳原子数为1~10的卤代烯基、碳原子数为1~10的炔基、碳原子数为1~10的卤代炔基、碳原子数为2~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、碳原子数为3~20的三烷基硅基、碳原子数为3~20的三烷基硅氧基、含芳基硅基、含芳基硅氧基、吡啶基、噻吩基、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、卤代苯酚基、卤代萘酚基中的一种;R 4 , R 5 , R 6 , and R 7 in the general formula I are independently selected from hydrogen atoms, halogen atoms, aromatic groups with 6 to 10 carbon atoms, and halogenated aromatic groups with 6 to 10 carbon atoms. One of the groups, an alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, or an alkenyl group with 1 to 10 carbon atoms Haloalkenyl, alkynyl with 1 to 10 carbon atoms, haloalkynyl with 1 to 10 carbon atoms, chain alkoxy with 2 to 10 carbon atoms, and chain alkoxy with 2 to 10 carbon atoms Chain alkenyloxy, chain alkynyloxy with 2 to 10 carbon atoms, cyclic alkoxy with 3 to 10 carbon atoms, cyclic alkenyloxy with 3 to 10 carbon atoms, carbon Trialkylsilyl groups with 3-20 atoms, trialkylsiloxy groups with 3-20 carbon atoms, aryl-containing silicon groups, aryl-containing silicon groups, pyridyl groups, thienyl groups, phenol groups, One of alkyl-containing phenol groups, alkenyl-containing phenol groups, alkynyl-containing phenol groups, nitrile-containing phenol groups, halogenated phenol groups, and halogenated naphthol groups;

通式Ⅰ中的M1、M2独立的选自卤素原子;M 1 and M 2 in the general formula I are independently selected from halogen atoms;

通式Ⅰ中的x为0~10的整数。x in the general formula I is an integer of 0-10.

本发明实施例含支链卤代磷酸酯所含的磷酸基团具有正极成膜功能,可以显著改善正极材料的循环稳定性和降低阻抗。含支链卤代磷酸酯所含的其他基团能够起到对磷酸基团的成膜增效作用,提高含支链卤代磷酸酯正负极界面的稳定性。所含的卤代基团赋予含支链卤代磷酸酯良好浸润性。因此,本发明实施例含支链卤代磷酸酯用于电解液中后,能够显著改善电解液的热稳定性,提高电解液成膜性能和浸润性能,同时能够有效降低发生产气和阻抗升高的不良现象发生。The phosphoric acid group contained in the branched-chain halophosphate in the embodiment of the present invention has the function of positive electrode film formation, which can significantly improve the cycle stability of the positive electrode material and reduce the impedance. The other groups contained in the branched-chain halogenated phosphate can play a synergistic effect on the film formation of the phosphoric acid group, and improve the stability of the positive and negative interface of the branched-chain-containing halogenated phosphate. The contained halo groups endow branched halophosphates with good wettability. Therefore, after the embodiment of the present invention contains branched-chain halogenated phosphates used in the electrolyte, it can significantly improve the thermal stability of the electrolyte, improve the film-forming performance and wetting performance of the electrolyte, and at the same time effectively reduce the occurrence of gas production and impedance rise. High adverse events occur.

实施例中,通式Ⅰ中的R1至R7中的至少一基团为链状基团时,该链状基团包括直链基团或/和支链基团。该些含有或为直链基团或/和支链基团的链状基团能够提高其与含支链卤代磷酸酯所含的磷酸酯基团之间的成膜增效作用,以提升含支链卤代磷酸酯的热稳定作用。In an embodiment, when at least one group among R 1 to R 7 in the general formula I is a chain group, the chain group includes straight chain groups or/and branched chain groups. These chain groups that contain or be straight-chain groups or/and branched-chain groups can improve the film-forming synergistic effect between them and the phosphate groups contained in branched-chain halogenated phosphoric acid esters, so as to improve Thermal stabilization of branched-chain halophosphates.

在上述R1至R7中的至少一基团为链状基团时,实施例中,该链状基团包含卤素原子、氧原子或不饱和键官能团中的至少一种。具体实施例中,链状基团包含不饱和键官能团时,不饱和键官能团包括碳碳双键、碳碳三键、碳氮双键、碳氮三键、碳氧双键、硫氧双键、磷氧双键、酰胺、酰亚胺、磺酰胺、磺酰亚胺、磷酰胺、磷酰亚胺、羧酸酯、磺酸酯和磷酸酯中的至少一种。其中,R4、R5、R6、R7中的至少一基团为芳香基团时,该芳香基团包括但不限于苯基、联苯基、萘基中的至少一种。另些具体实施例中,该些不饱和键官能团的位置在端基或/和者内侧。该些链状基团能够进一步提高对磷酸基团的成膜增效作用,提高含支链卤代磷酸酯正负极界面的稳定性,提高含支链卤代磷酸酯正负极界面的稳定性。When at least one group among the above-mentioned R 1 to R 7 is a chain group, in an embodiment, the chain group includes at least one of a halogen atom, an oxygen atom or an unsaturated bond functional group. In a specific embodiment, when the chain group includes an unsaturated bond functional group, the unsaturated bond functional group includes a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-nitrogen double bond, a carbon-nitrogen triple bond, a carbon-oxygen double bond, and a sulfur-oxygen double bond , phosphorus oxygen double bond, amides, imides, sulfonamides, sulfonimides, phosphoramides, phosphorimides, carboxylates, sulfonates and phosphates. Wherein, when at least one group among R 4 , R 5 , R 6 , and R 7 is an aromatic group, the aromatic group includes but is not limited to at least one of phenyl, biphenyl, and naphthyl. In other specific embodiments, the position of these unsaturated bond functional groups is inside the end group or/and. These chain groups can further improve the film-forming synergistic effect on phosphoric acid groups, improve the stability of the positive and negative interfaces containing branched-chain halophosphates, and improve the stability of the positive and negative interfaces containing branched-chain halophosphates. sex.

实施例中,当上述R1至R7中的至少一基团为卤代基团时,卤代基团为部分取代或全取代。具体实施例中,该卤代基团中的卤原子可以是氟、氯、溴或碘中的至少一种。该卤代基团能够进一步提高含支链卤代磷酸酯产物的浸润性。In an embodiment, when at least one group among the aforementioned R 1 to R 7 is a halogenated group, the halogenated group is partially substituted or fully substituted. In a specific embodiment, the halogen atom in the halogeno group can be at least one of fluorine, chlorine, bromine or iodine. The halogenated group can further improve the wettability of the branched-chain halogenated phosphoric acid ester product.

通式Ⅰ中的M1、M2为卤素原子,以改善含支链卤代磷酸酯的浸润性,实施例中,M1、M2所示的卤素原子为氟、氯、溴、碘原子中的至少一种,进一步实施例中,M1、M2所示的卤素原子为氟,此时,含支链卤代磷酸酯如下述结构式Ⅰ1所示的含支链二氟磷酸酯,以进一步提高了含支链卤代磷酸酯的浸润性,而且添加电解液中后不附带杂质元素或杂质元素少,从而提高相应电解质或电解液纯度和相应的化学性能。M 1 and M 2 in the general formula I are halogen atoms to improve the wettability of branched-chain halophosphates. In the examples, the halogen atoms represented by M 1 and M 2 are fluorine, chlorine, bromine, and iodine atoms At least one of them, in a further embodiment, the halogen atoms represented by M 1 and M 2 are fluorine, at this time, the branched-chain-containing halophosphate is as shown in the following structural formula I 1 containing branch-containing difluorophosphate, In order to further improve the wettability of the branched-chain halogenated phosphoric acid ester, and add no impurity elements or few impurity elements to the electrolyte, thereby improving the purity and corresponding chemical properties of the corresponding electrolyte or electrolyte.

实施例中,含支链卤代磷酸酯至少包括如下分子结构式Ⅰ1至结构式Ⅰ7中至少一种:In an embodiment, the branched-chain-containing halogenated phosphoric acid ester includes at least one of the following molecular structural formulas I 1 to structural formula I 7 :

Figure BDA0003106642530000071
Figure BDA0003106642530000071

Figure BDA0003106642530000081
Figure BDA0003106642530000081

其中,通式Ⅰ2至Ⅰ7中的R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R34独立的选自氢原子、卤素原子、碳原子数为6~10的芳香基团、碳原子数为6~10的卤代芳香基团、碳原子数为1~10的烷基、碳原子数为1~10的卤代烷基、碳原子数为1~10的烯基、碳原子数为1~10的卤代烯基、碳原子数为1~10的炔基、碳原子数为1~10的卤代炔基、碳原子数为2~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、碳原子数为3~20的三烷基硅基、碳原子数为3~20的三烷基硅氧基、含芳基硅基、含芳基硅氧基、联苯基、萘基、吡啶基、噻吩基、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、单卤代苯酚基、多卤代苯酚基中的一种;m、n、o、p、y、z独立的为0~10的整数。该些类型的含支链卤代磷酸酯具有更优异的正极成膜功能和浸润性以及降低阻抗,热稳定性更优异。Among them, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 are independently selected from hydrogen atom, halogen atom , aromatic groups with 6 to 10 carbon atoms, halogenated aromatic groups with 6 to 10 carbon atoms, alkyl groups with 1 to 10 carbon atoms, halogenated alkyl groups with 1 to 10 carbon atoms, carbon Alkenyl with 1 to 10 atoms, haloalkenyl with 1 to 10 carbon atoms, alkynyl with 1 to 10 carbon atoms, haloalkynyl with 1 to 10 carbon atoms, Chained alkoxy groups with 2 to 10 carbon atoms, chained alkenyloxy groups with 2 to 10 carbon atoms, chain alkynyloxy groups with 2 to 10 carbon atoms, and cyclic alkanes with 3 to 10 carbon atoms Oxygen, cyclic alkenyloxy with 3 to 10 carbon atoms, trialkylsilyl with 3 to 20 carbon atoms, trialkylsilyloxy with 3 to 20 carbon atoms, aryl silicon aryl-containing siloxy, biphenyl, naphthyl, pyridyl, thienyl, phenol, alkyl-containing phenol, alkenyl-containing phenol, alkynyl-containing phenol, nitrile-containing One of phenol group, monohalogenated phenol group and polyhalogenated phenol group; m, n, o, p, y, z are independently integers of 0-10. These types of branched-chain-containing halogenated phosphates have better positive film-forming function and wettability, lower impedance, and better thermal stability.

其中,上述通式Ⅰ2至Ⅰ7中的R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R34中的至少一基团为链状基团时,该链状基团包括直链基团或/和支链基团。该些含有或为直链基团或/和支链基团的链状基团能够提高其与含支链卤代磷酸酯所含的磷酸酯基团之间的成膜增效作用,以提升含支链卤代磷酸酯的热稳定作用。Among them, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 in the above general formulas I 2 to I 7 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 are chains When a chain-like group is used, the chain-like group includes a straight-chain group or/and a branched-chain group. These chain groups that contain or be straight-chain groups or/and branched-chain groups can improve the film-forming synergistic effect between them and the phosphate groups contained in branched-chain halogenated phosphoric acid esters, so as to improve Thermal stabilization of branched-chain halophosphates.

在上述通式Ⅰ2至Ⅰ7中的R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R34中的至少一基团为链状基团时,实施例中,该链状基团包含卤素原子、氧原子或不饱和键官能团中的至少一种。具体实施例中,当该链状基团包含不饱和键官能团时,该不饱和键官能团包括碳碳双键、碳碳三键、碳氮双键、碳氮三键、碳氧双键、硫氧双键、磷氧双键、酰胺、酰亚胺、磺酰胺、磺酰亚胺、磷酰胺、磷酰亚胺、羧酸酯、磺酸酯和磷酸酯中的至少一种。其中,R8至R34中的至少一基团为芳香基团时,该芳香基团包括但不限于苯基、联苯基、萘基中的至少一种。另些具体实施例中,该些不饱和键官能团的位置在端基或/和者内侧。该些链状基团能够进一步提高对磷酸基团的成膜增效作用,提高含支链卤代磷酸酯正负极界面的稳定性,提高含支链卤代磷酸酯正负极界面的稳定性。R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , At least one of R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , and R 34 is a chain In the case of a group, in an embodiment, the chain group contains at least one of a halogen atom, an oxygen atom or an unsaturated bond functional group. In a specific embodiment, when the chain group contains an unsaturated bond functional group, the unsaturated bond functional group includes a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-nitrogen double bond, a carbon-nitrogen triple bond, a carbon-oxygen double bond, a sulfur At least one of oxygen double bond, phosphorus oxygen double bond, amide, imide, sulfonamide, sulfonimide, phosphoramide, phosphorimide, carboxylate, sulfonate and phosphate. Wherein, when at least one group among R 8 to R 34 is an aromatic group, the aromatic group includes but is not limited to at least one of phenyl, biphenyl, and naphthyl. In other specific embodiments, the position of these unsaturated bond functional groups is inside the end group or/and. These chain groups can further improve the film-forming synergistic effect on phosphoric acid groups, improve the stability of the positive and negative interfaces containing branched-chain halophosphates, and improve the stability of the positive and negative interfaces containing branched-chain halophosphates. sex.

实施例中,当上述通式Ⅰ2至Ⅰ7中的R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R34中的至少一基团为卤代基团时,卤代基团为部分取代或全取代。具体实施例中,该卤代基团中的卤原子可以是氟、氯、溴或碘中的至少一种。该卤代基团能够进一步提高含支链卤代磷酸酯产物的浸润性。In the embodiment, when R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 in the above general formulas I 2 to I 7 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 When the group is a halogenated group, the halogenated group is partially substituted or fully substituted. In a specific embodiment, the halogen atom in the halogeno group can be at least one of fluorine, chlorine, bromine or iodine. The halogenated group can further improve the wettability of the branched-chain halogenated phosphoric acid ester product.

基于上述含支链卤代磷酸酯所含的各基团,具体实施例中,上文含支链卤代磷酸酯具体至少可以是包含如下式1至式20所示化合物中的至少一种:Based on the groups contained in the above-mentioned branched-chain-containing halogenated phosphoric acid esters, in specific embodiments, the above-mentioned branched-chain-containing halogenated phosphoric acid esters may at least include at least one of the compounds shown in the following formulas 1 to 20:

Figure BDA0003106642530000091
Figure BDA0003106642530000091

式1至式20所示的含支链卤代磷酸酯具有更优异的正极成膜功能和浸润性以及低阻抗特性,热稳定性更优异。当然,式1至式20仅仅是上文结构式Ⅰ所示含支链卤代磷酸酯的部分举例,上文结构式Ⅰ所示含支链卤代磷酸酯还可以是基于上述R1至R34所示基团范围内的其他化合物,而且其他化合物也具有优异的正极成膜功能和浸润性以及热稳定性。The branched-chain-containing halogenated phosphoric acid esters represented by formulas 1 to 20 have better positive electrode film-forming function, wettability and low impedance characteristics, and have better thermal stability. Of course, formula 1 to formula 20 are only some examples of the branched-chain halogenated phosphoric acid ester shown in the above structural formula I, and the branched-chain halogenated phosphoric acid ester shown in the above structural formula I can also be based on the above R 1 to R 34 Other compounds within the scope of the indicated group, and other compounds also have excellent positive electrode film-forming function and wettability and thermal stability.

另一方面,本发明实施例提供了上文本发明实施例含支链卤代磷酸酯的制备方法。本发明实施例含支链卤代磷酸酯的制备方法包括如下步骤:On the other hand, the embodiment of the present invention provides the preparation method of the branched-chain halogenated phosphoric acid ester in the above embodiment of the invention. The preparation method of the embodiment of the present invention contains the branched chain halophosphate comprises the following steps:

S01:将如下结构式ⅠA所示的反应物A与如下结构式ⅠB所示的反应物B于第一非水溶液中进行第一取代反应,生成如下结构式Ⅰ所示的含支链卤代磷酸酯产物;根据反应物A、反应物B,该第一取代反应的化学反应式(1)所示:S01: The reactant A shown in the following structural formula I A and the reactant B shown in the following structural formula I B are subjected to the first substitution reaction in the first non-aqueous solution to generate the branched chain-containing halogenated phosphoric acid ester shown in the following structural formula I Product; According to reactant A, reactant B, shown in the chemical reaction formula (1) of this first substitution reaction:

Figure BDA0003106642530000092
Figure BDA0003106642530000092

经第一取代反应生成的结构式Ⅰ所示的含支链卤代磷酸酯产物为上文本发明实施例结构式Ⅰ所示的含支链卤代磷酸酯。因此,步骤S01中的式ⅠA和Ⅰ中的R1至R7如上文结构式Ⅰ所示的本发明实施例含支链卤代磷酸酯所含的R1至R7。具体的如R1、R2、R3独立的选自碳原子数为1~10的烷基、碳原子数为1~10的烯基、碳原子数为1~10的炔基、碳原子数为1~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、三甲基硅基、三甲基硅氧基、含卤素的烷基、苯基、联苯基、萘基、吡啶基、噻吩基、卤代苯基、卤代联苯、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、卤代苯酚基、卤代萘酚基中的一种。R4、R5、R6、R7分别独立的选自氢原子、卤素原子、碳原子数为6~10的芳香基团、碳原子数为6~10的卤代芳香基团中的一种基团,碳原子数为1~10的烷基、碳原子数为1~10的卤代烷基、碳原子数为1~10的烯基、碳原子数为1~10的卤代烯基、碳原子数为1~10的炔基、碳原子数为1~10的卤代炔基、碳原子数为2~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、碳原子数为3~20的三烷基硅基、碳原子数为3~20的三烷基硅氧基、含芳基硅基、含芳基硅氧基、吡啶基、噻吩基、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、卤代苯酚基、卤代萘酚基中的一种。x为0~10的整数。The branched-chain halogenated phosphoric acid ester product represented by the structural formula I generated through the first substitution reaction is the branched-chain halogenated phosphoric acid ester represented by the structural formula I of the above invention embodiment. Therefore, R 1 to R 7 in the formulas I A and I in step S01 are the same as the R 1 to R 7 contained in the branched-chain halophosphate in the embodiment of the present invention shown in the above structural formula I. Specifically, for example, R 1 , R 2 , and R 3 are independently selected from alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 1 to 10 carbon atoms, alkynyl groups with 1 to 10 carbon atoms, and carbon atoms Chain alkoxyl with 1 to 10 carbon atoms, chain alkenyloxy with 2 to 10 carbon atoms, chain alkynyloxy with 2 to 10 carbon atoms, cyclic chain with 3 to 10 carbon atoms Alkoxy, cyclic alkenyloxy with 3 to 10 carbon atoms, trimethylsilyl, trimethylsilyloxy, halogen-containing alkyl, phenyl, biphenyl, naphthyl, pyridyl, Thienyl, halogenated phenyl, halogenated biphenyl, phenol, alkyl-containing phenol, alkenyl-containing phenol, alkynyl-containing phenol, nitrile-containing phenol, halogenated phenol, halogen One of the naphthol groups. R 4 , R 5 , R 6 , and R 7 are each independently selected from a hydrogen atom, a halogen atom, an aromatic group with 6 to 10 carbon atoms, and a halogenated aromatic group with 6 to 10 carbon atoms. A group, an alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, a haloalkenyl group with 1 to 10 carbon atoms, Alkynyl with 1 to 10 carbon atoms, haloalkynyl with 1 to 10 carbon atoms, chain alkoxy with 2 to 10 carbon atoms, chain alkenyloxy with 2 to 10 carbon atoms Group, chain alkynyloxy group with 2 to 10 carbon atoms, cyclic alkoxy group with 3 to 10 carbon atoms, cyclic alkenyloxy group with 3 to 10 carbon atoms, 3 to 10 carbon atoms 20 trialkylsilyl groups, trialkylsiloxy groups with 3 to 20 carbon atoms, aryl-containing silyl groups, aryl-containing siloxy groups, pyridyl groups, thienyl groups, phenol groups, and alkyl-containing phenol groups One of group, alkenyl-containing phenol group, alkynyl-containing phenol group, nitrile-containing phenol group, halogenated phenol group, halogenated naphthol group. x is an integer of 0-10.

基于上述结构式ⅠA所示的反应物A以及其所含的基团R1-R7所示的基团种类,实施例中,反应物A至少包括如下结构式A1至A6中的至少一种:Based on the reactant A shown in the above structural formula I A and the group types represented by the groups R 1- R 7 contained in it, in the embodiment, the reactant A includes at least one of the following structural formulas A 1 to A 6 kind:

Figure BDA0003106642530000101
Figure BDA0003106642530000101

其中,通式A1至A 6中的R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R34独立的选自氢原子、卤素原子、碳原子数为6~10的芳香基团、碳原子数为6~10的卤代芳香基团、碳原子数为1~10的烷基、碳原子数为1~10的卤代烷基、碳原子数为1~10的烯基、碳原子数为1~10的卤代烯基、碳原子数为1~10的炔基、碳原子数为1~10的卤代炔基、碳原子数为2~10的链状烷氧基、碳原子数为2~10的链状烯氧基、碳原子数为2~10的链状炔氧基、碳原子数为3~10的环状烷氧基、碳原子数为3~10的环状烯氧基、碳原子数为3~20的三烷基硅基、碳原子数为3~20的三烷基硅氧基、含芳基硅基、含芳基硅氧基、吡啶基、噻吩基、苯酚基、含烷基的苯酚基、含烯基的苯酚基、含炔基的苯酚基、含腈基的苯酚基、单卤代苯酚基、多卤代苯酚基中的一种;m、n、o、p、y、z独立的为0~10的整数。该些反应物A能够与反应物B生成上文结构式Ⅰ2至结构式Ⅰ7所示的含支链卤代磷酸酯,而且能够提高第二取代反应的效率和目标产物的得率。Among them, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 are independently selected from hydrogen atom, halogen atom , aromatic groups with 6 to 10 carbon atoms, halogenated aromatic groups with 6 to 10 carbon atoms, alkyl groups with 1 to 10 carbon atoms, halogenated alkyl groups with 1 to 10 carbon atoms, carbon Alkenyl with 1 to 10 atoms, haloalkenyl with 1 to 10 carbon atoms, alkynyl with 1 to 10 carbon atoms, haloalkynyl with 1 to 10 carbon atoms, Chained alkoxy groups with 2 to 10 carbon atoms, chained alkenyloxy groups with 2 to 10 carbon atoms, chain alkynyloxy groups with 2 to 10 carbon atoms, and cyclic alkanes with 3 to 10 carbon atoms Oxygen, cyclic alkenyloxy with 3 to 10 carbon atoms, trialkylsilyl with 3 to 20 carbon atoms, trialkylsilyloxy with 3 to 20 carbon atoms, aryl silicon aryl group, pyridyl group, thienyl group, phenol group, alkyl group containing phenol group, alkenyl group containing phenol group, alkynyl group containing phenol group, nitrile group containing phenol group, monohalogenated phenol One of the group and the polyhalogenated phenol group; m, n, o, p, y, z are independently integers of 0-10. These reactants A can form the branched-chain halogenated phosphoric acid esters shown in the above structural formula I 2 to structural formula I 7 with the reactant B, and can improve the efficiency of the second substitution reaction and the yield of the target product.

进一步实施例中,如上文本发明实施例结构式Ⅰ所示的含支链卤代磷酸酯,当上述R1至R34中的至少一基团为链状基团时,该链状基团包括直链基团或支链基团。该些链状基团能够提高其与磷酸酯基团之间的成膜增效作用,以提升含支链卤代磷酸酯的热稳定作用。In a further embodiment, the branched-chain-containing halogenated phosphoric acid ester shown in the structural formula I of the invention embodiment above, when at least one of the above-mentioned R 1 to R 34 is a chain group, the chain group includes a straight Chain group or branched group. These chain groups can improve the film-forming synergistic effect between it and the phosphate group, so as to improve the thermal stability of the branched-chain halogenated phosphate.

进一步地,当上述R1至R34中的至少一基团为链状基团时,该链状基团包含卤素原子、氧原子或不饱和键官能团中的至少一种。具体实施例中,当该链状基团包含不饱和键官能团时,不饱和键官能团包括碳碳双键、碳碳三键、碳氮双键、碳氮三键、碳氧双键、硫氧双键、磷氧双键、酰胺、酰亚胺、磺酰胺、磺酰亚胺、磷酰胺、磷酰亚胺、羧酸酯、磺酸酯和磷酸酯中的至少一种。另些具体实施例中,该链状基团包含不饱和键官能团时,不饱和键官能团的位置在端基或/和者内侧。该些链状基团特别是含该些含不饱和基团时,其能够进一步提高对磷酸基团的成膜增效作用,提高含支链卤代磷酸酯正负极界面的稳定性,提高含支链卤代磷酸酯正负极界面的稳定性。Further, when at least one group among the aforementioned R 1 to R 34 is a chain group, the chain group includes at least one of a halogen atom, an oxygen atom or an unsaturated bond functional group. In a specific embodiment, when the chain group includes an unsaturated bond functional group, the unsaturated bond functional group includes a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-nitrogen double bond, a carbon-nitrogen triple bond, a carbon-oxygen double bond, a sulfur-oxygen At least one of a double bond, a phosphorus-oxygen double bond, an amide, an imide, a sulfonamide, a sulfonimide, a phosphoramide, a phosphorimide, a carboxylate, a sulfonate, and a phosphoric acid ester. In other specific embodiments, when the chain group includes an unsaturated bond functional group, the position of the unsaturated bond functional group is inside the end group or/and. These chain groups, especially when containing these unsaturated groups, can further improve the film-forming synergistic effect on phosphoric acid groups, improve the stability of the positive and negative electrode interfaces containing branched-chain halogenated phosphates, and improve Stability of positive and negative interfaces containing branched halophosphates.

实施例中,当上述R1至R34中的至少一基团为卤代基团时,卤代基团为部分取代或全取代。具体实施例中,该卤代基团中的卤原子可以是氟、氯、溴或碘中的至少一种。该卤代基团能够进一步提高含支链卤代磷酸酯产物的浸润性。In an embodiment, when at least one group among the aforementioned R 1 to R 34 is a halogenated group, the halogenated group is partially substituted or fully substituted. In a specific embodiment, the halogen atom in the halogeno group can be at least one of fluorine, chlorine, bromine or iodine. The halogenated group can further improve the wettability of the branched-chain halogenated phosphoric acid ester product.

实施例中,步骤S01中的化合物A可以按照根据具体的化合物直接市购获得,当然可以按照现有的合成方法合成化合物A。当合成化合物A时,具体实施例中,以式10所需的原料乙炔基六氟异丙醇为例说明化合物A的合成,其合成路线的反应式如下所示:In the embodiment, the compound A in step S01 can be directly obtained from the market according to the specific compound, and of course the compound A can be synthesized according to the existing synthesis method. When compound A is synthesized, in specific examples, the synthesis of compound A is illustrated by taking the raw material ethynyl hexafluoroisopropanol required by formula 10 as an example, and the reaction formula of its synthetic route is as follows:

Figure BDA0003106642530000111
Figure BDA0003106642530000111

按照上述乙炔基六氟异丙醇的合成反应式,其具体的制备方法如下:According to the synthetic reaction formula of above-mentioned ethynyl hexafluoroisopropanol, its concrete preparation method is as follows:

SA1:室温条件下向反应釜中加入THF 50mL,然后加入乙炔钠4.8g(0.1mol),0℃条件下搅拌0.5h;在另一反应釜中将THF 30mL与16.6g(0.1mol)六氟丙酮在0℃条件下混合;将乙炔钠的THF溶液加入到六氟丙酮的THF溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持温度平稳,乙炔钠的THF溶液溶液加入完毕后保持温度不变继续反应3h;反应完成后向反应釜中加入水2ml,缓慢升至室温,常压蒸馏除去溶剂THF,然后加入50ml DMC萃取,过滤后将DMC溶液使用无水硫酸镁干燥12h后常压蒸馏除去溶剂DMC,然后减压蒸馏得到粘稠状无色液体17.9g,产率为93%。即为乙炔基六氟异丙醇。SA1: Add THF 50mL to the reaction kettle at room temperature, then add 4.8g (0.1mol) of sodium acetylide, and stir at 0°C for 0.5h; add THF 30mL and 16.6g (0.1mol) hexafluoro Mix acetone at 0°C; add the THF solution of sodium acetylide to the THF solution of hexafluoroacetone, stir throughout the addition process and keep the temperature at 0°C, control the dropping rate to keep the temperature stable, and the THF solution of sodium acetylide is added Afterwards, keep the temperature constant and continue the reaction for 3 hours; after the reaction is completed, add 2ml of water to the reaction kettle, slowly rise to room temperature, distill off the solvent THF under normal pressure, then add 50ml of DMC for extraction, filter and dry the DMC solution with anhydrous magnesium sulfate for 12 hours Afterwards, the solvent DMC was removed by atmospheric distillation, and then 17.9 g of viscous colorless liquid was obtained by distillation under reduced pressure, with a yield of 93%. That is ethynyl hexafluoroisopropanol.

SA2:在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C5H2F6O[M]+为192.13。1H NMR(400MHz,CDCl3)δ:6.48(Br,1H),3.61(s,1H);13C NMR(100MHz,CDCl3)δ:106.3,92.7,88.3,72.1。证明所得无色液体为乙炔基六氟异丙醇。通过卡氏水分测定仪和电位滴定仪测定水分为21ppm,酸度为15ppm,氯离子浓度为2ppm。SA2: In the glove box, take 0.1 mL of the obtained colorless liquid, add it into 2 mL of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and use a gas chromatography-mass spectrometer (Thermo Fisher Scientific ) for analysis, the analysis result showed that GC-MS (ESI) calcd for C 5 H 2 F 6 O[M] + was 192.13. 1 H NMR (400MHz, CDCl 3 ) δ: 6.48 (Br, 1H), 3.61 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ: 106.3, 92.7, 88.3, 72.1. The obtained colorless liquid was proved to be ethynyl hexafluoroisopropanol. Moisture measured by Karl Fischer moisture analyzer and potentiometric titrator is 21ppm, acidity is 15ppm, and chloride ion concentration is 2ppm.

另一具体实施例中,以式17所需的原料(1-五氟苯基)3-丁烯-1-醇为例说明化合物A的合成,其合成路线的反应式如下所示:In another specific embodiment, the synthesis of compound A is illustrated by taking the raw material (1-pentafluorophenyl) 3-buten-1-ol required by formula 17 as an example, and the reaction formula of its synthetic route is as follows:

Figure BDA0003106642530000112
Figure BDA0003106642530000112

SA3:室温条件下向反应釜中加入THF 50mL,然后加入五氟苯甲醛19.6g(0.1mol),0℃条件下搅拌0.5h;将1-丁烯基溴化镁的THF溶液(1-丁烯基溴化镁含量为16g)加入到六氟丙酮的THF溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持温度平稳,1-丁烯基溴化镁的THF溶液加入完毕后保持温度不变继续反应3h;反应完成后向反应釜中加入水2ml,缓慢升至室温,常压蒸馏除去溶剂THF,然后加入50ml DMC萃取,过滤后将DMC溶液使用无水硫酸镁干燥12h后常压蒸馏除去溶剂DMC,然后减压蒸馏得到粘稠状无色液体21.7g,产率为91%。即为(1-五氟苯基)3-丁烯-1-醇。SA3: Add THF 50mL to the reaction kettle at room temperature, then add 19.6g (0.1mol) of pentafluorobenzaldehyde, and stir at 0°C for 0.5h; THF solution of 1-butenylmagnesium bromide (1-butyl The content of alkenylmagnesium bromide is 16g) into the THF solution of hexafluoroacetone, stirring throughout the adding process and keeping the temperature at 0°C, controlling the dropping rate to keep the temperature stable, and the THF solution of 1-butenylmagnesium bromide has been added Afterwards, keep the temperature constant and continue the reaction for 3 hours; after the reaction is completed, add 2ml of water to the reaction kettle, slowly rise to room temperature, distill off the solvent THF under normal pressure, then add 50ml of DMC for extraction, filter and dry the DMC solution with anhydrous magnesium sulfate for 12 hours Afterwards, the solvent DMC was removed by atmospheric distillation, and then 21.7 g of viscous colorless liquid was obtained by distillation under reduced pressure, with a yield of 91%. That is (1-pentafluorophenyl) 3-buten-1-ol.

SA4:在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C10H7F5O[M]+为238.18。1H NMR(400MHz,CDCl3)δ:7.37(Br,1H),5.82(m,1H)5.13(m,1H),4.91(m,1H),4.88(m,1H),2.56(m,2H);13C NMR(100MHz,CDCl3)δ:145.2,142.2,136.4,134.3,116.4,113.7,62.2,42.4。证明所得无色液体为(1-五氟苯基)3-丁烯-1-醇。通过卡氏水分测定仪和电位滴定仪测定水分为16ppm,酸度为18ppm,氯离子浓度为1.5ppm。SA4: In the glove box, take 0.1 mL of the obtained colorless liquid, add it into 2 mL of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and use a gas chromatography-mass spectrometer (Thermo Fisher Scientific ) for analysis, the analysis result showed that GC-MS (ESI) calcd for C 10 H 7 F 5 O[M] + was 238.18. 1 H NMR (400MHz, CDCl 3 ) δ: 7.37 (Br, 1H), 5.82 (m, 1H), 5.13 (m, 1H), 4.91 (m, 1H), 4.88 (m, 1H), 2.56 (m, 2H) ); 13 C NMR (100MHz, CDCl 3 ) δ: 145.2, 142.2, 136.4, 134.3, 116.4, 113.7, 62.2, 42.4. The obtained colorless liquid proved to be (1-pentafluorophenyl)3-buten-1-ol. Moisture measured by Karl Fischer moisture analyzer and potentiometric titrator is 16ppm, acidity is 18ppm, and chloride ion concentration is 1.5ppm.

步骤S01中的式ⅠB和Ⅰ中的M1、M2如上文结构式Ⅰ所示的本发明实施例含支链卤代磷酸酯所含的M1、M2,式ⅠB中的M3为卤素原子,因此,M1、M2、M3独立的为卤素原子。实施例中,该卤代基团中的卤原子可以是氟、氯、溴或碘中的至少一种。具体实施例中,式ⅠB所示的化合物B可以是三卤化磷如PF3、PCl3、PBr3、PI3中的至少一种。In step S01, M 1 and M 2 in formula I B and I are as shown in the above structural formula I. M 1 and M 2 contained in the embodiment of the present invention contain branched-chain halophosphates, and M 3 in formula I B is a halogen atom, therefore, M 1 , M 2 , and M 3 are independently a halogen atom. In an embodiment, the halogen atom in the halogeno group may be at least one of fluorine, chlorine, bromine or iodine. In a specific embodiment, the compound B represented by formula IB may be at least one of phosphorus trihalides such as PF 3 , PCl 3 , PBr 3 , and PI 3 .

实施例中,在化学反应式(1)所示的第一取代反应体系中,控制反应物A与反应物B是按照摩尔比为1:(1~6)进一步为1:(1~2)的比例混合于第一非水溶液中。具体实施例中,反应物A与反应物B的摩尔比为1:1、1:1.5、1:2、1:2.5、1:3、1:3.5、1:4、1:4.5、1:5、1:5.5、1:6等典型而非限制性的比例。In the embodiment, in the first substitution reaction system shown in the chemical reaction formula (1), the control reactant A and the reactant B are according to the molar ratio of 1: (1 ~ 6) and further 1: (1 ~ 2) The ratio is mixed in the first non-aqueous solution. In a specific embodiment, the molar ratio of reactant A to reactant B is 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1: 5. Typical and non-limiting ratios such as 1:5.5, 1:6, etc.

另些实施例中,在化学反应式(1)所示的第一取代反应体系中,控制反应物A与第一非水溶液的质量比为1:(1~6)。具体实施例中,反应物A与第一非水溶液的质量比为1:1、1:1.5、1:2、1:2.5、1:3、1:3.5、1:4、1:4.5、1:5、1:5.5、1:6等典型而非限制性的比例。In other embodiments, in the first substitution reaction system shown in the chemical reaction formula (1), the mass ratio of the reactant A to the first non-aqueous solution is controlled to be 1: (1-6). In a specific embodiment, the mass ratio of reactant A to the first non-aqueous solution is 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1 :5, 1:5.5, 1:6 and other typical and non-limiting ratios.

通过反应物A与反应物B的比例和浓度的调整,提高第一取代反应正向反应速率,提高第一取代反应的效率。同时使反应物完全反应、减少杂质的产生,并节约反应物用量降低合成成本。By adjusting the ratio and concentration of the reactant A to the reactant B, the forward reaction rate of the first substitution reaction is increased, and the efficiency of the first substitution reaction is improved. At the same time, the reactants are completely reacted, the generation of impurities is reduced, and the amount of reactants is saved to reduce the synthesis cost.

实施例中,第一取代反应的温度为-20~40℃。具体可以是-20℃、-15℃、-10℃、-5℃、0℃、5℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃等典型而非限制性的温度。.通过对取代反应的温度控制和优化,提高取代反应的效率。In an embodiment, the temperature of the first substitution reaction is -20-40°C. Specifically, it can be -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, etc. Typical but not limited sexual temperature. .Through the temperature control and optimization of the substitution reaction, the efficiency of the substitution reaction is improved.

为了提高第一取代反应的效率,实施例中,在将反应物A与反应物B混合之前,理想是先将反应物A溶解于第一非水溶液中,配制反应物A的第一非水溶液;将反应物B溶解于第一非水溶液中,配制反应物B的第一非水溶液;然后将反应物A的第一非水溶液加入至反应物B的第一非水溶液中进行第一取代反应。In order to improve the efficiency of the first substitution reaction, in the embodiment, before mixing the reactant A and the reactant B, it is ideal to dissolve the reactant A in the first non-aqueous solution to prepare the first non-aqueous solution of the reactant A; Dissolving reactant B in the first non-aqueous solution to prepare a first non-aqueous solution of reactant B; then adding the first non-aqueous solution of reactant A to the first non-aqueous solution of reactant B to perform a first substitution reaction.

进一步实施例中,步骤S01中的第一取代反应包括先进行前段取代反应再进行后段取代反应的步骤;其中,前段取代反应是将反应物A逐渐加入至含有反应物B的第一非水溶液中直至添加完毕后继续反应1-2小时的取代反应阶段,后段取代反应为反应物A添加完毕并继续反应1-2小时后直至取代反应结束的阶段。其中,前段取代反应的温度为-20~0℃,具体可以是-20℃、-15℃、-10℃、-5℃、0℃等典型而非限制性的温度。后段取代反应的温度为0~40℃,具体可以是0℃、5℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃等典型而非限制性的温度。后段取代反应应该是充分的,如直至第一取代反应无任何气体产生为止。通过将取代反应设置为两阶段,提高第一取代反应的效率,降低副产物的生成,提高目标产物的得率。同时有利于避免反应过于剧烈,并吸收反应释放的热量。In a further embodiment, the first substitution reaction in step S01 includes the step of performing the first substitution reaction and then the second substitution reaction; wherein, the front substitution reaction is to gradually add reactant A to the first non-aqueous solution containing reactant B In the substitution reaction stage, the reaction is continued for 1-2 hours after the addition is completed, and the latter stage of the substitution reaction is the stage after the addition of reactant A is completed and the reaction is continued for 1-2 hours until the end of the substitution reaction. Wherein, the temperature of the preceding substitution reaction is -20 to 0°C, specifically -20°C, -15°C, -10°C, -5°C, 0°C and other typical but non-limiting temperatures. The temperature of the subsequent substitution reaction is 0-40°C, specifically 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C and other typical but non-limiting temperatures. The subsequent substitution reaction should be sufficient, such as until the first substitution reaction does not produce any gas. By setting the substitution reaction into two stages, the efficiency of the first substitution reaction is improved, the generation of by-products is reduced, and the yield of the target product is increased. At the same time, it is beneficial to avoid the reaction being too violent and absorb the heat released by the reaction.

实施例中,第一非水溶液选自乙腈、丙腈、1,3-二氧戊环、四氢呋喃、2-甲基四氢呋喃、2,5-二甲基四氢呋喃、1,4-二氧六环、乙二醇二甲醚、乙二醇二乙醚、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲酰胺、六甲基磷酰三胺、六甲基亚磷酰三胺、六乙基磷酰三胺、六乙基亚磷酰三胺、二甲基亚砜、二乙基亚砜、二氯甲烷、三氯甲烷、乙醚、丙醚、甲基叔丁基醚、乙基叔丁基醚、乙酸甲酯、乙酸乙酯、丙酸乙酯、乙酸丙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、正己烷、正庚烷、环己烷、苯、甲苯、二甲苯中的至少一种。该些非水溶液能够有效溶解两反应物,而且能够有效减少副产物的生成,提高目标产物的得率。而且便于对目标产物的纯化,如采用浓缩纯化得到纯度高的含支链卤代磷酸酯。In an embodiment, the first non-aqueous solution is selected from acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous Triamine, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl Ether, ethyl tert-butyl ether, methyl acetate, ethyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, n-hexane, n-heptane, cyclohexane at least one of alkanes, benzene, toluene, and xylene. These non-aqueous solutions can effectively dissolve the two reactants, and can effectively reduce the formation of by-products and increase the yield of the target product. Moreover, it is convenient to purify the target product, such as adopting concentrated purification to obtain branched-chain-containing halogenated phosphoric acid ester with high purity.

另外,步骤S01的在进行第一取代反应过程中所生成的副产物气体可以用水吸收,以提高环保性或副产物的再利用。In addition, the by-product gas generated during the first substitution reaction in step S01 can be absorbed with water to improve environmental protection or reuse of by-products.

经步骤S01中的第一取代反应结束后,还包括对结构式Ⅰ所示的含支链卤代磷酸酯产物进行分离纯化处理的步骤,该纯化处理包括将经第一取代反应后的混合物除去第一非水溶液后,对粗品进行蒸馏处理或者采用非水溶液进行重结晶并干燥处理。具体实施例中,当粗品流动性差如粘滞挂壁,将粗品溶解于第三非水溶液中进行重结晶处理、固液分离处理并进行干燥处理,获得纯的含支链卤代磷酸酯产物。其中,干燥为真空干燥,如真空干燥温度为0~80℃,干燥时长为2~6h。当粗品流动性好如不出现粘滞挂壁现象,将粗品直接进行减压蒸馏处理得到获得纯的含支链卤代磷酸酯产物。如减压蒸馏温度为20~300℃。After the first substitution reaction in step S01 is completed, it also includes the step of separating and purifying the branched-chain halogenated phosphoric acid ester product shown in the structural formula I. The purification treatment includes removing the first substitution reaction from the mixture After a non-aqueous solution, the crude product is distilled or recrystallized using a non-aqueous solution and dried. In a specific embodiment, when the fluidity of the crude product is poor such as sticking to the wall, the crude product is dissolved in the third non-aqueous solution for recrystallization treatment, solid-liquid separation treatment and drying treatment to obtain a pure branched-chain halogenated phosphoric acid ester product. Wherein, the drying is vacuum drying, for example, the vacuum drying temperature is 0-80° C., and the drying time is 2-6 hours. When the fluidity of the crude product is good, if there is no sticky wall hanging phenomenon, the crude product is directly subjected to vacuum distillation to obtain a pure branched-chain-containing halogenated phosphoric acid ester product. Such as vacuum distillation temperature is 20 ~ 300 ℃.

具体实施例中,用于重结晶的第三非水溶液为乙腈、丙腈、1,3-二氧戊环、四氢呋喃、2-甲基四氢呋喃、2,5-二甲基四氢呋喃、1,4-二氧六环、乙二醇二甲醚、乙二醇二乙醚、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲酰胺、六甲基磷酰三胺、六甲基亚磷酰三胺、六乙基磷酰三胺、六乙基亚磷酰三胺、二甲基亚砜、二乙基亚砜、二氯甲烷、三氯甲烷、乙醚、丙醚、甲基叔丁基醚、乙基叔丁基醚、乙酸甲酯、乙酸乙酯、丙酸乙酯、乙酸丙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、正己烷、正庚烷、环己烷、苯、甲苯、二甲苯中的至少一种。In a specific embodiment, the third non-aqueous solution used for recrystallization is acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4- Dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphoric triamide, Methyl phosphorous triamide, hexaethyl phosphorous triamide, hexaethyl phosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, Methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, n-hexane, n- At least one of heptane, cyclohexane, benzene, toluene, and xylene.

当步骤S01中的结构式ⅠB中的M1、M2、M3独立的选自氯、溴、碘原子中的任一种也即是反应物B为氯、溴、碘中的至少一种的三卤化磷具体如PCl3、PBr3、PI3时,上述含支链卤代磷酸酯的制备方法还包括如下步骤S02:When M 1 , M 2 , and M 3 in the structural formula I B in step S01 are independently selected from any of chlorine, bromine, and iodine atoms, that is, the reactant B is at least one of chlorine, bromine, and iodine When the phosphorus trihalides are specifically PCl 3 , PBr 3 , and PI 3 , the method for preparing the branched-chain-containing halogenated phosphoric acid ester further includes the following step S02:

步骤S02:将经第一取代反应生成的结构式Ⅰ所示的含支链卤代磷酸酯产物与氟化物于第二非水溶液中进行第二取代反应,生成如下述通式Ⅰ1所示的含支链二氟磷酸酯产物。Step S02: Perform a second substitution reaction with the branched-chain halophosphate product represented by the structural formula I shown in the first substitution reaction and fluoride in the second non-aqueous solution to generate the halogenated phosphoric acid ester product shown in the following general formula I Branched-chain difluorophosphate product.

具体地,根据结构式Ⅰ所示的含支链卤代磷酸酯产物,该第二取代反应的化学反应式(2)所示,需要说明的是,化学反应式(2)所示结构式Ⅰ中的M1、M2均非氟原子:Specifically, according to the branched-chain halogenated phosphoric acid ester product shown in structural formula I, the chemical reaction formula (2) of the second substitution reaction is shown. It should be noted that the chemical reaction formula (2) shown in structural formula I Both M 1 and M 2 are not fluorine atoms:

Figure BDA0003106642530000121
Figure BDA0003106642530000121

通过对第一取代反应生成产物进行氟取代反应,使得生成的含支链二氟磷酸酯产物具有更加优异的浸润性,而且添加电解液中后不附带杂质元素或杂质元素少,从而提高相应电解质或电解液纯度和相应的化学性能。为提高含支链卤代磷酸酯制备方法的效率,在化学反应式(2)所示的第二取代反应中,结构式Ⅰ所示的含支链卤代磷酸酯产物也可不经纯化直接用的粗品或直接向经第一取代反应后的混合物溶液中添加。By performing a fluorine substitution reaction on the product generated by the first substitution reaction, the resulting branched-chain difluorophosphate product has more excellent wettability, and after being added to the electrolyte, there are no or few impurity elements, thereby improving the corresponding electrolyte. Or electrolyte purity and corresponding chemical properties. In order to improve the efficiency of the preparation method containing branched chain halogenated phosphoric acid ester, in the second substitution reaction shown in chemical reaction formula (2), the containing branched chain halogenated phosphoric acid ester product shown in structural formula I also can directly use without purification Add the crude product directly to the mixture solution after the first substitution reaction.

实施例中,结构式Ⅰ所示的含支链卤代磷酸酯产物与氟化物是按照摩尔比为1:(1~6)的比例混合于第二非水溶液中并进行第二取代反应。具体实施例中,结构式Ⅰ所示的含支链卤代磷酸酯产物与氟化物的摩尔比为1:1、1:1.5、1:2、1:2.5、1:3、1:3.5、1:4、1:4.5、1:5、1:5.5、1:6等典型而非限制性的比例。In an embodiment, the branched-chain halogenated phosphoric acid ester product represented by the structural formula I and the fluoride are mixed in the second non-aqueous solution according to a molar ratio of 1: (1-6), and the second substitution reaction is performed. In a specific embodiment, the molar ratio of the branched-chain halogenated phosphoric acid ester product represented by the structural formula I to the fluoride is 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1 :4, 1:4.5, 1:5, 1:5.5, 1:6 and other typical but non-limiting ratios.

另些实施例中,结构式Ⅰ所示的含支链卤代磷酸酯产物与第二非水溶液的质量比为1:(1~10)。具体实施例中,含支链卤代磷酸酯产物与第二非水溶液的质量比为1:1、1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9、1:10等典型而非限制性的比例。In other embodiments, the mass ratio of the branched chain-containing halogenated phosphoric acid ester product represented by the structural formula I to the second non-aqueous solution is 1: (1-10). In a specific embodiment, the mass ratio of the branched-chain halogenated phosphate product to the second non-aqueous solution is 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10 and other typical and non-limiting ratios.

通过上述化学反应式(2)中结构式Ⅰ所示的含支链卤代磷酸酯产物与氟化物的比例和浓度的调整,提高第二取代反应的效率。同时使反应物完全反应、减少杂质的产生,并节约反应物用量降低合成成本。The efficiency of the second substitution reaction is improved by adjusting the ratio and concentration of the branched-chain halogenated phosphoric acid ester product and fluoride represented by the structural formula I in the above chemical reaction formula (2). At the same time, the reactants are completely reacted, the generation of impurities is reduced, and the amount of reactants is saved to reduce the synthesis cost.

实施例中,第二取代反应的温度为-20~80℃。具体可以是-20℃、-15℃、-10℃、-5℃、0℃、5℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃等典型而非限制性的温度。.通过对取代反应的温度控制和优化,提高取代反应的效率。通过对取代反应的温度控制和优化,提高取代反应的效率。基于该取代反应的温度,第二取代反应应该是充分的,如反应时长为3~12h,具体可以是3h、4h、5h、6h、7h、8h、9h、10h、11h、12h等典型而非限制性的反应时间。In an embodiment, the temperature of the second substitution reaction is -20-80°C. Specifically, it can be -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C °C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, etc. are typical and non-limiting temperatures. .Through the temperature control and optimization of the substitution reaction, the efficiency of the substitution reaction is improved. Through the temperature control and optimization of the substitution reaction, the efficiency of the substitution reaction is improved. Based on the temperature of the substitution reaction, the second substitution reaction should be sufficient. For example, the reaction time is 3 to 12 hours, specifically 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, etc. Restricted reaction time.

实施例中,氟化物选氟化氢(HF)、三乙胺氟化氢(Et3N·3HF)、吡啶氟化氢(Py·HF)、氟化钾(KF)、氟化钠(NaF)、氟化镁(MgF2)、氟化锌(ZnF2)、氟化铝(AlF3)、三氟化锑(SbF3)、五氟化锑(SbF5)、四氟化硫(SF4)、六氟化硫(SF6)中的至少一种。该些氟化物能够有效与结构式Ⅰ所示的含支链卤代磷酸酯发生取代反应,提高第二取代反应的效率和提高含支链二氟磷酸酯产物的得率。In the embodiment, the fluoride is selected from hydrogen fluoride (HF), triethylamine hydrogen fluoride (Et 3 N 3HF), pyridine hydrogen fluoride (Py HF), potassium fluoride (KF), sodium fluoride (NaF), magnesium fluoride ( MgF 2 ), zinc fluoride (ZnF 2 ), aluminum fluoride (AlF 3 ), antimony trifluoride (SbF 3 ), antimony pentafluoride (SbF 5 ), sulfur tetrafluoride (SF 4 ), hexafluoride at least one of sulfur (SF 6 ). These fluorides can effectively undergo a substitution reaction with the branched-chain-containing halogenated phosphoric acid ester shown in the structural formula I, thereby improving the efficiency of the second substitution reaction and increasing the yield of branched-chain-containing difluorophosphate ester products.

实施例中,第二非水溶液选自乙腈、丙腈、1,3-二氧戊环、四氢呋喃、2-甲基四氢呋喃、2,5-二甲基四氢呋喃、1,4-二氧六环、乙二醇二甲醚、乙二醇二乙醚、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲酰胺、六甲基磷酰三胺、六甲基亚磷酰三胺、六乙基磷酰三胺、六乙基亚磷酰三胺、二甲基亚砜、二乙基亚砜、二氯甲烷、三氯甲烷、乙醚、丙醚、甲基叔丁基醚、乙基叔丁基醚、乙酸甲酯、乙酸乙酯、丙酸乙酯、乙酸丙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、正己烷、正庚烷、环己烷、苯、甲苯、二甲苯中的至少一种。该些非水溶液能够有效溶解两反应物,而且能够有效减少副产物的生成,提高目标产物的得率。In an embodiment, the second non-aqueous solution is selected from acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous Triamine, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl Ether, ethyl tert-butyl ether, methyl acetate, ethyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, n-hexane, n-heptane, cyclohexane at least one of alkanes, benzene, toluene, and xylene. These non-aqueous solutions can effectively dissolve the two reactants, and can effectively reduce the formation of by-products and increase the yield of the target product.

另外,待步骤S02中的第二取代反应结束后,也还包括对结构式Ⅰ1所示的含支链二氟磷酸酯产物进行分离纯化处理的步骤,该纯化处理包括将经第二取代反应后的混合物除去第二非水溶液后,对粗品进行蒸馏处理或者采用非水溶液进行重结晶并干燥处理。具体实施例中,当粗品流动性差如粘滞挂壁,将粗品溶解于第四非水溶液中进行重结晶处理、固液分离处理并进行干燥处理,获得纯的含支链卤代磷酸酯产物。其中,干燥为真空干燥,如真空干燥温度为0~80℃,干燥时长为2~6h。当粗品流动性好如不出现粘滞挂壁现象,将粗品直接进行减压蒸馏处理得到获得纯的含支链卤代磷酸酯产物。如减压蒸馏温度为20~300℃。In addition, after the second substitution reaction in step S02 is completed, it also includes the step of separating and purifying the branched-chain difluorophosphate product shown in the structural formula I1 . After removing the second non-aqueous solution, the crude product is distilled or recrystallized using a non-aqueous solution and dried. In a specific embodiment, when the fluidity of the crude product is poor such as sticking to the wall, the crude product is dissolved in the fourth non-aqueous solution for recrystallization treatment, solid-liquid separation treatment and drying treatment to obtain a pure branched-chain halogenated phosphoric acid ester product. Wherein, the drying is vacuum drying, for example, the vacuum drying temperature is 0-80° C., and the drying time is 2-6 hours. When the fluidity of the crude product is good, if there is no sticky wall hanging phenomenon, the crude product is directly subjected to vacuum distillation to obtain a pure branched-chain-containing halogenated phosphoric acid ester product. Such as vacuum distillation temperature is 20 ~ 300 ℃.

具体实施例中,用于重结晶的第四非水溶液为乙腈、丙腈、1,3-二氧戊环、四氢呋喃、2-甲基四氢呋喃、2,5-二甲基四氢呋喃、1,4-二氧六环、乙二醇二甲醚、乙二醇二乙醚、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲酰胺、六甲基磷酰三胺、六甲基亚磷酰三胺、六乙基磷酰三胺、六乙基亚磷酰三胺、二甲基亚砜、二乙基亚砜、二氯甲烷、三氯甲烷、乙醚、丙醚、甲基叔丁基醚、乙基叔丁基醚、乙酸甲酯、乙酸乙酯、丙酸乙酯、乙酸丙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、正己烷、正庚烷、环己烷、苯、甲苯、二甲苯中的至少一种。In a specific embodiment, the fourth non-aqueous solution used for recrystallization is acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4- Dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphoric triamide, Methyl phosphorous triamide, hexaethyl phosphorous triamide, hexaethyl phosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, Methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, n-hexane, n- At least one of heptane, cyclohexane, benzene, toluene, and xylene.

由上述本发明实施例含支链卤代磷酸酯制备方法制备的目标产物含支链卤代磷酸酯含有磷酸酯基团等功能基团,赋予制备的含支链卤代磷酸酯具有优异成膜性能和浸润性能以及低阻抗特性,其热稳定性高。另外,含支链卤代磷酸酯制备方法通过一步反应生成目标产物,目标产物得率高,副反应少,工艺条件易控,其制备获得的含支链卤代磷酸酯的得率和性能稳定。同时,采用非水溶液作为反应溶剂,还能够降低对目标产物的纯化难度。另外,还能够有效通过调节反应条件提高反应效率和提高目标产物的得率。The target product prepared by the method for preparing branched-chain-containing halogenated phosphoric acid ester according to the above-mentioned embodiment of the present invention contains functional groups such as phosphate groups, which endows the prepared branched-chain-containing halogenated phosphoric acid ester with excellent film-forming properties. Performance and wetting properties as well as low impedance characteristics, its high thermal stability. In addition, the method for preparing the branched-chain halogenated phosphoric acid ester generates the target product through a one-step reaction, the yield of the target product is high, the side reactions are few, the process conditions are easy to control, and the yield and performance of the branched-chain-containing halogenated phosphoric acid ester prepared by the method are stable. . At the same time, using a non-aqueous solution as a reaction solvent can also reduce the difficulty of purifying the target product. In addition, it can also effectively improve the reaction efficiency and the yield of the target product by adjusting the reaction conditions.

再一方面,基于上文本发明实施例含支链卤代磷酸酯及其制备方法,本发明实施例还提供一种电解液添加剂。本发明实施例电解液添加剂含有上文本发明实施例含支链卤代磷酸酯。当上文本发明实施例含支链卤代磷酸酯作为电解液添加剂时,其水分≤100ppm,酸度≤100ppm,氯离子含量≤50ppm。其纯度高,充分发挥本发明实施例卤代磷酸酯的上述作用。当然,该电解质盐还可以进一步含有其添加剂,也即是该电解液添加剂可以单独含有上文含支链卤代磷酸酯,也可以与其添加剂进行复配形成混合添加剂。其他添加剂可以是电解液领域的添加剂,并可以根据需要进行选择其他添加剂的种类和与上文含支链卤代磷酸酯的配比量。由于电解液添加剂含有上文含支链卤代磷酸酯,因此,本发明实施例电解液添加剂能够显著改善电解液的热稳定性,提高其成膜性能和浸润性能以及低阻抗特性。In another aspect, based on the above embodiments of the invention containing branched chain halogenated phosphoric acid esters and their preparation methods, the embodiments of the invention also provide an electrolyte additive. The electrolyte additive of the embodiment of the present invention contains the branched-chain halogenated phosphoric acid ester in the above embodiment of the invention. When the embodiment of the above invention contains branched-chain halogenated phosphoric acid ester as an electrolyte additive, its water content is ≤100ppm, its acidity is ≤100ppm, and its chloride ion content is ≤50ppm. Its purity is high, and the above-mentioned functions of the halogenated phosphoric acid ester of the embodiment of the present invention can be fully exerted. Of course, the electrolyte salt may further contain its additives, that is, the electrolyte additive may contain the above-mentioned branched-chain-containing halogenated phosphoric acid ester alone, or may be compounded with its additives to form a mixed additive. Other additives can be additives in the electrolyte field, and the types of other additives and the ratio of the above branched-chain-containing halogenated phosphoric acid esters can be selected according to needs. Since the electrolyte additive contains the above-mentioned branched-chain-containing halogenated phosphate, the electrolyte additive in the embodiment of the present invention can significantly improve the thermal stability of the electrolyte, improve its film-forming performance, wetting performance and low impedance characteristics.

基于上文含支链卤代磷酸酯及其制备方法和电解液添加剂,本发明实施例还提供一种电解液。该电解液含有上文电解液添加剂,也即是含有上文含支链卤代磷酸酯。因此,本发明实施例电解液的成膜性能和浸润性能以及热稳定性好,可以显著提升二次电池高低温、循环和存储等性能,同时还能抑制二次电池产气以及阻抗增长,提高了二次电池安全性能和综合性能。Based on the above-mentioned halogenated phosphoric acid ester containing branched chains, its preparation method and electrolyte additive, an embodiment of the present invention also provides an electrolyte. The electrolyte contains the above electrolyte additive, that is, contains the above branched-chain-containing halogenated phosphoric acid ester. Therefore, the film-forming performance, wetting performance and thermal stability of the electrolyte in the embodiment of the present invention are good, which can significantly improve the high and low temperature, cycle and storage performance of the secondary battery, and can also suppress the gas production and impedance growth of the secondary battery, and improve the performance of the secondary battery. The safety performance and comprehensive performance of the secondary battery are improved.

实施例中,以该电解液的总质量为100%计,上文含支链卤代磷酸酯在电解液中的质量浓度为0.1%-5%,具体可以是0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%等典型而非限制性的含量。通过控制和调节上文含支链卤代磷酸酯在电解液中的浓度,一方面充分发挥上文含支链卤代磷酸酯对电解液热稳定性改善作用,提高其成膜性能和浸润性能,抑制阻抗增长;另一方面,可以与电解液中的其它成分起到功能互补的作用,进一步提高电解液的稳定性,抑制二次电池产气现象,从提高二次电池的安全性以及电化学性能。In an embodiment, based on the total mass of the electrolyte as 100%, the mass concentration of the above branched chain-containing halogenated phosphoric acid ester in the electrolyte is 0.1%-5%, specifically 0.5%, 1%, 1.5% , 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and other typical and non-limiting contents. By controlling and adjusting the concentration of the above branched-chain-containing halogenated phosphates in the electrolyte, on the one hand, the above-mentioned branched-chain-containing halogenated phosphates can fully exert the effect of improving the thermal stability of the electrolyte, and improve its film-forming performance and wetting performance , to inhibit the growth of impedance; on the other hand, it can play a complementary role with other components in the electrolyte, further improve the stability of the electrolyte, inhibit the gas production of the secondary battery, and improve the safety and battery life of the secondary battery. chemical properties.

另外,电解液除了含有上文含支链卤代磷酸酯之外,还包括电解液必含的组分如溶剂、电解质锂盐或进一步还可以含有应用于电解液中的其他组分,其他组分可以单独发挥作用,也可以与上文含支链卤代磷酸酯起到增效协同作用。In addition, in addition to the above branched-chain-containing halogenated phosphate, the electrolyte also includes components that must be contained in the electrolyte such as solvents, electrolyte lithium salts, or other components that are used in the electrolyte. Other components Parts can play a role alone, and can also play a synergistic effect with the above branched-chain-containing halogenated phosphoric acid ester.

其中,电解液所含的溶剂为非水溶液,定义为第五非水溶液,在一些实施例中,该第五非水溶液可以但不仅仅为碳酸酯类溶剂,其中碳酸酯为链状或环状的碳酸酯。在一些具体实施例中,碳酸酯为链状或环状的碳酸酯。在一些具体实施例中,环状碳酸酯选自碳酸乙烯酯(EC)、碳酸亚乙烯酯(VC)、乙烯基碳酸乙烯酯(VEC)、碳酸丙烯酯(PC)、γ-丁内酯中的至少一种;链状碳酸酯选自碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯、碳酸甲乙酯(EMC)、碳酸甲丙酯、碳酸乙丙酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯中的至少一种。Wherein, the solvent contained in the electrolyte solution is a non-aqueous solution, which is defined as the fifth non-aqueous solution. In some embodiments, the fifth non-aqueous solution can be but not only a carbonate solvent, wherein the carbonate is a chain or cyclic Carbonate. In some embodiments, the carbonates are chain or cyclic carbonates. In some specific embodiments, the cyclic carbonate is selected from ethylene carbonate (EC), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), propylene carbonate (PC), gamma-butyrolactone At least one of; Chain carbonate is selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate, ethylene propyl carbonate, At least one of methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate.

具体实施例中,电解质锂盐包括LiPF6、LiBF4、LiClO4、LiSbF6、LiAsF6、LiTDI、LiN(SO2C2F5)2、LiN(SO2CF3)2、LiN(SO3C2F5)2、LiN(SO2F)2、LiN(SO2C6F5)2、LiN(SO3C6F5)2、LiSO3CF3、LiSO3C2F5、LiSO3C4F9、LiSO3C6H5、LiSO3C6F5中的一种或多种。In a specific embodiment, the electrolyte lithium salt includes LiPF 6 , LiBF 4 , LiClO 4 , LiSbF 6 , LiAsF 6 , LiTDI, LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 ) 2 , LiN(SO 3 C 2 F 5 ) 2 , LiN(SO 2 F) 2 , LiN(SO 2 C 6 F 5 ) 2 , LiN(SO 3 C 6 F 5 ) 2 , LiSO 3 CF 3 , LiSO 3 C 2 F 5 , LiSO One or more of 3 C 4 F 9 , LiSO 3 C 6 H 5 , LiSO 3 C 6 F 5 .

具体实施例中,其他添加剂包括但不仅限于1,3-丙磺酸内酯(PS)、1,3-丙烯磺酸内酯(PES)、亚硫酸乙烯酯(ES)、硫酸乙烯酯(DTD)、二氟草酸硼酸锂(LiODFB)、双草酸硼酸锂(LiBOB)中的一种或多种。In a specific embodiment, other additives include but not limited to 1,3-propane sultone (PS), 1,3-propene sultone (PES), vinyl sulfite (ES), vinyl sulfate (DTD ), one or more of lithium difluorooxalate borate (LiODFB), lithium bisoxalate borate (LiBOB).

另外,上述电解液可以是锂离子电池电解液或锂金属电池电解液。In addition, the above electrolytic solution may be an electrolytic solution for a lithium ion battery or an electrolytic solution for a lithium metal battery.

基于上文电解液,本发明实施例还提供了一种二次电池。本发明实施例二次电池包括正极、负极等必要的部件,还包电解液,各部件和电解液按照锂离子电池组装要求进行组装。Based on the above electrolyte, the embodiment of the present invention also provides a secondary battery. The secondary battery of the embodiment of the present invention includes necessary components such as positive electrode and negative electrode, and electrolyte solution, and the components and electrolyte solution are assembled according to the assembly requirements of lithium-ion batteries.

其中,二次电池所含的电解液为上文本发明实施例电解液。因此,本发明实施例二次电池的在高低温下均具有良好的循环性能和存储性能,降低了二次电池产气以及阻抗增长等不良现象发生,安全性高,综合化学性能好,使用寿命更长。Wherein, the electrolyte contained in the secondary battery is the electrolyte of the above-mentioned embodiment of the invention. Therefore, the secondary battery of the embodiment of the present invention has good cycle performance and storage performance at high and low temperatures, reduces secondary battery gas production and impedance growth, and has high safety, good comprehensive chemical properties, and long service life. longer.

二次电池所含的正极可以是常规正极结构,如包括正极集流体和结合在正极集流体表面的正极活性层,其中,正极活性层包括正极活性材料、粘结剂、导电剂以及增稠剂(如需要)等组分。实施例中,正极活性物质可选自LiaCoO2(0.5<a<1.3)、LiaNiO2(0.5<a<1.3)、LiaMnO2(0.5<a<1.3)、LiaMn2O4(0.5<a<1.3)、Lia(NixCoyMnz)O2(0.5<a<1.3,0<x<1,0<y<1,0<z<1,x+y+z=1)、LiaNi1-xCoxO2(0.5<a<1.3,0<x<1)、LiaCo1-xMnxO2(0.5<a<1.3,0≤x<1)、LiaNi1-xMnxO2(0.5<a<1.3,0≤x<1)、Lia(NixCoyMnz)O4(0.5<a<1.3,0<x<2,0<y<2,0<z<2,x+y+z=2)、LiaMn2-xNxO4(0.5<a<1.3,0<x<2)、LiaMn2-xNxO4(0.5<a<1.3,0<y<2)、和LiaNPO4(0.5<a<1.3)中的任何一种或两种以上的混合物;N选自Fe、Ni、Co、Mn、Zn、Al、Cr、Mg、Zr、Mo、W、V、Ti、B、F和Y中的一种或多种。正极活性物质还可以是Li-Ni/Co/Mn氧化物;更进一步为Lia(NixCoyMnz)O2,其中0.90≤a≤1.10,0.3≤x≤0.9,0.05≤y<0.5,0.05≤z<0.5,且x+y+z=1;更进一步为Li(NixCoyMnz)O2,其中0.3≤x≤0.9,0.05≤y<0.5,0.05≤z<0.5,并且x+y+z=1。具体实施例中,正极活性物质可以为LiNi0.6Co0.2Mn0.2O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.1Mn0.1O2、LiNi1/3Co1/3Mn1/3O2中的一种或多种的混合。且正极活性物质的质量占正极活性浆料的质量的88%-98%。The positive electrode contained in the secondary battery can be a conventional positive electrode structure, such as including a positive electrode current collector and a positive electrode active layer bonded to the surface of the positive electrode current collector, wherein the positive electrode active layer includes a positive electrode active material, a binder, a conductive agent and a thickener (if necessary) and other components. In an embodiment, the positive electrode active material can be selected from Li a CoO 2 (0.5<a<1.3), Li a NiO 2 (0.5<a<1.3), Li a MnO 2 (0.5<a<1.3), Li a Mn 2 O 4 (0.5<a<1.3), Li a (Ni x Co y Mn z )O 2 (0.5<a<1.3, 0<x<1, 0<y<1, 0<z<1, x+y +z=1), Li a Ni 1-x Co x O 2 (0.5<a<1.3, 0<x<1), Li a Co 1-x Mn x O 2 (0.5<a<1.3, 0≤x <1), Li a Ni 1-x Mn x O 2 (0.5<a<1.3, 0≤x<1), Li a (Ni x Co y Mn z )O 4 (0.5<a<1.3, 0<x <2, 0<y<2, 0<z<2, x+y+z=2), Li a Mn 2-x N x O 4 (0.5<a<1.3, 0<x<2), Li a Any one or a mixture of two or more of Mn 2-x N x O 4 (0.5<a<1.3, 0<y<2), and Li a NPO 4 (0.5<a<1.3); N is selected from Fe , one or more of Ni, Co, Mn, Zn, Al, Cr, Mg, Zr, Mo, W, V, Ti, B, F and Y. The positive electrode active material can also be Li-Ni/Co/Mn oxide; further Li a ( Nix Co y Mn z )O 2 , where 0.90≤a≤1.10, 0.3≤x≤0.9, 0.05≤y<0.5 , 0.05≤z<0.5, and x+y+ z =1; further Li(Nix Co y Mn z )O 2 , where 0.3≤x≤0.9, 0.05≤y<0.5, 0.05≤z<0.5, And x+y+z=1. In a specific embodiment, the positive electrode active material can be LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 1/3 Co 1/3 Mn 1/3 O A mixture of one or more of 2 . And the mass of the positive electrode active material accounts for 88%-98% of the mass of the positive electrode active slurry.

二次电池所含的负极可以是常规负极结构,如包括负极集流体和结合在负极集流体表面的负极活性层,其中,负极活性层包括能够使锂离子嵌入和脱出的负极活性物质、导电剂、粘结剂、增稠剂(如需要)等组分。实施例中,负极活性物质可选自碳材料(诸如结晶碳、无定形碳、碳复合物和碳纤维)、锂金属、锂与其他元素的合金等能够发生锂离子嵌入和脱出的至少一种。结晶碳的非限制实例包括石墨基材料,如人造石墨、天然石墨、石墨化焦炭、石墨化MCMB、石墨化MPCF等。无定形碳的非限制实例可包括软碳(低温焙烧碳)、硬碳、焦炭、中间相碳微球(MCMB)、中间相沥青基碳纤维(MPCF)等。与锂金属形成合金的其他元素,包括铝、锌、铋、镉、锑、硅、铅、锡、镓或铟等元素中的一种或多种。且负极活性物质的质量占负极活性浆料的质量的90%-96%。The negative electrode contained in the secondary battery can be a conventional negative electrode structure, such as including a negative electrode current collector and a negative electrode active layer combined on the surface of the negative electrode current collector, wherein the negative electrode active layer includes a negative electrode active material capable of intercalating and extracting lithium ions, a conductive agent , binder, thickener (if necessary) and other components. In an embodiment, the negative electrode active material can be selected from at least one of carbon materials (such as crystalline carbon, amorphous carbon, carbon composites, and carbon fibers), lithium metal, alloys of lithium and other elements, and the like that can intercalate and extract lithium ions. Non-limiting examples of crystalline carbon include graphite-based materials such as artificial graphite, natural graphite, graphitized coke, graphitized MCMB, graphitized MPCF, and the like. Non-limiting examples of amorphous carbon may include soft carbon (low temperature fired carbon), hard carbon, coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fiber (MPCF), and the like. Other elements that form alloys with lithium metal include one or more of elements such as aluminum, zinc, bismuth, cadmium, antimony, silicon, lead, tin, gallium or indium. And the mass of the negative electrode active material accounts for 90%-96% of the mass of the negative electrode active slurry.

需要说明的是,上述正极集流体(或负极集流体)和正极活性材料层(或负极活性材料层)仅提供了一种常用的位置关系,即将正极活性浆料(或负极活性浆料)涂覆于正极集流体(或负极集流体)表面形成正极活性材料层(或负极活性材料层),不应理解为其是对本发明实施例所提供的二次电池的限制。根据实际情况,结合对二次电池性能的要求可对集流体和活性材料进行改变,如将正极活性物质(或负极活性物质)及助剂的混合粉料填充在空心正极集流体(或空心负极集流体)的内部等各种方式。It should be noted that the above-mentioned positive electrode current collector (or negative electrode current collector) and positive electrode active material layer (or negative electrode active material layer) only provide a common positional relationship, that is, the positive electrode active slurry (or negative electrode active slurry) is coated with The positive electrode active material layer (or negative electrode active material layer) formed on the surface of the positive electrode current collector (or negative electrode current collector) should not be construed as a limitation to the secondary battery provided by the embodiments of the present invention. According to the actual situation, combined with the requirements for the performance of the secondary battery, the current collector and the active material can be changed, such as filling the mixed powder of the positive electrode active material (or negative electrode active material) and additives in the hollow positive electrode current collector (or hollow negative electrode Collector) in various ways.

实施例中,形成正极活性成的正极活性浆料和形成负极活性成的负极活性浆料时还需要加入溶剂,该溶剂作用为分散电极活性材料、粘合剂、导电材料等,可以为非水溶液或含水溶剂。为高纯去离子水时,高纯度去离子水的电导率≤3us/cm,非水溶液可包括N-甲基-2-吡咯烷酮(NMP)、二甲基甲酰胺、二甲基乙酰胺、N,N-二甲基氨基丙胺、环氧乙烷、四氢呋喃等,其中的水分含量≤100ppm。In an embodiment, a solvent needs to be added when forming the positive electrode active slurry of the positive electrode active component and the negative electrode active slurry of the negative electrode active component. The solvent is used to disperse electrode active materials, binders, conductive materials, etc. or aqueous solvents. When it is high-purity deionized water, the conductivity of high-purity deionized water is ≤3us/cm, and the non-aqueous solution can include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, N , N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran, etc., where the moisture content is ≤100ppm.

实施例中,正极、负极所用导电剂可选自石墨基导电剂、炭黑基导电剂、金属基或金属化合物基导电剂。石墨基导电剂的应用实例包括人造石墨、天然石墨等。炭黑基导电剂的应用实例包括乙炔黑、科琴黑(ketjen black)、超导乙炔炭黑(denka black)、热裂炭黑(thermal black)、槽法炭黑(channel black)等。金属基或金属化合物基的导电剂的应用实例包括锡、氧化锡、磷酸锡、氧化钛、钛酸钾、钙钛矿材料例如LaSrCoO3或LaSrMnO3等中的至少一种,且正、负极导电剂的质量分别占正、负极活性浆料的质量的0.1%-6%。当导电剂的质量比小于0.1%时,会导致电化学性能劣化,当含量大于6%时,会减少正负极活性材料的含量,导致电池的能量密度变低。需要说明的是导电剂可以提高材料导电性,任何在电池体系中不会发生化学反应且是电子导体的材料皆可作为导电剂使用。In an embodiment, the conductive agent used in the positive electrode and the negative electrode can be selected from graphite-based conductive agents, carbon black-based conductive agents, metal-based or metal compound-based conductive agents. Application examples of the graphite-based conductive agent include artificial graphite, natural graphite, and the like. Application examples of the carbon black-based conductive agent include acetylene black, ketjen black, superconducting acetylene black (denka black), thermal black, channel black, and the like. Application examples of metal-based or metal compound-based conductive agents include at least one of tin, tin oxide, tin phosphate, titanium oxide, potassium titanate, perovskite materials such as LaSrCoO3 or LaSrMnO3 , etc., and the positive and negative electrodes are conductive The mass of the additive accounts for 0.1%-6% of the mass of the positive and negative electrode active slurry respectively. When the mass ratio of the conductive agent is less than 0.1%, the electrochemical performance will be deteriorated, and when the content is greater than 6%, the content of positive and negative active materials will be reduced, resulting in lower energy density of the battery. It should be noted that the conductive agent can improve the conductivity of the material, and any material that does not undergo chemical reactions in the battery system and is an electronic conductor can be used as a conductive agent.

实施例中,正、负极所用粘结剂可以选自聚偏二氟乙烯(PVDF)、聚六氟丙烯-聚偏二氟乙烯(HFP/PVDF)的共聚物、聚醋酸乙烯酯、聚乙烯醇、聚环氧乙烷、聚乙烯吡咯烷酮、烷基化聚环氧乙烷、聚乙烯基醚、聚甲基丙烯酸甲酯、聚丙烯酸乙酯、聚四氟乙烯、聚氯乙烯、聚丙烯腈、聚乙烯基吡啶、丁苯橡胶、丙烯腈-丁二烯橡胶等中的至少一种,且正、负极粘结剂的质量分别占正、负极活性浆料质量的1%-6%。粘结剂含量过低,正负极活性材料与集流体之间的粘接强度不足,粘结剂含量太高,粘接强度会增强,但是会减少正负极活性材料的含量,不利于提高电池的能量密度。In an embodiment, the binder used for the positive and negative electrodes can be selected from polyvinylidene fluoride (PVDF), polyhexafluoropropylene-polyvinylidene fluoride (HFP/PVDF) copolymer, polyvinyl acetate, polyvinyl alcohol , polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, polyvinyl ether, polymethyl methacrylate, polyethyl acrylate, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, At least one of polyvinylpyridine, styrene-butadiene rubber, acrylonitrile-butadiene rubber, etc., and the mass of the positive and negative electrode binders account for 1%-6% of the mass of the positive and negative electrode active slurry, respectively. If the binder content is too low, the bonding strength between the positive and negative active materials and the current collector will be insufficient; if the binder content is too high, the bonding strength will be enhanced, but it will reduce the content of the positive and negative active materials, which is not conducive to improving The energy density of the battery.

实施例中,负极增稠剂可以使用羟甲基纤维素、羟乙基纤维素、羟丙基纤维素等,其质量占负极活性浆料的质量的1%-4%。增稠剂没有特别限制,只要可用于调节负极活性材料浆料的粘度即可。In an embodiment, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc. may be used as the negative electrode thickener, and its mass accounts for 1%-4% of the mass of the negative electrode active slurry. The thickener is not particularly limited as long as it can be used to adjust the viscosity of the negative active material slurry.

另外,正极所含的正极集流体和负极所含的负极集流体可以但不仅仅为铝、铝合金等,形貌可以但不限于箔(foil)或网(mesh)等。In addition, the positive electrode current collector contained in the positive electrode and the negative electrode current collector contained in the negative electrode can be, but not only, aluminum, aluminum alloy, etc., and the shape can be, but not limited to, foil (foil) or mesh (mesh).

二次电池所含的隔膜主要为离子提供迁移所需的离子通道,同时将正极、负极隔离开防止正极和负极发生短路,一般使用烯烃聚合物膜(例如聚丙烯、聚乙烯、聚乙烯/聚丙烯、聚乙烯/聚丙烯/聚乙烯和聚丙烯/聚乙烯/聚丙烯)或者多层膜(multiple-film)、微孔膜以及它们的织造和非织造物。具体可采用三层复合隔膜,其厚度为12μm-36μm,孔隙率为30%-70%。为提升隔膜热稳定性,可以在隔膜表面涂覆一层或多层结构稳定的树脂或陶瓷材料。The separator contained in the secondary battery mainly provides ion channels for ions to migrate, and at the same time separates the positive and negative electrodes to prevent short circuit between the positive and negative electrodes. Generally, olefin polymer films (such as polypropylene, polyethylene, polyethylene/polyethylene) are used. propylene, polyethylene/polypropylene/polyethylene and polypropylene/polyethylene/polypropylene) or multiple-films, microporous films and their woven and non-woven fabrics. Specifically, a three-layer composite diaphragm can be used, the thickness of which is 12 μm-36 μm, and the porosity is 30%-70%. In order to improve the thermal stability of the diaphragm, one or more layers of structurally stable resin or ceramic material can be coated on the surface of the diaphragm.

实施例中,二次电池可以为方形,圆柱或软包等形式。另外,二次电池可以锂离子电池,也可以是锂金属电池。二次电池除了可应用于常规的移动通讯工具、个人电脑等用途之外,还适合于高电压、高功率和高温驱动等体系,如电动汽车、电动船舶、电动飞机等。此外,二次电池还可以与内燃机、燃料电池、太阳能电池、超级电容器等相互组合,用于混动汽车、电动自行车、物流车、船舶、飞机、机床以及其他高功率、高电压或高温驱动的其它用途。In an embodiment, the secondary battery may be in the form of a square, a cylinder, or a soft pack. In addition, the secondary battery may be a lithium ion battery or a lithium metal battery. In addition to being used in conventional mobile communication tools and personal computers, secondary batteries are also suitable for high-voltage, high-power and high-temperature drive systems, such as electric vehicles, electric ships, and electric aircraft. In addition, secondary batteries can also be combined with internal combustion engines, fuel cells, solar cells, supercapacitors, etc., for use in hybrid vehicles, electric bicycles, logistics vehicles, ships, aircraft, machine tools, and other high-power, high-voltage or high-temperature drives. other purposes.

为使本发明上述实施细节和操作能清楚地被本领域技术人员理解,以及本发明实施例含支链卤代磷酸酯及其制备方法、电解液和二次电池的进步性能显著的体现,以下通过多个实施例来举例说明上述技术方案。In order to make the above-mentioned implementation details and operations of the present invention clearly understood by those skilled in the art, as well as the embodiments of the present invention containing branched-chain halogenated phosphoric acid esters and their preparation methods, electrolytes and secondary batteries, the improved performance is significantly reflected, as follows The foregoing technical solution is illustrated by a plurality of embodiments.

A.含支链卤代磷酸酯及其制备方法实施例A. Examples of branched-chain-containing halogenated phosphoric acid esters and their preparation methods

实施例A1Example A1

本实施例提供一种1,4-戊二炔-3-醇二氯磷酸酯、1,4-戊二炔-3-醇二氟磷酸酯(上文式1)及其制备方法。This embodiment provides 1,4-pentadiyn-3-ol dichlorophosphate, 1,4-pentadiyn-3-ol difluorophosphate (formula 1 above) and a preparation method thereof.

本实施例1,4-戊二炔-3-醇二氯磷酸酯制备方法具体如下:Present embodiment 1,4-pentadiyn-3-alcohol dichlorophosphate preparation method is specifically as follows:

S1:室温条件下向反应釜中加入二氯甲烷40mL,然后加入1,4-戊二烯-3-醇8.41g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷40mL与18g POCl3在0℃条件下混合;将1,4-戊二烯-3-醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,1,4-戊二烯-3-醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到1,4-戊二炔-3-醇二氯磷酸酯。S1: Add 40mL of dichloromethane to the reaction kettle at room temperature, then add 8.41g (0.1mol) of 1,4-pentadien-3-ol, and stir at room temperature for 0.5h; Mix 40mL with 18g POCl 3 at 0°C; add the dichloromethane solution of 1,4-pentadien-3-ol to the dichloromethane solution of POCl 3 , stir throughout the addition process and keep the temperature at 0°C , control the rate of addition to keep the gas production rate stable, keep the temperature constant after the addition of the dichloromethane solution of 1,4-pentadien-3-ol and continue the reaction until no gas is produced in the system as the end point of the reaction, the HCl gas produced by the reaction is used Absorbed in pure water to obtain hydrochloric acid, which can be sold as an industrial raw material; after the reaction is completed, dichloromethane is removed by distillation at room temperature and atmospheric pressure, and then excess POCl is removed by distillation under reduced pressure at room temperature to obtain a viscous yellow liquid and 1,4- pentadiyne -3-ol dichlorophosphate.

本实施例1,4-戊二炔-3-醇二氟磷酸酯制备方法具体如下:The preparation method of 1,4-pentadiyn-3-alcohol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入40mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,85℃减压蒸馏得到无色液体14.6g,产率为87%。S2: Add 40 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, distill off acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 85°C to obtain 14.6 g of a colorless liquid with a yield of 87%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C5H7O2PF2[M]+为168.14。1HNMR(400MHz,CDCl3)δ:5.89(m,2H),5.29(m,2H),5.28(m,2H),4.96(m,1H);13C NMR(100MHz,CDCl3)δ:139.0,116.4,79.3。证明所得无色液体为1,4-戊二烯-3-醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为21ppm,酸度为27ppm,氯离子浓度为18ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 5 H 7 O 2 PF 2 [M] + is 168.14. 1 H NMR (400MHz, CDCl 3 ) δ: 5.89 (m, 2H), 5.29 (m, 2H), 5.28 (m, 2H), 4.96 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ: 139.0 , 116.4, 79.3. The resulting colorless liquid proved to be 1,4-pentadien-3-ol difluorophosphate. Moisture measured by Karl Fischer moisture analyzer and potentiometric titrator is 21ppm, acidity is 27ppm, and chloride ion concentration is 18ppm.

实施例A2Example A2

本实施例提供一种1,5-己二烯-3-醇二氯磷酸酯、1,5-己二烯-3-醇二氟磷酸酯(上文式2)及其制备方法。This embodiment provides a 1,5-hexadien-3-ol dichlorophosphate, 1,5-hexadien-3-ol difluorophosphate (Formula 2 above) and a preparation method thereof.

本实施例1,5-己二烯-3-醇二氯磷酸酯制备方法具体如下:Present embodiment 1,5-hexadien-3-alcohol dichlorophosphate preparation method is specifically as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入1,5-己二烯-3-醇9.81g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将1,5-己二烯-3-醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,1,5-己二烯-3-醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到1,5-己二烯-3-醇二氯磷酸酯。S1: Add 50mL of dichloromethane to the reaction kettle at room temperature, then add 9.81g (0.1mol) of 1,5-hexadien-3-ol, and stir at room temperature for 0.5h; Mix 50mL with 18g POCl 3 at 0°C; add the dichloromethane solution of 1,5-hexadien-3-ol to the dichloromethane solution of POCl 3 , stir the whole process and keep the temperature at 0°C , control the rate of addition to keep the gas production rate stable, keep the temperature constant after adding the dichloromethane solution of 1,5-hexadien-3-ol and continue the reaction until no gas is generated in the system as the reaction end point, the HCl gas produced by the reaction is used Pure water is absorbed to obtain hydrochloric acid, which can be sold as an industrial raw material; after the reaction is completed, dichloromethane is removed by distillation at room temperature and atmospheric pressure, and then excess POCl is removed by distillation under reduced pressure at room temperature to obtain a viscous yellow liquid, and 1,5 - hexadiene is obtained -3-ol dichlorophosphate.

本实施例1,5-己二烯-3-醇二氟磷酸酯制备方法具体如下:Present embodiment 1,5-hexadien-3-alcohol difluorophosphate preparation method is specifically as follows:

S2:向上述步骤S1中向上述粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,90℃减压蒸馏得到无色液体16.0g,产率为88%。S2: Add 50mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15g of KF to the solution in batches and then raise the temperature to 60°C for 3 hours; no gas is released during the reaction , and then standing and settling to cool to room temperature, filtered under normal pressure to obtain a light yellow solution, distilled off acetonitrile at room temperature and reduced pressure to obtain a yellow liquid, and distilled under reduced pressure at 90°C to obtain 16.0 g of a colorless liquid, with a yield of 88%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C6H9O2PF2[M]+为182.13。1HNMR(400MHz,CDCl3)δ:5.89(m,1H),5.82(m,1H),5.29(m,1H),5.28(m,1H),5.13(d,1H),4.88(d,1H),4.31(m,1H),2.33(m,2H);13C NMR(100MHz,CDCl3)δ:135.7,131.4,119.5,116.4,75.8,40.1。证明所得无色液体为1,5-己二烯-3-醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为17ppm,酸度为26ppm,氯离子浓度为17ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 6 H 9 O 2 PF 2 [M] + is 182.13. 1 HNMR (400MHz, CDCl 3 ) δ: 5.89(m,1H),5.82(m,1H),5.29(m,1H),5.28(m,1H),5.13(d,1H),4.88(d,1H ), 4.31 (m, 1H), 2.33 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ: 135.7, 131.4, 119.5, 116.4, 75.8, 40.1. The resulting colorless liquid proved to be 1,5-hexadien-3-ol difluorophosphate. The moisture measured by the Karl Fischer moisture analyzer and the potentiometric titrator is 17ppm, the acidity is 26ppm, and the chloride ion concentration is 17ppm.

实施例A3Example A3

本实施例提供一种1,6-庚二烯-4-醇二氯磷酸酯、1,6-庚二烯-4-醇二氟磷酸酯(上文式3)及其制备方法。This embodiment provides a 1,6-heptadien-4-ol dichlorophosphate, 1,6-heptadien-4-ol difluorophosphate (Formula 3 above) and a preparation method thereof.

本实施例1,6-庚二烯-4-醇二氯磷酸酯制备方法具体如下:Present embodiment 1,6-heptadien-4-alcohol dichlorophosphate preparation method is specific as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入1,6-庚二烯-4-醇11.2g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将1,6-庚二烯-4-醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,1,6-庚二烯-4-醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到1,6-庚二烯-4-醇二氯磷酸酯。S1: Add 50mL of dichloromethane to the reaction kettle at room temperature, then add 11.2g (0.1mol) of 1,6-heptadien-4-ol, and stir at room temperature for 0.5h; Mix 50mL with 18g POCl 3 at 0°C; add the dichloromethane solution of 1,6-heptadien-4-ol to the dichloromethane solution of POCl 3 , stir throughout the addition process and keep the temperature at 0°C , control the rate of addition to keep the gas production rate stable, keep the temperature constant after adding the dichloromethane solution of 1,6-heptadien-4-ol and continue the reaction until the system has no gas generation as the reaction end point, the HCl gas produced by the reaction is used Pure water is absorbed to obtain hydrochloric acid, which can be sold as an industrial raw material; after the reaction is completed, dichloromethane is removed by distillation at room temperature and atmospheric pressure, and then excess POCl is removed by distillation under reduced pressure at room temperature to obtain a viscous yellow liquid and 1,6 - heptadiene -4-ol dichlorophosphate.

本实施例1,6-庚二烯-4-醇二氟磷酸酯制备方法具体如下:Present embodiment 1,6-heptadien-4-alcohol difluorophosphate preparation method is specifically as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,90℃减压蒸馏得到无色液体17.5g,产率为89%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, distill off acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 90°C to obtain 17.5 g of a colorless liquid with a yield of 89%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C7H11O2PF2[M]+为196.15。1HNMR(400MHz,CDCl3)δ:5.82(m,2H),5.13(d,2H),4.88(d,2H),3.66(m,1H),2.27(m,4H);13CNMR(100MHz,CDCl3)δ:132.5,115.8,72.3,39.2。证明所得无色液体为1,6-庚二烯-4-醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为20ppm,酸度为28ppm,氯离子浓度为18ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 7 H 11 O 2 PF 2 [M] + is 196.15. 1 HNMR (400MHz, CDCl 3 ) δ: 5.82 (m, 2H), 5.13 (d, 2H), 4.88 (d, 2H), 3.66 (m, 1H), 2.27 (m, 4H); 13 CNMR (100MHz, CDCl 3 ) δ: 132.5, 115.8, 72.3, 39.2. The resulting colorless liquid proved to be 1,6-heptadien-4-ol difluorophosphate. Moisture measured by Karl Fischer moisture meter and potentiometric titrator is 20ppm, acidity is 28ppm, and chloride ion concentration is 18ppm.

实施例A4Example A4

本实施例提供一种2,4,6-三甲基-1,6-庚二烯-4-醇二氯磷酸酯、2,4,6-三甲基-1,6-庚二烯-4-醇二氟磷酸酯(上文式4)及其制备方法。This example provides a kind of 2,4,6-trimethyl-1,6-heptadien-4-ol dichlorophosphate, 2,4,6-trimethyl-1,6-heptadiene- 4-Alcohol difluorophosphates (Formula 4 above) and methods for their preparation.

本实施例2,4,6-三甲基-1,6-庚二烯-4-醇二氯磷酸酯制备方法具体如下:The preparation method of 2,4,6-trimethyl-1,6-heptadien-4-ol dichlorophosphate in this embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入2,4,6-三甲基-1,6-庚二烯-4-醇15.4g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将2,4,6-三甲基-1,6-庚二烯-4-醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,2,4,6-三甲基-1,6-庚二烯-4-醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到2,4,6-三甲基-1,6-庚二烯-4-醇二氯磷酸酯。S1: Add 50 mL of dichloromethane to the reaction kettle at room temperature, then add 15.4 g (0.1 mol) of 2,4,6-trimethyl-1,6-heptadien-4-ol, and stir at room temperature for 0.5 h; In another reactor, mix 50mL of dichloromethane and 18g of POCl 3 at 0°C; add the dichloromethane solution of 2,4,6-trimethyl-1,6-heptadien-4-ol To the dichloromethane solution of POCl 3 , stirring throughout the addition process and keeping the temperature at 0°C, controlling the rate of addition to keep the gas production rate stable, 2,4,6-trimethyl-1,6-heptadiene-4- After adding the dichloromethane solution of alcohol, keep the temperature constant and continue to react until the system has no gas generation as the reaction end point. The HCl gas generated by the reaction is absorbed by pure water to obtain hydrochloric acid, which can be sold as industrial raw materials; after the reaction is completed, distill at room temperature and atmospheric pressure Dichloromethane was removed, and excess POCl3 was distilled off under reduced pressure at room temperature to obtain a viscous yellow liquid to obtain 2,4,6-trimethyl-1,6-heptadien-4-ol dichlorophosphate.

本实施例2,4,6-三甲基-1,6-庚二烯-4-醇二氟磷酸酯制备方法具体如下:The preparation method of 2,4,6-trimethyl-1,6-heptadien-4-ol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中向上述粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,95℃减压蒸馏得到无色液体21.4g,产率为90%。S2: Add 50mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15g of KF to the solution in batches and then raise the temperature to 60°C for 3 hours; no gas is released during the reaction , and then standing and settling to cool to room temperature and then filtering under normal pressure to obtain a light yellow solution, distilling off acetonitrile at room temperature and under reduced pressure to obtain a yellow liquid, and distilling under reduced pressure at 95°C to obtain 21.4 g of a colorless liquid with a yield of 90%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C10H17O2PF2[M]+为238.23。1HNMR(400MHz,CDCl3)δ:5.11(d,2H),4.92(d,2H),2.21(s,4H),1.79(s,6H),1.30(s,3H);13CNMR(100MHz,CDCl3)δ:141.1,114.7,66.3,51.4,25.2,22.8。证明所得无色液体为2,4,6-三甲基-1,6-庚二烯-4-醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为22ppm,酸度为31ppm,氯离子浓度为21ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, the analysis result shows that GC-MS (ESI) calcd for C 10 H 17 O 2 PF 2 [M] + is 238.23. 1 HNMR (400MHz, CDCl 3 ) δ: 5.11 (d, 2H), 4.92 (d, 2H), 2.21 (s, 4H), 1.79 (s, 6H), 1.30 (s, 3H); 13 CNMR (100MHz, CDCl 3 ) δ: 141.1, 114.7, 66.3, 51.4, 25.2, 22.8. The obtained colorless liquid proved to be 2,4,6-trimethyl-1,6-heptadien-4-ol difluorophosphate. The moisture measured by the Karl Fischer moisture analyzer and the potentiometric titrator is 22ppm, the acidity is 31ppm, and the chloride ion concentration is 21ppm.

实施例A5Example A5

本实施例提供一种2,5-二甲基-1,5-己二烯-3-醇二氯磷酸酯、2,5-二甲基-1,5-己二烯-3-醇二氟磷酸酯(上文式5)及其制备方法。This embodiment provides a kind of 2,5-dimethyl-1,5-hexadien-3-ol dichlorophosphate, 2,5-dimethyl-1,5-hexadien-3-ol dichlorophosphate Fluorophosphate esters (Formula 5 above) and methods for their preparation.

本实施例2,5-二甲基-1,5-己二烯-3-醇二氯磷酸酯制备方法具体如下:The preparation method of 2,5-dimethyl-1,5-hexadien-3-ol dichlorophosphate in this embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入2,5-二甲基-1,5-己二烯-3-醇12.6g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将2,5-二甲基-1,5-己二烯-3-醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,2,5-二甲基-1,5-己二烯-3-醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到2,5-二甲基-1,5-己二烯-3-醇二氯磷酸酯。S1: Add 50 mL of dichloromethane to the reaction kettle at room temperature, then add 12.6 g (0.1 mol) of 2,5-dimethyl-1,5-hexadien-3-ol, and stir at room temperature for 0.5 h; Mix 50mL of dichloromethane and 18g of POCl 3 in a reaction kettle at 0°C; add the dichloromethane solution of 2,5-dimethyl-1,5-hexadien- 3 -ol to the In dichloromethane solution, stir throughout the addition process and keep the temperature at 0°C, control the rate of addition to keep the gas production rate stable, dichloromethane solution of 2,5-dimethyl-1,5-hexadien-3-ol After the addition, keep the temperature constant and continue to react until the system has no gas generation as the reaction end point. The HCl gas produced by the reaction is absorbed by pure water to obtain hydrochloric acid, which can be sold as industrial raw materials; after the reaction is completed, methylene chloride is removed by distillation at room temperature and atmospheric pressure, and then Excess POCl3 was distilled off under reduced pressure at room temperature to obtain viscous yellow liquid, and 2,5-dimethyl-1,5-hexadien-3-ol dichlorophosphate was obtained.

本实施例2,5-二甲基-1,5-己二烯-3-醇二氟磷酸酯制备方法具体如下:The preparation method of 2,5-dimethyl-1,5-hexadien-3-ol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,95℃减压蒸馏得到无色液体18.5g,产率为88%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, remove acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 95°C to obtain 18.5 g of a colorless liquid with a yield of 88%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C8H13O2PF2[M]+为210.23。1HNMR(400MHz,CDCl3)δ:5.32(d,1H),5.18(d,1H),5.11(d,1H),4.92(d,1H),4.31(m,1H),2.46(m,2H),1.79(s,6H);13C NMR(100MHz,CDCl3)δ:143.8,142.5,112.3,111.3,77.9,42.1,22.6,17.3。证明所得无色液体为2,5-二甲基-1,5-己二烯-3-醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为22ppm,酸度为28ppm,氯离子浓度为18ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 8 H 13 O 2 PF 2 [M] + is 210.23. 1 HNMR (400MHz, CDCl 3 )δ: 5.32(d,1H),5.18(d,1H),5.11(d,1H),4.92(d,1H),4.31(m,1H),2.46(m,2H ), 1.79 (s, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ: 143.8, 142.5, 112.3, 111.3, 77.9, 42.1, 22.6, 17.3. The resulting colorless liquid proved to be 2,5-dimethyl-1,5-hexadien-3-ol difluorophosphate. Moisture measured by Karl Fischer moisture analyzer and potentiometric titrator is 22ppm, acidity is 28ppm, and chloride ion concentration is 18ppm.

实施例A6Example A6

本实施例提供一种三烯丙基甲醇二氯磷酸酯、三烯丙基甲醇二氟磷酸酯(上文式6)及其制备方法。This embodiment provides triallylmethanol dichlorophosphate, triallylmethanol difluorophosphate (Formula 6 above) and a preparation method thereof.

本实施例三烯丙基甲醇二氯磷酸酯制备方法具体如下:The preparation method of triallylmethanol dichlorophosphate of the present embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入三烯丙基甲醇15.2g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将三烯丙基甲醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,三烯丙基甲醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到三烯丙基甲醇二氯磷酸酯。S1: Add 50mL of dichloromethane to the reaction kettle at room temperature, then add 15.2g (0.1mol) of triallylmethanol, and stir at room temperature for 0.5h; in another reaction kettle, add 50mL of dichloromethane and 18g POCl Mix at 0°C; add the dichloromethane solution of triallylmethanol to the dichloromethane solution of POCl3, stir throughout the addition process and keep the temperature at 0°C, control the rate of addition to keep the gas production rate stable, triallyl After the addition of the dichloromethane solution of base methanol, keep the temperature constant and continue the reaction until no gas is produced in the system. Dichloromethane was distilled off, and then excess POCl was distilled off under reduced pressure at room temperature to obtain a viscous yellow liquid, and triallylmethanol dichlorophosphate was obtained.

本实施例三烯丙基甲醇二氟磷酸酯制备方法具体如下:The preparation method of triallylmethanol difluorophosphate of the present embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,110℃减压蒸馏得到无色液体20.5g,产率为87%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, distill off acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 110°C to obtain 20.5 g of a colorless liquid with a yield of 87%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C10H15O2PF2[M]+为236.24。1HNMR(400MHz,CDCl3)δ:5.82(m,3H),5.13(d,3H),4.88(d,3H),2.21(d,6H);13C NMR(100MHz,CDCl3)δ:131.4,118.5,71.7,41.4。证明所得无色液体为三烯丙基甲醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为21ppm,酸度为28ppm,氯离子浓度为17ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, the analysis result shows that GC-MS (ESI) calcd for C 10 H 15 O 2 PF 2 [M] + is 236.24. 1 HNMR (400MHz, CDCl 3 ) δ: 5.82(m, 3H), 5.13(d, 3H), 4.88(d, 3H), 2.21(d, 6H); 13 C NMR (100MHz, CDCl 3 ) δ: 131.4 , 118.5, 71.7, 41.4. The obtained colorless liquid was proved to be triallylmethanol difluorophosphate. The moisture measured by the Karl Fischer moisture analyzer and the potentiometric titrator is 21ppm, the acidity is 28ppm, and the chloride ion concentration is 17ppm.

实施例A7Example A7

本实施例提供一种1,4-戊二炔-3-醇二氯磷酸酯、1,4-戊二炔-3-醇二氟磷酸酯(上文式7)及其制备方法。This embodiment provides a 1,4-pentadiyn-3-ol dichlorophosphate, 1,4-pentadiyn-3-ol difluorophosphate (Formula 7 above) and a preparation method thereof.

本实施例1,4-戊二炔-3-醇二氯磷酸酯制备方法具体如下:Present embodiment 1,4-pentadiyn-3-alcohol dichlorophosphate preparation method is specifically as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入1,4-戊二炔-3-醇8g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将1,4-戊二炔-3-醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,1,4-戊二炔-3-醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到1,4-戊二炔-3-醇二氯磷酸酯。S1: Add 50mL of dichloromethane to the reaction kettle at room temperature, then add 8g (0.1mol) of 1,4-pentadiyn-3-ol, and stir at room temperature for 0.5h; add 50mL of dichloromethane to another reaction kettle Mix with 18g POCl 3 at 0°C; add the dichloromethane solution of 1,4-pentadiyn-3-ol to the dichloromethane solution of POCl 3 , stir throughout the addition process and keep the temperature at 0°C, Control the rate of addition to keep the rate of gas production stable. After adding the dichloromethane solution of 1,4-pentadiyn-3-ol, keep the temperature constant and continue the reaction until no gas is produced in the system. Absorbed in water to obtain hydrochloric acid, which can be sold as an industrial raw material; after the reaction is completed, dichloromethane is removed by distillation at room temperature and pressure, and then excess POCl is removed by distillation under reduced pressure at room temperature to obtain a viscous yellow liquid, and 1,4- pentadiyne- 3-Alkyl dichlorophosphate.

本实施例1,4-戊二炔-3-醇二氟磷酸酯制备方法具体如下:The preparation method of 1,4-pentadiyn-3-alcohol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,85℃减压蒸馏得到无色液体14.6g,产率为89%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, remove acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 85°C to obtain 14.6 g of a colorless liquid with a yield of 89%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C5H3O2PF2[M]+为164.12。1HNMR(400MHz,CDCl3)δ:5.68(m,1H),3.61(d,2H);13C NMR(100MHz,CDCl3)δ:80.4,72.8,59.7。证明所得无色液体为1,4-戊二炔-3-醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为18ppm,酸度为22ppm,氯离子浓度为16ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 5 H 3 O 2 PF 2 [M] + is 164.12. 1 H NMR (400 MHz, CDCl 3 ) δ: 5.68 (m, 1H), 3.61 (d, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ: 80.4, 72.8, 59.7. The resulting colorless liquid proved to be 1,4-pentadiyn-3-ol difluorophosphate. Moisture measured by Karl Fischer moisture analyzer and potentiometric titrator is 18ppm, acidity is 22ppm, and chloride ion concentration is 16ppm.

实施例A8Example A8

本实施例提供一种1-己烯-5-炔-3-醇二氯磷酸酯、1-己烯-5-炔-3-醇二氟磷酸酯(上文式8)及其制备方法。This embodiment provides a 1-hexen-5-yn-3-ol dichlorophosphate, 1-hexen-5-yn-3-ol difluorophosphate (formula 8 above) and a preparation method thereof.

本实施例1-己烯-5-炔-3-醇二氯磷酸酯制备方法具体如下:The preparation method of 1-hexene-5-yn-3-alcohol dichlorophosphate in this embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入1-己烯-5-炔-3-醇9.6g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将1-己烯-5-炔-3-醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,1-己烯-5-炔-3-醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到1-己烯-5-炔-3-醇二氯磷酸酯。S1: Add 50mL of dichloromethane to the reaction kettle at room temperature, then add 9.6g (0.1mol) of 1-hexen-5-yn-3-ol, and stir at room temperature for 0.5h; Mix 50mL of methane with 18g of POCl 3 at 0°C; add the dichloromethane solution of 1-hexen-5-yn-3-ol to the dichloromethane solution of POCl 3 , stir the whole process and keep the temperature at 0°C, control the rate of addition to keep the rate of gas production stable, keep the temperature constant after adding the dichloromethane solution of 1-hexene-5-yn-3-ol, and continue the reaction until no gas is produced in the system. HCl gas is absorbed by pure water to obtain hydrochloric acid, which can be sold as an industrial raw material; after the reaction is completed, dichloromethane is removed by distillation at room temperature and atmospheric pressure, and then excess POCl is removed by distillation under reduced pressure at room temperature to obtain a viscous yellow liquid and 1 -hexene -5-yn-3-ol dichlorophosphate.

本实施例1-己烯-5-炔-3-醇二氟磷酸酯制备方法具体如下:The preparation method of 1-hexene-5-yn-3-alcohol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,90℃减压蒸馏得到无色液体15.8g,产率为88%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, distill off acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 90°C to obtain 15.8 g of a colorless liquid with a yield of 88%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C6H7O2PF2[M]+为180.12。1HNMR(400MHz,CDCl3)δ:5.89(m,1H),5.29(m,1H),5.28(m,1H),4.30(m,1H),3.06(m,1H),2.52(m,2H);13C NMR(100MHz,CDCl3)δ:135.7,116.4,86.2,74.5,69.7,32.8。证明所得无色液体为1-己烯-5-炔-3-醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为22ppm,酸度为26ppm,氯离子浓度为17ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 6 H 7 O 2 PF 2 [M] + is 180.12. 1 HNMR (400MHz, CDCl 3 ) δ: 5.89(m,1H),5.29(m,1H),5.28(m,1H),4.30(m,1H),3.06(m,1H),2.52(m,2H ); 13 C NMR (100MHz, CDCl 3 ) δ: 135.7, 116.4, 86.2, 74.5, 69.7, 32.8. The resulting colorless liquid proved to be 1-hexen-5-yn-3-ol difluorophosphate. Moisture measured by Karl Fischer moisture meter and potentiometric titrator is 22ppm, acidity is 26ppm, and chloride ion concentration is 17ppm.

实施例A9Example A9

本实施例提供一种乙烯基六氟异丙醇二氯磷酸酯、乙烯基六氟异丙醇二氟磷酸酯(上文式9)及其制备方法。This embodiment provides a vinyl hexafluoroisopropanol dichlorophosphate, vinyl hexafluoroisopropanol difluorophosphate (formula 9 above) and a preparation method thereof.

本实施例乙烯基六氟异丙醇二氯磷酸酯制备方法具体如下:The preparation method of vinyl hexafluoroisopropanol dichlorophosphate in this embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入乙烯基六氟异丙醇19.4g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将乙烯基六氟异丙醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,乙烯基六氟异丙醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到乙烯基六氟异丙醇二氯磷酸酯。S1: Add 50mL of dichloromethane to the reaction kettle at room temperature, then add 19.4g (0.1mol) of vinyl hexafluoroisopropanol, and stir at room temperature for 0.5h; in another reaction kettle, add 50mL of dichloromethane and 18g POCl 3 Mix at 0°C; add the dichloromethane solution of vinyl hexafluoroisopropanol to the dichloromethane solution of POCl 3 , stir throughout the addition process and keep the temperature at 0°C, and control the rate of addition to maintain the gas production rate Stable, after adding the dichloromethane solution of vinyl hexafluoroisopropanol, keep the temperature constant and continue the reaction until no gas is produced in the system. Dichloromethane was removed by distillation at room temperature and normal pressure after the reaction was completed, and then excess POCl was removed by distillation under reduced pressure at room temperature to obtain a viscous yellow liquid, and to obtain vinyl hexafluoroisopropanol dichlorophosphate.

本实施例乙烯基六氟异丙醇二氟磷酸酯制备方法具体如下:The preparation method of vinyl hexafluoroisopropanol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,85℃减压蒸馏得到无色液体25.6g,产率为92%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, remove acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 85°C to obtain 25.6 g of a colorless liquid with a yield of 92%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C5H3O2PF8[M]+为278.06。1HNMR(400MHz,CDCl3)δ:5.89(m,1H),5.29(m,1H),5.28(m,1H),13C NMR(100MHz,CDCl3)δ:145.7,124.4,109.5,99.2。证明所得无色液体为乙烯基六氟异丙醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为20ppm,酸度为22ppm,氯离子浓度为17ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 5 H 3 O 2 PF 8 [M] + is 278.06. 1 H NMR (400MHz, CDCl 3 ) δ: 5.89 (m, 1H), 5.29 (m, 1H), 5.28 (m, 1H), 13 C NMR (100 MHz, CDCl 3 ) δ: 145.7, 124.4, 109.5, 99.2. The obtained colorless liquid was proved to be vinyl hexafluoroisopropanol difluorophosphate. Moisture measured by Karl Fischer moisture meter and potentiometric titrator is 20ppm, acidity is 22ppm, and chloride ion concentration is 17ppm.

实施例A10Example A10

本实施例提供一种乙炔基六氟异丙醇二氯磷酸酯、乙炔基六氟异丙醇二氟磷酸酯(上文式10)及其制备方法。This embodiment provides ethynyl hexafluoroisopropanol dichlorophosphate, ethynyl hexafluoroisopropanol difluorophosphate (formula 10 above) and a preparation method thereof.

本实施例乙炔基六氟异丙醇二氯磷酸酯制备方法具体如下:The preparation method of ethynyl hexafluoroisopropanol dichlorophosphate in this embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入乙炔基六氟异丙醇19.2g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将乙炔基六氟异丙醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,乙炔基六氟异丙醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到乙炔基六氟异丙醇二氯磷酸酯。S1: Add 50 mL of dichloromethane to the reactor at room temperature, then add 19.2 g (0.1 mol) of ethynyl hexafluoroisopropanol, and stir at room temperature for 0.5 h; in another reactor, add 50 mL of dichloromethane and 18 g of POCl 3 Mix at 0°C; add the dichloromethane solution of ethynyl hexafluoroisopropanol to the dichloromethane solution of POCl 3 , stir throughout the addition process and keep the temperature at 0°C, and control the rate of addition to maintain the gas production rate Stable, after adding the dichloromethane solution of ethynyl hexafluoroisopropanol, keep the temperature constant and continue the reaction until no gas is generated in the system. Dichloromethane was removed by distillation at room temperature and atmospheric pressure after the reaction was completed, and then excess POCl was removed by distillation under reduced pressure at room temperature to obtain a viscous yellow liquid, which obtained ethynyl hexafluoroisopropanol dichlorophosphate.

本实施例乙炔基六氟异丙醇二氟磷酸酯制备方法具体如下:The preparation method of ethynyl hexafluoroisopropanol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,90℃减压蒸馏得到无色液体24.8g,产率为90%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, remove acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 90°C to obtain 24.8 g of a colorless liquid with a yield of 90%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C5HO2PF8[M]+为276.05。1H NMR(400MHz,CDCl3)δ:3.61(s,1H);13C NMR(100MHz,CDCl3)δ:103.1,93.7,88.3,72.1。证明所得无色液体为乙炔基六氟异丙醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为18ppm,酸度为26ppm,氯离子浓度为18ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 5 HO 2 PF 8 [M] + is 276.05. 1 H NMR (400 MHz, CDCl 3 ) δ: 3.61 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ: 103.1, 93.7, 88.3, 72.1. It was proved that the obtained colorless liquid was ethynyl hexafluoroisopropanol difluorophosphate. The moisture measured by the Karl Fischer moisture analyzer and the potentiometric titrator is 18ppm, the acidity is 26ppm, and the chloride ion concentration is 18ppm.

实施例A11Example A11

本实施例提供一种烯丙基六氟异丙醇二氯磷酸酯、烯丙基六氟异丙醇二氟磷酸酯(上文式11)及其制备方法。This embodiment provides an allyl hexafluoroisopropanol dichlorophosphate, allyl hexafluoroisopropanol difluorophosphate (formula 11 above) and a preparation method thereof.

本实施例烯丙基六氟异丙醇二氯磷酸酯制备方法具体如下:The preparation method of allyl hexafluoroisopropanol dichlorophosphate in this embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入烯丙基六氟异丙醇20.8g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将烯丙基六氟异丙醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,烯丙基六氟异丙醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到烯丙基六氟异丙醇二氯磷酸酯。S1: Add 50mL of dichloromethane to the reaction kettle at room temperature, then add 20.8g (0.1mol) of allyl hexafluoroisopropanol, and stir at room temperature for 0.5h; in another reaction kettle, add 50mL of dichloromethane and 18g Mix POCl 3 at 0°C; add the dichloromethane solution of allyl hexafluoroisopropanol to the dichloromethane solution of POCl 3 , stir throughout the addition process and keep the temperature at 0°C, and control the rate of addition to maintain the yield. The gas velocity is stable. After adding the dichloromethane solution of allyl hexafluoroisopropanol, keep the temperature constant and continue the reaction until the system has no gas generation as the reaction end point. The HCl gas generated by the reaction is absorbed by pure water to obtain hydrochloric acid. Industrial raw materials are sold; after the reaction is completed, dichloromethane is distilled off at room temperature and under normal pressure, and then excess POCl is distilled off under reduced pressure at room temperature to obtain a viscous yellow liquid, and allyl hexafluoroisopropanol dichlorophosphate is obtained.

本实施例烯丙基六氟异丙醇二氟磷酸酯制备方法具体如下:The preparation method of allyl hexafluoroisopropanol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中向上述粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,90℃减压蒸馏得到无色液体25.7g,产率为88%。S2: Add 50mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15g of KF to the solution in batches and then raise the temperature to 60°C for 3 hours; no gas is released during the reaction , then left to settle and cool to room temperature, filtered under normal pressure to obtain a light yellow solution, distilled off acetonitrile at room temperature and reduced pressure to obtain a yellow liquid, and distilled under reduced pressure at 90° C. to obtain 25.7 g of a colorless liquid, with a yield of 88%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示LC-MS(ESI)calcd for C6H5O2PF8[M]+为292.14。1HNMR(400MHz,CDCl3)δ:5.82(m,1H),5.13(d,1H),4.88(d,1H),2.21(d,2H),13C NMR(100MHz,CDCl3)δ:131.4,118.7,118.5,95.7,4.8。证明所得无色液体为烯丙基六氟异丙醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为22ppm,酸度为25ppm,氯离子浓度为17ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, the analysis result showed that LC-MS (ESI) calcd for C 6 H 5 O 2 PF 8 [M] + was 292.14. 1 H NMR (400MHz, CDCl 3 ) δ: 5.82(m, 1H), 5.13(d, 1H), 4.88(d, 1H), 2.21(d, 2H), 13 C NMR (100MHz, CDCl 3 ) δ: 131.4 , 118.7, 118.5, 95.7, 4.8. The obtained colorless liquid was proved to be allyl hexafluoroisopropanol difluorophosphate. Moisture measured by Karl Fischer moisture analyzer and potentiometric titrator is 22ppm, acidity is 25ppm, and chloride ion concentration is 17ppm.

实施例A12Example A12

本实施例提供一种炔丙基六氟异丙醇二氯磷酸酯、炔丙基六氟异丙醇二氟磷酸酯(上文式12)及其制备方法。This embodiment provides propargyl hexafluoroisopropanol dichlorophosphate, propargyl hexafluoroisopropanol difluorophosphate (formula 12 above) and a preparation method thereof.

本实施例炔丙基六氟异丙醇二氯磷酸酯制备方法具体如下:The preparation method of propargyl hexafluoroisopropanol dichlorophosphate in this embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入炔丙基六氟异丙醇20.6g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将炔丙基六氟异丙醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,炔丙基六氟异丙醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到炔丙基六氟异丙醇二氯磷酸酯。S1: Add 50 mL of dichloromethane to the reactor at room temperature, then add 20.6 g (0.1 mol) of propargyl hexafluoroisopropanol, and stir at room temperature for 0.5 h; in another reactor, add 50 mL of dichloromethane and 18 g POCl 3 was mixed at 0°C; the dichloromethane solution of propargyl hexafluoroisopropanol was added to the dichloromethane solution of POCl 3 , the whole process of adding was stirred and the temperature was kept at 0°C, and the rate of addition was controlled to maintain the production rate. The gas velocity is stable. After adding the dichloromethane solution of propargyl hexafluoroisopropanol, keep the temperature constant and continue the reaction until no gas is generated in the system. Industrial raw materials are sold; after the reaction is completed, dichloromethane is distilled off at room temperature and under normal pressure, and then excess POCl is distilled off under reduced pressure at room temperature to obtain a viscous yellow liquid, and propargyl hexafluoroisopropanol dichlorophosphate is obtained.

本实施例炔丙基六氟异丙醇二氟磷酸酯制备方法具体如下:The preparation method of propargyl hexafluoroisopropanol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,90℃减压蒸馏得到无色液体25.5g,产率为88%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, remove acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 90°C to obtain 25.5 g of a colorless liquid with a yield of 88%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示LC-MS(ESI)calcd for C6H3O2PF8[M]+为290.06。1HNMR(400MHz,CDCl3)δ:3.06(t,1H),2.28(d,2H),13C NMR(100MHz,CDCl3)δ:117.4,94.4,82.7,71.3,-7.6。证明所得无色液体为炔丙基六氟异丙醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为25ppm,酸度为28ppm,氯离子浓度为21ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, the analysis result showed that LC-MS (ESI) calcd for C 6 H 3 O 2 PF 8 [M] + was 290.06. 1 H NMR (400 MHz, CDCl 3 ) δ: 3.06 (t, 1H), 2.28 (d, 2H), 13 C NMR (100 MHz, CDCl 3 ) δ: 117.4, 94.4, 82.7, 71.3, -7.6. The obtained colorless liquid was proved to be propargyl hexafluoroisopropanol difluorophosphate. Moisture measured by Karl Fischer moisture analyzer and potentiometric titrator is 25ppm, acidity is 28ppm, and chloride ion concentration is 21ppm.

实施例A13Example A13

本实施例提供一种五氟苄醇二氯磷酸酯、五氟苄醇二氟磷酸酯(上文式13)及其制备方法。This embodiment provides a pentafluorobenzyl alcohol dichlorophosphate, pentafluorobenzyl alcohol difluorophosphate (formula 13 above) and a preparation method thereof.

本实施例五氟苄醇二氯磷酸酯制备方法具体如下:The preparation method of pentafluorobenzyl alcohol dichlorophosphate of the present embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入五氟苄醇19.8g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将五氟苄醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,五氟苄醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到五氟苄醇二氯磷酸酯。S1: Add 50mL of dichloromethane to the reaction kettle at room temperature, then add 19.8g (0.1mol) of pentafluorobenzyl alcohol, and stir at room temperature for 0.5h; in another reaction kettle, add 50mL of dichloromethane and 18g POCl Mix under the condition of ℃; add the dichloromethane solution of pentafluorobenzyl alcohol into the dichloromethane solution of POCl3 , stir the whole process of adding and keep the temperature at 0 ℃, control the dropping speed to keep the gas production rate stable, pentafluorobenzyl alcohol After the dichloromethane solution is added, keep the temperature constant and continue to react until the system has no gas generation as the end point of the reaction. The HCl gas generated by the reaction is absorbed by pure water to obtain hydrochloric acid, which can be sold as industrial raw materials; after the reaction is completed, it is removed by distillation at room temperature and normal pressure. Dichloromethane, then distilled off excess POCl at room temperature under reduced pressure to obtain a viscous yellow liquid, giving pentafluorobenzyl alcohol dichlorophosphate.

本实施例五氟苄醇二氟磷酸酯制备方法具体如下:The preparation method of pentafluorobenzyl alcohol difluorophosphate of the present embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,115℃减压蒸馏得到无色液体25.7g,产率为91%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, distill off acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 115°C to obtain 25.7 g of a colorless liquid with a yield of 91%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示LC-MS(ESI)calcd for C7H2O2PF7[M]+为282.15。1HNMR(400MHz,CDCl3)δ:5.29(d,2H);13C NMR(100MHz,CDCl3)δ:145.2,142.2,136.4,113.7,54.0。证明所得无色液体为五氟苄醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为20ppm,酸度为25ppm,氯离子浓度为18ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, the analysis result showed that LC-MS (ESI) calcd for C 7 H 2 O 2 PF 7 [M] + was 282.15. 1 H NMR (400 MHz, CDCl 3 ) δ: 5.29 (d, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ: 145.2, 142.2, 136.4, 113.7, 54.0. The obtained colorless liquid was proved to be pentafluorobenzyl alcohol difluorophosphate. Moisture measured by Karl Fischer moisture analyzer and potentiometric titrator is 20ppm, acidity is 25ppm, and chloride ion concentration is 18ppm.

实施例A14Example A14

本实施例提供一种1-五氟苯基炔丙醇二氯磷酸酯、1-五氟苯基炔丙醇二氟磷酸酯(上文式14)及其制备方法。This embodiment provides 1-pentafluorophenyl propargyl alcohol dichlorophosphate, 1-pentafluorophenyl propargyl alcohol difluorophosphate (formula 14 above) and a preparation method thereof.

本实施例1-五氟苯基炔丙醇二氯磷酸酯制备方法具体如下:The preparation method of the present embodiment 1-pentafluorophenyl propargyl alcohol dichlorophosphate is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入1-五氟苯基炔丙醇22.2g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将1-五氟苯基炔丙醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,1-五氟苯基炔丙醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到1-五氟苯基炔丙醇二氯磷酸酯;S1: Add 50mL of dichloromethane to the reaction kettle at room temperature, then add 22.2g (0.1mol) of 1-pentafluorophenyl propargyl alcohol, and stir at room temperature for 0.5h; in another reaction kettle, add 50mL of dichloromethane and Mix 18g of POCl 3 at 0°C; add the dichloromethane solution of 1-pentafluorophenyl propargyl alcohol to the dichloromethane solution of POCl 3 , stir throughout the addition process and keep the temperature at 0°C, and control the rate of addition Keep the gas production rate stable. After adding the dichloromethane solution of 1-pentafluorophenyl propargyl alcohol, keep the temperature constant and continue the reaction until the system has no gas generation as the reaction end point. The HCl gas generated by the reaction is absorbed by pure water to obtain hydrochloric acid. Hydrochloric acid can be sold as an industrial raw material; after the reaction is completed, dichloromethane is removed by distillation at room temperature and atmospheric pressure, and then excess POCl is removed by distillation under reduced pressure at room temperature to obtain a viscous yellow liquid, and 1 -pentafluorophenyl propargyl alcohol dichlorophosphate ;

本实施例1-五氟苯基炔丙醇二氟磷酸酯制备方法具体如下:The preparation method of the present embodiment 1-pentafluorophenyl propargyl alcohol difluorophosphate is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,125℃减压蒸馏得到无色液体26.9g,产率为88%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, distill off acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 125°C to obtain 26.9 g of a colorless liquid with a yield of 88%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C9H2O2PF7[M]+为306.16。1HNMR(400MHz,CDCl3)δ:5.92(m,1H),3.61(d,1H);13C NMR(100MHz,CDCl3)δ:145.2,142.2,136.4,113.7,83.6,74.9,55.9。证明所得无色液体为1-五氟苯基炔丙醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为22ppm,酸度为28ppm,氯离子浓度为18ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 9 H 2 O 2 PF 7 [M] + is 306.16. 1 H NMR (400MHz, CDCl 3 ) δ: 5.92 (m, 1H), 3.61 (d, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ: 145.2, 142.2, 136.4, 113.7, 83.6, 74.9, 55.9. It was proved that the obtained colorless liquid was 1-pentafluorophenylpropargyl difluorophosphate. Moisture measured by Karl Fischer moisture analyzer and potentiometric titrator is 22ppm, acidity is 28ppm, and chloride ion concentration is 18ppm.

实施例A15Example A15

本实施例提供一种1-五氟苯基烯丙醇二氯磷酸酯、1-五氟苯基烯丙醇二氟磷酸酯(上文式15)及其制备方法。This embodiment provides 1-pentafluorophenyl allyl alcohol dichlorophosphate, 1-pentafluorophenyl allyl alcohol difluorophosphate (formula 15 above) and a preparation method thereof.

本实施例1-五氟苯基烯丙醇二氯磷酸酯制备方法具体如下:The preparation method of the present embodiment 1-pentafluorophenyl allyl alcohol dichlorophosphate is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入1-五氟苯基烯丙醇22.4g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将1-五氟苯基烯丙醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,1-五氟苯基烯丙醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到1-五氟苯基烯丙醇二氯磷酸酯;S1: Add 50mL of dichloromethane to the reaction kettle at room temperature, then add 22.4g (0.1mol) of 1-pentafluorophenyl allyl alcohol, and stir at room temperature for 0.5h; in another reaction kettle, add 50mL of dichloromethane and Mix 18g of POCl 3 at 0°C; add the dichloromethane solution of 1-pentafluorophenyl allyl alcohol to the dichloromethane solution of POCl 3 , stir throughout the addition process and keep the temperature at 0°C, and control the rate of addition Keep the gas production rate stable. After adding the dichloromethane solution of 1-pentafluorophenyl allyl alcohol, keep the temperature constant and continue the reaction until no gas is generated in the system as the reaction end point. The HCl gas generated by the reaction is absorbed by pure water to obtain hydrochloric acid. Hydrochloric acid can be sold as an industrial raw material; after the reaction is completed, dichloromethane is removed by distillation at room temperature and atmospheric pressure, and then excess POCl is removed by distillation under reduced pressure at room temperature to obtain a viscous yellow liquid, and 1 -pentafluorophenyl allyl alcohol dichlorophosphate ;

本实施例1-五氟苯基烯丙醇二氟磷酸酯制备方法具体如下:The preparation method of the present embodiment 1-pentafluorophenyl allyl alcohol difluorophosphate is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,125℃减压蒸馏得到无色液体26.8g,产率为87%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, remove acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 125°C to obtain 26.8 g of a colorless liquid with a yield of 87%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C9H4O2PF7[M]+为308.15。1HNMR(400MHz,CDCl3)δ:6.30(m,1H),5.56(m,1H),5.00(m,1H),4.99(m,1H);13C NMR(100MHz,CDCl3)δ:145.2,142.2,138.6,136.4,116.4,113.7,65.7。证明所得无色液体为1-五氟苯基烯丙醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为20ppm,酸度为27ppm,氯离子浓度为18ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 9 H 4 O 2 PF 7 [M] + is 308.15. 1 HNMR (400MHz, CDCl 3 ) δ: 6.30 (m, 1H), 5.56 (m, 1H), 5.00 (m, 1H), 4.99 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ: 145.2 , 142.2, 138.6, 136.4, 116.4, 113.7, 65.7. It was proved that the obtained colorless liquid was 1-pentafluorophenyl allyl alcohol difluorophosphate. The moisture measured by the Karl Fischer moisture analyzer and the potentiometric titrator is 20ppm, the acidity is 27ppm, and the chloride ion concentration is 18ppm.

实施例A16Example A16

本实施例提供一种(1-五氟苯基)3-丁炔-1-醇二氯磷酸酯、(1-五氟苯基)3-丁炔-1-醇二氟磷酸酯(上文式16)及其制备方法。This embodiment provides a kind of (1-pentafluorophenyl) 3-butyn-1-ol dichlorophosphate, (1-pentafluorophenyl) 3-butyn-1-ol difluorophosphate (above Formula 16) and preparation method thereof.

本实施例(1-五氟苯基)3-丁炔-1-醇二氯磷酸酯制备方法具体如下:The preparation method of (1-pentafluorophenyl) 3-butyn-1-ol dichlorophosphate of the present embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入(1-五氟苯基)3-丁炔-1-醇23.6g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将(1-五氟苯基)3-丁炔-1-醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,(1-五氟苯基)3-丁炔-1-醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到(1-五氟苯基)3-丁炔-1-醇二氯磷酸酯;S1: Add 50 mL of dichloromethane to the reactor at room temperature, then add 23.6 g (0.1 mol) of (1-pentafluorophenyl) 3-butyn-1-ol, and stir at room temperature for 0.5 h; Mix 50 mL of dichloromethane and 18 g of POCl 3 at 0°C; add the dichloromethane solution of (1-pentafluorophenyl) 3-butyn-1-ol to the dichloromethane solution of POCl 3 , Stir throughout the addition process and keep the temperature at 0°C, control the rate of addition to keep the gas production rate stable, and keep the temperature constant after adding the dichloromethane solution of (1-pentafluorophenyl) 3-butyn-1-ol to continue the reaction When no gas is produced in the system as the end of the reaction, the HCl gas produced by the reaction is absorbed by pure water to obtain hydrochloric acid, which can be sold as an industrial raw material; after the reaction is completed, dichloromethane is removed by distillation at room temperature and pressure, and then excess POCl is removed by distillation at room temperature and under reduced pressure. Viscous yellow liquid was obtained, and (1-pentafluorophenyl) 3-butyn-1-ol dichlorophosphate was obtained;

本实施例(1-五氟苯基)3-丁炔-1-醇二氟磷酸酯制备方法具体如下:The preparation method of (1-pentafluorophenyl) 3-butyn-1-ol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,125℃减压蒸馏得到无色液体28.5g,产率为89%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, distill off acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 125°C to obtain 28.5 g of a colorless liquid with a yield of 89%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C10H4O2PF7[M]+为320.12。1HNMR(400MHz,CDCl3)δ:4.90(m,1H),3.06(m,1H),2.69(m,2H);13C NMR(100MHz,CDCl3)δ:145.2,136.4,113.7,86.2,69.7,60.9,26.5。证明所得无色液体为(1-五氟苯基)3-丁炔-1-醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为21ppm,酸度为28ppm,氯离子浓度为17ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 10 H 4 O 2 PF 7 [M] + is 320.12. 1 HNMR (400MHz, CDCl 3 ) δ: 4.90(m, 1H), 3.06(m, 1H), 2.69(m, 2H); 13 C NMR (100MHz, CDCl 3 ) δ: 145.2, 136.4, 113.7, 86.2, 69.7, 60.9, 26.5. The obtained colorless liquid proved to be (1-pentafluorophenyl) 3-butyn-1-ol difluorophosphate. The moisture measured by the Karl Fischer moisture analyzer and the potentiometric titrator is 21ppm, the acidity is 28ppm, and the chloride ion concentration is 17ppm.

实施例A17Example A17

本实施例提供一种(1-五氟苯基)3-丁烯-1-醇二氯磷酸酯、(1-五氟苯基)3-丁烯-1-醇二氟磷酸酯(上文式17)及其制备方法。This embodiment provides a kind of (1-pentafluorophenyl) 3-buten-1-ol dichlorophosphate, (1-pentafluorophenyl) 3-buten-1-ol difluorophosphate (above Formula 17) and preparation method thereof.

本实施例(1-五氟苯基)3-丁烯-1-醇二氯磷酸酯制备方法具体如下:The preparation method of (1-pentafluorophenyl) 3-buten-1-ol dichlorophosphate of the present embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入(1-五氟苯基)3-丁烯-1-醇23.8g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将(1-五氟苯基)3-丁烯-1-醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,(1-五氟苯基)3-丁烯-1-醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到(1-五氟苯基)3-丁烯-1-醇二氯磷酸酯;S1: Add 50 mL of dichloromethane to the reactor at room temperature, then add 23.8 g (0.1 mol) of (1-pentafluorophenyl) 3-buten-1-ol, and stir at room temperature for 0.5 h; Mix 50 mL of dichloromethane and 18 g of POCl 3 at 0°C; add (1-pentafluorophenyl) 3-buten-1-ol in dichloromethane solution to POCl 3 in dichloromethane solution, Stir throughout the addition process and keep the temperature at 0°C, control the rate of addition to keep the gas production rate stable, and keep the temperature constant after adding the methylene chloride solution of (1-pentafluorophenyl) 3-buten-1-ol to continue the reaction When no gas is produced in the system as the end of the reaction, the HCl gas produced by the reaction is absorbed by pure water to obtain hydrochloric acid, which can be sold as an industrial raw material; after the reaction is completed, dichloromethane is removed by distillation at room temperature and pressure, and then excess POCl is removed by distillation at room temperature and under reduced pressure. Viscous yellow liquid was obtained, and (1-pentafluorophenyl) 3-buten-1-ol dichlorophosphate was obtained;

本实施例(1-五氟苯基)3-丁烯-1-醇二氟磷酸酯制备方法具体如下:The preparation method of (1-pentafluorophenyl) 3-buten-1-ol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,125℃减压蒸馏得到无色液体28.3g,产率为88%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, remove acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 125°C to obtain 28.3 g of a colorless liquid with a yield of 88%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C10H6O2PF7[M]+为322.15。1HNMR(400MHz,CDCl3)δ:5.82(m,1H),5.13(d,1H),4.91(m,1H),4.88(m,1H),2.62(m,2H);13CNMR(100MHz,CDCl3)δ:145.2,142.2,136.4,134.3,116.4,113.7,62.2,39.2。证明所得无色液体为(1-五氟苯基)3-丁烯-1-醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为20ppm,酸度为26ppm,氯离子浓度为19ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 10 H 6 O 2 PF 7 [M] + is 322.15. 1 HNMR (400MHz, CDCl 3 ) δ: 5.82 (m, 1H), 5.13 (d, 1H), 4.91 (m, 1H), 4.88 (m, 1H), 2.62 (m, 2H); 13 CNMR (100MHz, CDCl 3 ) δ: 145.2, 142.2, 136.4, 134.3, 116.4, 113.7, 62.2, 39.2. The obtained colorless liquid proved to be (1-pentafluorophenyl) 3-buten-1-ol difluorophosphate. The moisture measured by the Karl Fischer moisture analyzer and the potentiometric titrator is 20ppm, the acidity is 26ppm, and the chloride ion concentration is 19ppm.

实施例A18Example A18

本实施例提供一种(1,1-二五氟苯基)3-丁烯-1-醇二氯磷酸酯、(1,1-二五氟苯基)3-丁烯-1-醇二氟磷酸酯(上文式18)及其制备方法。This embodiment provides a kind of (1,1-dipentafluorophenyl) 3-buten-1-ol dichlorophosphate, (1,1-dipentafluorophenyl) 3-buten-1-ol dichlorophosphate Fluorophosphate esters (formula 18 above) and methods for their preparation.

本实施例(1,1-二五氟苯基)3-丁烯-1-醇二氯磷酸酯制备方法具体如下:The preparation method of (1,1-dipentafluorophenyl) 3-buten-1-ol dichlorophosphate in this embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入(1,1-二五氟苯基)3-丁烯-1-醇40.4g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将(1,1-二五氟苯基)3-丁烯-1-醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,(1,1-二五氟苯基)3-丁烯-1-醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到(1,1-二五氟苯基)3-丁烯-1-醇二氯磷酸酯;S1: Add 50 mL of dichloromethane to the reaction kettle at room temperature, then add 40.4 g (0.1 mol) of (1,1-dipentafluorophenyl) 3-buten-1-ol, and stir at room temperature for 0.5 h; Mix 50 mL of dichloromethane and 18 g of POCl 3 in a reaction kettle at 0°C; add (1,1-dipentafluorophenyl) 3 -buten-1-ol in dichloromethane to the In the dichloromethane solution, stir the whole process of adding and keep the temperature at 0°C, control the rate of addition to keep the gas production rate stable, the dichloromethane solution of (1,1-dipentafluorophenyl) 3-buten-1-ol After the addition, keep the temperature constant and continue to react until the system has no gas generation as the reaction end point. The HCl gas produced by the reaction is absorbed by pure water to obtain hydrochloric acid, which can be sold as industrial raw materials; after the reaction is completed, methylene chloride is removed by distillation at room temperature and atmospheric pressure, and then Excessive POCl was distilled off under reduced pressure at room temperature to obtain a viscous yellow liquid to obtain (1,1-dipentafluorophenyl) 3 -buten-1-ol dichlorophosphate;

本实施例(1,1-二五氟苯基)3-丁烯-1-醇二氟磷酸酯制备方法具体如下:The preparation method of (1,1-dipentafluorophenyl) 3-buten-1-ol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,155℃减压蒸馏得到无色液体42.9g,产率为88%。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, distill off acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 155°C to obtain 42.9 g of a colorless liquid with a yield of 88%.

在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo FisherScientific)进行分析,分析结果显示GC-MS(ESI)calcd for C16H5O2PF12[M]+为488.24。1HNMR(400MHz,CDCl3)δ:5.82(m,1H),5.13(d,1H),4.88(d,1H),2.91(d,2H);13C NMR(100MHz,CDCl3)δ:145.5,140.8,137.5,130.8,120.2,115.8,57.1,44.6。证明所得无色液体为(1,1-二五氟苯基)3-丁烯-1-醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为20ppm,酸度为28ppm,氯离子浓度为12ppm。In the glove box, take 0.1 mL of the obtained colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, filter the suspended matter with an organic filter membrane, take a small amount of the filtrate and inject it with a syringe, and conduct the analysis by GC (Thermo Fisher Scientific) Analysis, analysis results show that GC-MS (ESI) calcd for C 16 H 5 O 2 PF 12 [M] + is 488.24. 1 HNMR (400MHz, CDCl 3 ) δ: 5.82(m, 1H), 5.13(d, 1H), 4.88(d, 1H), 2.91(d, 2H); 13 C NMR (100MHz, CDCl 3 ) δ: 145.5 , 140.8, 137.5, 130.8, 120.2, 115.8, 57.1, 44.6. It was proved that the obtained colorless liquid was (1,1-dipentafluorophenyl) 3-buten-1-ol difluorophosphate. Moisture measured by Karl Fischer moisture analyzer and potentiometric titrator is 20ppm, acidity is 28ppm, and chloride ion concentration is 12ppm.

实施例A19Example A19

本实施例提供一种(1,1-二五氟苯基)3-丁炔-1-醇二氯磷酸酯、(1,1-二五氟苯基)3-丁炔-1-醇二氟磷酸酯(上文式19)及其制备方法。This embodiment provides a kind of (1,1-dipentafluorophenyl) 3-butyn-1-ol dichlorophosphate, (1,1-dipentafluorophenyl) 3-butyn-1-ol dichlorophosphate Fluorophosphate esters (formula 19 above) and methods for their preparation.

本实施例(1,1-二五氟苯基)3-丁炔-1-醇二氯磷酸酯制备方法具体如下:The preparation method of (1,1-dipentafluorophenyl) 3-butyn-1-ol dichlorophosphate in this embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入(1,1-二五氟苯基)3-丁炔-1-醇40.2g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将(1,1-二五氟苯基)3-丁炔-1-醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,(1,1-二五氟苯基)3-丁炔-1-醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到(1,1-二五氟苯基)3-丁炔-1-醇二氯磷酸酯;S1: Add 50 mL of dichloromethane to the reactor at room temperature, then add 40.2 g (0.1 mol) of (1,1-dipentafluorophenyl) 3-butyn-1-ol, and stir at room temperature for 0.5 h; Mix 50 mL of dichloromethane and 18 g of POCl 3 in a reaction kettle at 0°C; add (1,1-dipentafluorophenyl) 3 -butyn-1-ol in dichloromethane to the In dichloromethane solution, stir throughout the addition process and keep the temperature at 0°C, control the rate of addition to keep the gas production rate stable, (1,1-dipentafluorophenyl) 3-butyn-1-ol in dichloromethane solution After the addition, keep the temperature constant and continue to react until the system has no gas generation as the reaction end point. The HCl gas produced by the reaction is absorbed by pure water to obtain hydrochloric acid, which can be sold as industrial raw materials; after the reaction is completed, methylene chloride is removed by distillation at room temperature and atmospheric pressure, and then Excessive POCl was distilled off at room temperature under reduced pressure to obtain a viscous yellow liquid to obtain (1,1-dipentafluorophenyl) 3 -butyn-1-ol dichlorophosphate;

本实施例(1,1-二五氟苯基)3-丁炔-1-醇二氟磷酸酯制备方法具体如下:The preparation method of (1,1-dipentafluorophenyl) 3-butyn-1-ol difluorophosphate in this embodiment is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,155℃减压蒸馏得到无色液体42.3g,产率为87%。在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo Fisher Scientific)进行分析,分析结果显示LC-MS(ESI)calcdfor C16H3O2PF12[M]+为486.25。1H NMR(400MHz,CDCl3)δ:3.06(m,1H),2.98(m,2H);13C NMR(100MHz,CDCl3)δ:145.5,140.8,137.5,115.8,86.2,69.7,55.8,32.3。证明所得无色液体为(1,1-二五氟苯基)3-丁炔-1-醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为21ppm,酸度为22ppm,氯离子浓度为13ppm。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, distill off acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 155°C to obtain 42.3 g of a colorless liquid with a yield of 87%. In the glove box, take 0.1 mL of the resulting colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, remove the suspended solids by filtering with an organic filter, take a small amount of the filtrate and inject it with a syringe, and pass through GC (Thermo Fisher Scientific) Analysis was carried out, and the analysis result showed that LC-MS (ESI) calcdfor C 16 H 3 O 2 PF 12 [M] + was 486.25. 1 H NMR (400MHz, CDCl 3 ) δ: 3.06 (m, 1H), 2.98 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ: 145.5, 140.8, 137.5, 115.8, 86.2, 69.7, 55.8, 32.3. It was proved that the obtained colorless liquid was (1,1-dipentafluorophenyl) 3-butyn-1-ol difluorophosphate. Moisture measured by Karl Fischer moisture analyzer and potentiometric titrator is 21ppm, acidity is 22ppm, and chloride ion concentration is 13ppm.

实施例A20Example A20

本实施例提供一种1,1-二(五氟苯基)甲醇二氯磷酸酯、1,1-二(五氟苯基)甲醇二氟磷酸酯(上文式19)及其制备方法。This embodiment provides 1,1-bis(pentafluorophenyl)methanol dichlorophosphate, 1,1-bis(pentafluorophenyl)methanol difluorophosphate (formula 19 above) and a preparation method thereof.

本实施例1,1-二(五氟苯基)甲醇二氯磷酸酯制备方法具体如下:The preparation method of 1,1-bis(pentafluorophenyl)methanol dichlorophosphate in this embodiment is as follows:

S1:室温条件下向反应釜中加入二氯甲烷50mL,然后加入1,1-二(五氟苯基)甲醇36.4g(0.1mol),室温搅拌0.5h;在另一反应釜中将二氯甲烷50mL与18g POCl3在0℃条件下混合;将1,1-二(五氟苯基)甲醇的二氯甲烷溶液加入到POCl3的二氯甲烷溶液中,加入过程全程搅拌并保持温度在0℃,控制滴加速度保持产气速度平稳,1,1-二(五氟苯基)甲醇的二氯甲烷溶液加入完毕后保持温度不变继续反应至体系无气体产生为反应终点,反应产生的HCl气体使用纯净水吸收得到盐酸,盐酸可以作为工业原料出售;反应完成后室温常压蒸馏除去二氯甲烷,然后室温减压蒸馏除去过量的POCl3得到粘稠状黄色液体,得到1,1-二(五氟苯基)甲醇二氯磷酸酯;S1: Add 50mL of dichloromethane to the reaction kettle at room temperature, then add 36.4g (0.1mol) of 1,1-bis(pentafluorophenyl)methanol, and stir at room temperature for 0.5h; Mix 50mL of methane and 18g of POCl 3 at 0°C; add the dichloromethane solution of 1,1-bis(pentafluorophenyl)methanol to the dichloromethane solution of POCl 3 , stir throughout the addition process and keep the temperature at 0°C, control the rate of addition to keep the gas production rate stable, keep the temperature constant after adding the dichloromethane solution of 1,1-bis(pentafluorophenyl)methanol and continue the reaction until no gas is produced in the system. HCl gas is absorbed by pure water to obtain hydrochloric acid, which can be sold as an industrial raw material; after the reaction is completed, dichloromethane is removed by distillation at room temperature and atmospheric pressure, and then excess POCl is removed by distillation at room temperature and reduced pressure to obtain a viscous yellow liquid, and 1,1- Bis(pentafluorophenyl)methanol dichlorophosphate;

本实施例1,1-二(五氟苯基)甲醇二氟磷酸酯制备方法具体如下:In this embodiment, the preparation method of 1,1-bis(pentafluorophenyl)methanol difluorophosphate is as follows:

S2:向上述步骤S1中粘稠状黄色液体中加入50mL乙腈后室温搅拌得到淡黄色溶液,向所述溶液中分批次加入KF15g然后升温至60℃反应3h;反应过程中无气体放出,然后静置沉降冷却至室温后常压过滤得到淡黄色溶液,常温减压蒸馏除去乙腈得到黄色液体,150℃减压蒸馏得到无色液体39.9g,产率为89%。在手套箱中,取所得无色液体0.1mL,加入2ml无水乙腈中使其完全溶解,使用有机滤膜过滤除去悬浮物,取少量滤液使用注射器进样,通过气质联用(Thermo Fisher Scientific)进行分析,分析结果显示LC-MS(ESI)calcdfor C13HO2PF12[M]+为448.16。1H NMR(400MHz,CDCl3)δ:6.16(d,1H);13CNMR(100MHz,CDCl3)δ:145.5,140.8,137.5,115.8,52.1。证明所得无色液体为1,1-二(五氟苯基)甲醇二氟磷酸酯。通过卡氏水分测定仪和电位滴定仪测定水分为20ppm,酸度为25ppm,氯离子浓度为12ppm。S2: Add 50 mL of acetonitrile to the viscous yellow liquid in the above step S1 and stir at room temperature to obtain a light yellow solution. Add 15 g of KF to the solution in batches and then raise the temperature to 60 ° C for 3 h; no gas is released during the reaction, and then After standing and settling to cool to room temperature, filter under normal pressure to obtain a light yellow solution, remove acetonitrile under reduced pressure at room temperature to obtain a yellow liquid, and distill under reduced pressure at 150°C to obtain 39.9 g of a colorless liquid with a yield of 89%. In the glove box, take 0.1 mL of the resulting colorless liquid, add it to 2 ml of anhydrous acetonitrile to dissolve it completely, remove the suspended solids by filtering with an organic filter, take a small amount of the filtrate and inject it with a syringe, and pass through GC (Thermo Fisher Scientific) Analysis was carried out, and the analysis result showed that LC-MS (ESI) calcdfor C 13 HO 2 PF 12 [M] + was 448.16. 1 H NMR (400 MHz, CDCl 3 ) δ: 6.16 (d, 1H); 13 CNMR (100 MHz, CDCl 3 ) δ: 145.5, 140.8, 137.5, 115.8, 52.1. It was proved that the obtained colorless liquid was 1,1-bis(pentafluorophenyl)methanol difluorophosphate. The moisture measured by the Karl Fischer moisture analyzer and the potentiometric titrator is 20ppm, the acidity is 25ppm, and the chloride ion concentration is 12ppm.

B.非水电解液实施例B. Examples of non-aqueous electrolytes

本实施例提供非水电解液电解液。This embodiment provides a non-aqueous electrolyte electrolyte.

非水电解液电解液配制:Non-aqueous electrolyte electrolyte preparation:

在氩气氛围的手套箱中(手套箱中H2O、O2含量低于0.1ppm)配置实施例非水电解液,将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)和碳酸二乙酯(DEC)以质量比为30:50:20的比例进行混合得到电解液溶液,然后向电解液溶液中加入六氟磷酸锂(LiPF6),使六氟磷酸锂(LiPF6)浓度为1.0mol/L。以非水电解液的总重量为100%计,加入二氟磷酸锂(LiO2PF2)、1,3-丙磺酸内酯(PS)和硫酸乙烯酯(DTD),使其质量分数都为1%,同时加入碳酸亚乙烯酯(VC)、双草酸二氟硼酸锂(LiBOB),使其质量分数都为0.5%,得到对照电解液样品,编号记为(1);In the glove box of argon atmosphere (in the glove box, H 2 O, O 2 content is lower than 0.1ppm) configuration embodiment non-aqueous electrolyte, ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dicarbonate Ethyl ester (DEC) was mixed at a mass ratio of 30:50:20 to obtain an electrolyte solution, and then lithium hexafluorophosphate (LiPF 6 ) was added to the electrolyte solution so that the concentration of lithium hexafluorophosphate (LiPF 6 ) was 1.0 mol/L. Based on the total weight of the non-aqueous electrolyte as 100%, lithium difluorophosphate (LiO 2 PF 2 ), 1,3-propane sultone (PS) and vinyl sulfate (DTD) were added so that the mass fractions was 1%, and simultaneously added vinylene carbonate (VC) and lithium bisoxalate difluoroborate (LiBOB) so that the mass fraction thereof was 0.5%, to obtain a control electrolyte sample, which was numbered as (1);

在氩气氛围的手套箱中(手套箱中H2O、O2含量低于0.1ppm)配置实施例非水电解液,将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)以质量比为30:70的比例进行混合得到电解液溶液,然后向电解液溶液中加入六氟磷酸锂(LiPF6),使六氟磷酸锂(LiPF6)浓度为1.0mol/L,以非水电解液的总重量为100%计,加入二氟磷酸锂(LiO2PF2)、1,3-丙磺酸内酯(PS)和硫酸乙烯酯(DTD),使其质量分数都为1%,同时加入碳酸亚乙烯酯(VC)、双草酸二氟硼酸锂(LiBOB),使其质量分数都为0.5%,然后分别加入式1~式20所示添加剂,使其质量分数都为1%。分别得到编号为(2)~(21)的电解液。In the glove box of argon atmosphere (H 2 O, O 2 content is lower than 0.1ppm in the glove box) configuration embodiment non-aqueous electrolyte, with ethylene carbonate (EC), ethyl methyl carbonate (EMC) with mass ratio Mix at a ratio of 30:70 to obtain an electrolyte solution, and then add lithium hexafluorophosphate (LiPF 6 ) to the electrolyte solution so that the concentration of lithium hexafluorophosphate (LiPF 6 ) is 1.0 mol/L, taking the total weight of the non-aqueous electrolyte as 100% Calculated, lithium difluorophosphate (LiO 2 PF 2 ), 1,3-propane sultone (PS) and vinyl sulfate (DTD) were added so that the mass fraction was 1%, and vinylene carbonate ( VC), bisoxalate lithium difluoroborate (LiBOB), so that the mass fraction is 0.5%, and then add the additives shown in formula 1 to formula 20 respectively, so that the mass fraction is 1%. Electrolyte solutions numbered (2) to (21) were obtained respectively.

上述编号(1)-(21)非水电解液所含的组分如下表1中所示:The components contained in the above-mentioned numbers (1)-(21) non-aqueous electrolyte are as shown in Table 1 below:

表1非水电解液主要成分Table 1 Main components of non-aqueous electrolyte

Figure BDA0003106642530000241
Figure BDA0003106642530000241

Figure BDA0003106642530000251
Figure BDA0003106642530000251

C.二次电池实施例C. Secondary Battery Example

实施例C1(对比例C1)Embodiment C1 (comparative example C1)

本实施例提供一种锂二次电池。该锂二次电池按照如下方法组装:This embodiment provides a lithium secondary battery. The lithium secondary battery is assembled as follows:

正极极片制备:Positive pole piece preparation:

以镍钴锰酸锂(LiNi0.8Co0.1Mn0.1O2,简称NCM811)三元材料作为正极活性物质,正极活性浆料按质量比96%正极活性物质+2%PVDF粘合剂+2%Super P导电炭黑溶于溶剂N-甲基吡咯烷酮中混合得到。然后将正极活性浆料均匀涂布在集流体铝箔上,涂布量为300g/m2,随后在80℃下烘干后进行冷压、切边、裁片、分条后,在80℃真空条件下干燥4h,焊接极耳,得到正极片。Nickel cobalt lithium manganese oxide (LiNi 0.8 Co 0.1 Mn 0.1 O 2 , referred to as NCM811) ternary material is used as the positive electrode active material, and the positive electrode active slurry is 96% positive electrode active material + 2% PVDF binder + 2% Super The P conductive carbon black is obtained by dissolving and mixing the solvent N-methylpyrrolidone. Then, the positive electrode active slurry is evenly coated on the aluminum foil of the current collector, and the coating amount is 300g/m 2 , and then dried at 80°C, cold-pressed, edge trimmed, cut into pieces, and stripped, and vacuumed at 80°C Dry for 4 hours under the same conditions, and weld the tabs to obtain the positive electrode sheet.

负极极片制备:Negative pole piece preparation:

以人造石墨作为负极活性物质,负极活性浆料按质量比96%负极活性物质+2%CMC/SBR粘合剂+2%Super P导电炭黑混合后加入去离子水中搅拌均匀得到,然后将负极活性浆料均匀涂布在集流体铜箔上,涂布量为200g/m2,随后在85℃下烘干后进行冷压、切边、裁片、分条后,在110℃真空条件下干燥4h,焊接极耳,得到负极片。Using artificial graphite as the negative electrode active material, the negative electrode active slurry is mixed according to the mass ratio of 96% negative electrode active material + 2% CMC/SBR binder + 2% Super P conductive carbon black, then added to deionized water and stirred evenly, and then the negative electrode The active slurry is evenly coated on the copper foil of the current collector, and the coating amount is 200g/m 2 , and then dried at 85°C, cold pressed, edge trimmed, cut into pieces, and stripped, and then vacuumed at 110°C After drying for 4 hours, the tabs were welded to obtain a negative electrode sheet.

软包锂离子电池的制备:Preparation of soft pack lithium ion battery:

将正极片、负极片以及陶瓷涂覆的PE隔膜经过叠片工艺制作成软包电芯,并在75℃下真空烘烤10h,使用上述编号为(1)的电解液对软包电芯进行注液,注液后静置24h,经过化成老化、夹具、分容等工序,得到软包电池编号为(A1)。The positive electrode sheet, the negative electrode sheet, and the ceramic-coated PE separator are made into a soft-packed battery cell through a lamination process, and vacuum-baked at 75°C for 10 hours, and the soft-packed battery cell is processed using the electrolyte numbered (1) above. Inject the liquid, let it stand for 24 hours after the liquid injection, and undergo processes such as formation and aging, fixtures, and volume separation to obtain a pouch battery numbered as (A1).

实施例C2-实施例C41Example C2-Example C41

本实施例提供一种锂二次电池。该锂二次电池按照如下方法组装:This embodiment provides a lithium secondary battery. The lithium secondary battery is assembled as follows:

除了在软包锂离子电池的制备过程中分别使用上述编号为(2)至编号为(21)的电解液对软包电芯分别进行注液,注液后静置24h,经过化成老化、夹具、分容等工序,分别得到软包电池编号为(A2)至(A21)。其它都与实施例C1相同。In addition to using the above-mentioned electrolyte solutions numbered (2) to (21) in the preparation process of the soft-packed lithium-ion battery to inject liquid into the soft-packed cells respectively, after the liquid injection, let it stand for 24 hours, and after chemical aging, fixture , capacity division and other processes, the numbers of soft pack batteries are obtained respectively (A2) to (A21). Others are the same as embodiment C1.

锂离子电池性能测试Lithium-ion battery performance test

为了保持实验的一致性,所有小软包电芯都使用相同体积的电解液。然后对制备好的小软包电芯进行充放电测试,使用LAND充放电测试系统对组装好的电芯进行如下性能测试。In order to maintain the consistency of the experiment, all the small pouch cells use the same volume of electrolyte. Then, charge and discharge tests were performed on the prepared small soft-pack batteries, and the following performance tests were performed on the assembled batteries using the LAND charge and discharge test system.

(一)、在正极极片制备过程中以镍钴锰酸锂(LiNi0.8Co0.1Mn0.1O2,简称NCM811)三元材料作为正极活性物质制作的软包电池测试如下:(1) During the preparation of the positive electrode sheet, the test of the pouch battery made of nickel-cobalt lithium manganate (LiNi 0.8 Co 0.1 Mn 0.1 O 2 , referred to as NCM811) ternary material as the positive active material is as follows:

1常温循环性能测试1 Normal temperature cycle performance test

将化成后的电池置于恒温25℃的烘箱中,使用1C恒流恒压(CC-CV)充电至电压为4.2V,截至电流为0.01C,然后用1C恒流(CC)放电至电压为3.0V。如此充/放电N次循环后,记录第一次和第N次循环后容量的保持率,以评估其常温循环性能。Place the formed battery in an oven at a constant temperature of 25°C, charge it with 1C constant current and constant voltage (CC-CV) to a voltage of 4.2V, cut off the current at 0.01C, and then discharge it with 1C constant current (CC) to a voltage of 3.0V. After such charging/discharging for N cycles, record the capacity retention rate after the first and Nth cycles to evaluate its normal temperature cycle performance.

25℃1C循环N次容量保持率计算公式如下:The formula for calculating the capacity retention rate of N cycles at 25°C and 1C is as follows:

第N次循环容量保持率(%)=(第N次循环放电容量/第一次循环放电量)×100%。Nth cycle capacity retention (%)=(Nth cycle discharge capacity/first cycle discharge capacity)×100%.

2.高温循环性能测试2. High temperature cycle performance test

将化成后的电池置于恒温45℃的烘箱中,使用1C恒流恒压(CC-CV)充电至电压为4.2V,截至电流为0.01C,然后用1C恒流(CC)放电至电压为3.0V。如此充/放电N次循环后,记录第一次和第N次循环后容量的保持率,以评估其高温循环性能。Place the formed battery in an oven at a constant temperature of 45°C, charge it with 1C constant current and constant voltage (CC-CV) to a voltage of 4.2V, and cut off the current at 0.01C, and then discharge it with 1C constant current (CC) to a voltage of 3.0V. After such charging/discharging for N cycles, record the capacity retention rate after the first and Nth cycles to evaluate its high-temperature cycle performance.

45℃1C循环N次容量保持率计算公式如下:The formula for calculating the capacity retention rate of N cycles at 45°C 1C is as follows:

第N次循环容量保持率(%)=(第N次循环放电容量/第一次循环放电量)×100%。Nth cycle capacity retention (%)=(Nth cycle discharge capacity/first cycle discharge capacity)×100%.

3.室温储存性能测试3. Room temperature storage performance test

将化成后的电芯在常温下用1C恒流恒压(CC-CV)充电至电压为4.2V,截至电流为0.01C,再用1C恒流(CC)放电至电压为3.0V,测量电池初始放电容量,再用1C恒流恒压(CC-CV)充电至电压为4.2V,截至电流为0.01C,测量电池的初始厚度,然后将电池在室温条件下储存N天后,测量电池的厚度,再以1C恒流(CC)放电至电压为3.0V,测量电池的保持容量,再用1C恒流恒压(CC-CV)充电至电压为4.2V,截至电流为0.01C,然后用1C恒流(CC)放电至电压为3.0V,测量恢复容量。Charge the formed cell at room temperature with 1C constant current and constant voltage (CC-CV) to a voltage of 4.2V, with a cut-off current of 0.01C, and then discharge it with 1C constant current (CC) to a voltage of 3.0V, and measure the battery Initial discharge capacity, then charged to 4.2V with 1C constant current and constant voltage (CC-CV), the cut-off current is 0.01C, measure the initial thickness of the battery, and then store the battery at room temperature for N days, then measure the thickness of the battery , and then discharged to a voltage of 3.0V with 1C constant current (CC) to measure the holding capacity of the battery, and then charged to a voltage of 4.2V with 1C constant current and constant voltage (CC-CV), and the cut-off current was 0.01C, and then charged with 1C Constant current (CC) discharge to a voltage of 3.0V, and measure the recovery capacity.

容量保持率、容量恢复率的计算公式如下:The calculation formulas of capacity retention rate and capacity recovery rate are as follows:

电池容量保持率(%)=保持容量/初始容量×100%;Battery capacity retention rate (%) = retention capacity/initial capacity × 100%;

电池容量恢复率(%)=恢复容量/初始容量×100%;Battery capacity recovery rate (%) = recovery capacity / initial capacity × 100%;

4.60℃高温储存性能测试4.60℃ high temperature storage performance test

将化成后的电芯在常温下用1C恒流恒压(CC-CV)充电至电压为4.2V,截至电流为0.01C,再用1C恒流(CC)放电至电压为3.0V,测量电池初始放电容量,再用1C恒流恒压(CC-CV)充电至电压为4.2V,截至电流为0.01C,测量电池的初始厚度,然后将电池在60℃条件下储存N天后,测量电池的厚度,再以1C恒流(CC)放电至电压为3.0V,测量电池的保持容量,再用1C恒流恒压(CC-CV)充电至电压为4.2V,截至电流为0.01C,然后用1C恒流(CC)放电至电压为3.0V,测量恢复容量。Charge the formed cell at room temperature with 1C constant current and constant voltage (CC-CV) to a voltage of 4.2V, with a cut-off current of 0.01C, and then discharge it with 1C constant current (CC) to a voltage of 3.0V, and measure the battery Initial discharge capacity, and then charged to a voltage of 4.2V with 1C constant current and constant voltage (CC-CV), the cut-off current is 0.01C, and the initial thickness of the battery is measured, and then the battery is stored at 60°C for N days, and the battery is measured. Thickness, then discharge with 1C constant current (CC) to a voltage of 3.0V, measure the holding capacity of the battery, and then use 1C constant current (CC-CV) to charge to a voltage of 4.2V, the cut-off current is 0.01C, and then use 1C constant current (CC) discharge to a voltage of 3.0V, and measure the recovery capacity.

容量保持率、容量恢复率的计算公式如下:The calculation formulas of capacity retention rate and capacity recovery rate are as follows:

电池容量保持率(%)=保持容量/初始容量×100%;Battery capacity retention rate (%) = retention capacity/initial capacity × 100%;

电池容量恢复率(%)=恢复容量/初始容量×100%;Battery capacity recovery rate (%) = recovery capacity / initial capacity × 100%;

5.60℃高温储存30天充电DCIR的增加率5. Increase rate of charging DCIR after 30 days of high temperature storage at 60°C

电芯的荷电状态(SOC)为50%条件下,将充电倍率(C-rate)依次设置为0.2C、0.33C、0.5C、1.0C、1.5C、2.0C、2.5C、3.0C(可根据实际情况调整倍率),然后分别以设置的充电倍率(C-rate)进行10秒的充电,连接电压的终止点构成直线,其斜率(slope)即为充电DCIR。将高温储存开始前电芯的DCIR设为“R1”,在60℃高温下储存30天后电芯的DCIR设为“R2”时,通过下面公式计算出充电DCIR的增加率:充电DCIR的增加率(%)=(R2-R1)/R1×100When the state of charge (SOC) of the battery cell is 50%, set the charging rate (C-rate) to 0.2C, 0.33C, 0.5C, 1.0C, 1.5C, 2.0C, 2.5C, 3.0C ( The rate can be adjusted according to the actual situation), and then charge at the set charge rate (C-rate) for 10 seconds, and the end point of the connection voltage forms a straight line, and its slope (slope) is the charging DCIR. Set the DCIR of the cell before high temperature storage as "R1", and set the DCIR of the cell as "R2" after storage at 60°C for 30 days, and calculate the increase rate of charging DCIR by the following formula: Increase rate of charging DCIR (%)=(R2-R1)/R1×100

电芯测试电压范围为3.0~4.2V,在室温条件下以1C恒流(CC)充放电循环600周后测试电池的容量保持率;在45℃条件下以1C恒流(CC)充放电循环400周后测试电池的容量保持率;分别在室温下储存100天和在60℃下存储21天后测试电池的容量保持率和恢复率;以及在60℃下存储30天后的电芯体积膨胀率和DCIR增长率。The cell test voltage range is 3.0-4.2V, and the capacity retention rate of the battery is tested after 600 cycles of charging and discharging with 1C constant current (CC) at room temperature; Test the capacity retention rate of the battery after 400 weeks; test the capacity retention rate and recovery rate of the battery after storage at room temperature for 100 days and 21 days at 60°C; and the cell volume expansion rate and DCIR growth rate.

具体数据如表2所示。The specific data are shown in Table 2.

表2电池性能测试结果Table 2 battery performance test results

Figure BDA0003106642530000261
Figure BDA0003106642530000261

Figure BDA0003106642530000271
Figure BDA0003106642530000271

通过表2的测试结果可知,使用本发明实施例含支链卤代磷酸酯作为添加剂使用有利于提升电池的常温循环性能、高温循环性能、常温存储性能和高温存储性能,同时还具有抑制电池存储过程中的DCIR增长的作用。其中,含不饱和键的添加剂效果优于不含不饱和键的添加剂,含炔基的添加剂效果优于含烯基的添加剂。卤代磷酸酯基团特别是二氟磷酸酯基团有助于降低阻抗,其它基团可以提升成膜能力或改善浸润性,通过卤代特别是二氟磷酸酯基团与其它基团的协同作用可以更好的提升电池的综合性能。From the test results in Table 2, it can be seen that using the branched-chain halogenated phosphate ester as an additive in the embodiment of the present invention is beneficial to improve the normal temperature cycle performance, high temperature cycle performance, normal temperature storage performance and high temperature storage performance of the battery, and also has the effect of inhibiting battery storage. The role of DCIR growth in the process. Among them, the effect of additives containing unsaturated bonds is better than that of additives without unsaturated bonds, and the effect of additives containing alkyne groups is better than that of additives containing alkenyl groups. The halophosphate group, especially the difluorophosphate group, helps to reduce the impedance, and other groups can improve the film-forming ability or improve the wettability, through the synergy between the halogenation, especially the difluorophosphate group and other groups The function can better improve the overall performance of the battery.

以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the present invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Claims (11)

1. A halogenated phosphate containing a branched chain has a molecular structural formula shown as the following general formula I:
Figure FDA0003106642520000011
wherein R in the general formula I 1 、R 2 、R 3 Independently selected from one of alkyl with 1 to 10 carbon atoms, alkenyl with 1 to 10 carbon atoms, alkynyl with 1 to 10 carbon atoms, chain alkoxy with 1 to 10 carbon atoms, chain alkenyloxy with 2 to 10 carbon atoms, chain alkynyloxy with 2 to 10 carbon atoms, cyclic alkoxy with 3 to 10 carbon atoms, cyclic alkenyloxy with 3 to 10 carbon atoms, trimethylsilyl, trimethylsiloxy, halogen-containing alkyl, phenyl, biphenyl, naphthyl, pyridyl, thienyl, halogenated phenyl, halogenated biphenyl, phenol, alkyl-containing phenol, alkenyl-containing phenol, alkynyl-containing phenol, nitrile-containing phenol, halogenated phenol and halogenated naphthol;
R 4 、R 5 、R 6 、R 7 one selected from a hydrogen atom, a halogen atom, an aromatic group having 6 to 10 carbon atoms, a halogenated aromatic group having 6 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, a halogenated alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a halogenated alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 2 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, a trialkylsiloxy group having 3 to 20 carbon atoms, an arylsilyl group, an arylsiloxy group, a pyridyl group, a thienyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group, and a halogenated naphthyl group;
M 1 、M 2 independently selected from halogen atoms;
x is an integer of 0 to 10.
2. The branched halophosphate of claim 1, wherein: the R is 1 To R 7 Is a chain group, the chain group comprises a straight chain group or a branched chain group; and/or
The R is 1 To R 7 At least one group in (b) is a chain group, and the chain group contains at least one of a halogen atom, an oxygen atom, or an unsaturated bond functional group; and/or
The R is 1 To R 7 Is a halogenated group, said halogenated group being partially or fully substituted; and/or
The M is 1 、M 2 The halogen atom is at least one of fluorine, chlorine, bromine and iodine atoms.
3. The branched halophosphate of claim 2, wherein: when the chain-like group contains an unsaturated bond functional group, the unsaturated bond functional group comprises at least one of a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-oxygen double bond, a sulfur-oxygen double bond, a phosphorus-oxygen double bond, an amide, an imide, a sulfonamide, a sulfimide, a phosphoramide, a phosphorus imide, a carboxylic ester, a sulfonic ester and a phosphate ester; and/or
When the chain-like group contains an unsaturated bond functional group, the position of the unsaturated bond functional group is on the inner side of the terminal group or/and the terminal group.
4. The branched halophosphate of claim 1, wherein: comprises the following molecular structural formula I 1 To structural formula I 7 At least one of:
Figure FDA0003106642520000021
wherein, the general formula I 2 To I 7 R in (1) 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 、R 31 、R 32 、R 33 、R 34 Independently selected from hydrogen atom, halogen atom, aromatic group with 6-10 carbon atoms, halogenated aromatic group with 6-10 carbon atoms, alkyl with 1-10 carbon atoms, halogenated alkyl with 1-10 carbon atoms, alkenyl with 1-10 carbon atoms, halogenated alkenyl with 1-10 carbon atoms, alkynyl with 1-10 carbon atoms, halogenated alkynyl with 1-10 carbon atoms, chain alkoxy with 2-10 carbon atoms, chain alkenyloxy with 2-10 carbon atoms, chain alkynyloxy with 2-10 carbon atoms, cyclic alkoxy with 3-10 carbon atoms, cyclic alkenyloxy with 3-10 carbon atoms, trialkylsilyl with 3-20 carbon atoms, carbon protogen3-20 times of the number of the subgroups of trialkylsiloxy, aryl-containing silicon, pyridyl, thienyl, phenolic group, alkyl-containing phenolic group, alkenyl-containing phenolic group, alkynyl-containing phenolic group, nitrile-containing phenolic group, monohalogenated phenolic group and polyhalogenated phenolic group;
m, n, o, p, y and z are independently integers of 0-10.
5. The branched halophosphate according to any one of claims 1 to 4, wherein: the halogenated phosphate containing branched chain comprises at least one of the compounds shown as the following formula 1 to formula 20:
Figure FDA0003106642520000031
6. a preparation method of halogenated phosphate containing branched chains comprises the following steps:
will be shown in the following structural formula I A A reactant A is shown and is shown in the following structural formula I B Carrying out a first substitution reaction on a reactant B in a first non-aqueous solution to generate a halogenated phosphate product containing a branched chain as shown in a structural formula I;
Figure FDA0003106642520000032
wherein, formula I A And R in I 1 、R 2 、R 3 Independently selected from alkyl with 1 to 10 carbon atoms, alkenyl with 1 to 10 carbon atoms, alkynyl with 1 to 10 carbon atoms, chain alkoxy with 1 to 10 carbon atoms, chain alkenyloxy with 2 to 10 carbon atoms, chain alkynyloxy with 2 to 10 carbon atoms, cyclic alkoxy with 3 to 10 carbon atoms, cyclic alkenyloxy with 3 to 10 carbon atoms, trimethylsilyl, trimethylsiloxy, halogen-containing alkyl, phenyl, biphenyl, naphthyl, pyridyl, thienyl, halogenated phenyl, halogenated biphenyl, phenol group and alkyl-containing alkylOne of phenol group, phenol group containing alkenyl group, phenol group containing alkynyl group, phenol group containing nitrile group, halogenated phenol group and halogenated naphthol group;
R 4 、R 5 、R 6 、R 7 one group independently selected from a hydrogen atom, a halogen atom, an aromatic group with 6-10 carbon atoms and a halogenated aromatic group with 6-10 carbon atoms, an alkyl group with 1-10 carbon atoms, a halogenated alkyl group with 1-10 carbon atoms, an alkenyl group with 1-10 carbon atoms, a halogenated alkenyl group with 1-10 carbon atoms, an alkynyl group with 1-10 carbon atoms, a halogenated alkynyl group with 1-10 carbon atoms, a chain alkoxy group with 2-10 carbon atoms, a chain alkenyloxy group with 2-10 carbon atoms, a chain alkynyloxy group with 2-10 carbon atoms, a cyclic alkoxy group with 3-10 carbon atoms, a cyclic alkenyloxy group with 3-10 carbon atoms, a trialkylsilyl group with 3-20 carbon atoms, a trialkylsiloxy group with 3-20 carbon atoms, a phenol group with an alkyl group, a phenol group with an alkenyl group, a phenol group with an alkyne group, a phenol group with a nitrile group, a halogenated phenol group with a halogenated naphthalene group;
M 1 、M 2 、M 3 independently selected from halogen atoms;
x is an integer of 0 to 10.
7. The method of claim 6, wherein: the reactant A and the reactant B are mixed according to a molar ratio of 1: (1-6) mixing in the first non-aqueous solution and carrying out the first substitution reaction; and/or
The mass ratio of the reactant A to the first non-aqueous solution is 1: (1-6); and/or
The temperature of the first substitution reaction is-20 to 40 ℃; and/or
The reactant A comprises the following structural formula A 1 To A 6 At least one of:
Figure FDA0003106642520000041
wherein, the general formula A 1 To A 6 R in (1) 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 、R 31 、R 32 、R 33 、R 34 One selected from hydrogen atoms, halogen atoms, aromatic groups with 6 to 10 carbon atoms, halogenated aromatic groups with 6 to 10 carbon atoms, alkyl groups with 1 to 10 carbon atoms, halogenated alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 1 to 10 carbon atoms, halogenated alkenyl groups with 1 to 10 carbon atoms, alkynyl groups with 1 to 10 carbon atoms, halogenated alkynyl groups with 1 to 10 carbon atoms, chain alkoxy groups with 2 to 10 carbon atoms, chain alkenyloxy groups with 2 to 10 carbon atoms, chain alkynyloxy groups with 2 to 10 carbon atoms, cyclic alkoxy groups with 3 to 10 carbon atoms, cyclic alkenyloxy groups with 3 to 10 carbon atoms, trialkylsilyl groups with 3 to 20 carbon atoms, trialkylsiloxy groups with 3 to 20 carbon atoms, aryl-containing silicon groups, pyridyl groups, thienyl groups, phenol groups, alkyl-containing phenol groups, alkenyl-containing phenol groups, alkyne-containing phenol groups, nitrile-containing phenol groups, monohalogenated phenol groups and halogenated phenol groups;
m, n, o, p, y and z are independent integers of 0-10;
and/or
The first substitution reaction comprises the steps of carrying out a front-stage substitution reaction and then carrying out a rear-stage substitution reaction; the former-stage substitution reaction is a substitution reaction stage of gradually adding the reactant A into the first non-aqueous solution containing the reactant B until the addition is finished and then continuing to react for 1-2 hours, and the later-stage substitution reaction is a stage of finishing the addition of the reactant A and continuing to react for 1-2 hours until the substitution reaction is finished; and the temperature of the front-stage substitution reaction is-20-0 ℃; the temperature of the back-stage substitution reaction is 0-40 ℃; and/or
The first non-aqueous solution is selected from at least one of acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N-hexane, N-heptane, cyclohexane, benzene, toluene, xylene; and/or
The M is 1 、M 2 When independently selected from any one of chlorine, bromine and iodine atoms, the method also comprises the following steps:
carrying out a second substitution reaction on the halogenated phosphate product containing the branched chain and shown in the structural formula I and generated by the first substitution reaction and fluoride in a second non-aqueous solution to generate the general formula I 1 The branched difluorophosphate ester-containing product shown;
Figure FDA0003106642520000051
8. the method for producing according to claim 7, characterized in that: the product of halogenated phosphate ester containing branched chain and fluoride shown in the structural formula I are mixed according to a molar ratio of 1: (1-6) in the second non-aqueous solution and carrying out the second substitution reaction; and/or
The mass ratio of the branched halogenated phosphate ester product shown in the structural formula I to the second non-aqueous solution is 1: (1-10); and/or
The temperature of the second substitution reaction is-20 to 80 ℃; and/or
The fluoride is at least one of hydrogen fluoride, triethylamine hydrogen fluoride, pyridine hydrogen fluoride, potassium fluoride, sodium fluoride, magnesium fluoride, zinc fluoride, aluminum fluoride, cesium fluoride, antimony trifluoride, antimony pentafluoride, sulfur tetrafluoride and sulfur hexafluoride; and/or
The second non-aqueous solution is selected from at least one of acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N-hexane, N-heptane, cyclohexane, benzene, toluene, xylene.
9. An electrolyte additive, characterized in that: a branched halophosphate comprising the branched halophosphate of any one of claims 1 to 5 or prepared by the method of any one of claims 6 to 8.
10. An electrolyte comprising an additive, characterized in that: the additive is the electrolyte additive of claim 9, and the mass concentration of the halogenated phosphate containing the branched chain in the electrolyte is 0.1-5%.
11. A secondary battery, characterized in that: comprising the electrolyte of claim 10.
CN202110645241.1A 2021-06-08 2021-06-08 Halogenated phosphate containing branched chain, preparation method and application thereof Pending CN115448947A (en)

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