Vinylene carbonate mixture and method for its preparing

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes a method for preparing vinylene carbonate mixture. Method involves interaction of monohaloethylene carbonate of the formula (II): wherein X means halogen atom with a dehydrohalogenating agent at temperature in the range 40-80°C but preferably at 60°C in organic solvent medium wherein ethylene carbonate is used as an organic solvent. As a dehydrohalogenating agent method involves using amine, in particular, trialkylamine but preferably triethylamine, and monochloroethylene carbonate is used as monohaloethylene carbonate preferably. Interaction is carried out in inert gas atmosphere preferably. Invention provides preparing vinylene carbonate mixture by a simple and economy method with the high content of vinylene carbonate in the end product. Method provides easily isolation of vinylene carbonate from the prepared mixture by distillation off, for example, under vacuum in the film evaporator. Also, invention relates to a crude vinylene carbonate mixture prepared by above described method that is designated as an additive for lithium-ionic batteries as a component of surface coating material as a monomer for preparing polyvinylene carbonate.

EFFECT: improved preparing method.

7 cl, 3 ex

 

The present invention relates to vinylnorbornene mixture used, for example, as an additive for lithium-ion batteries, as a component of materials, surface coatings or as a monomer for polyvinylcarbazole, and to the way it was received.

In SoC., 77, 3789-3793 (1955) described a method of obtaining vinylnorbornene, in which the first stage of the synthesis by the chlorination of ethylene carbonate resulting gain monochlorotoluene. In the second stage by boiling under reflux during the night, spend the reaction solution monochloracetate in diethyl ether with triethylamine and removal of hydrogen chloride receive vinylenecarbonate. After removal of the diethyl ether and distillation to yield 59% receive raw vinylenecarbonate and subsequent rectification it clear. Negative features of this method are, therefore, the long duration of the reaction, relatively complex processing of the reaction product to remove unwanted components, such as solvents, and relatively low yield of the target product.

Closest to the claimed method is a method described in JP 11-180974 in which vinylenecarbonate produced by the interaction of chlorochromate with triethylamine at 40-90°in the medium of organic solvent, and as the e organic solvent used tetrahydrofuran.

The aim of the present invention is to develop a method of obtaining vinylnorbornene mixture, which makes it simple and economical to obtain a product with a high content of vinylnorbornene that can be selected.

This objective is achieved by providing a method according to claim 1 of the claims. Benefits and/or preferred variants of this method are presented in the dependent claims.

Thus, the object of the invention is a method for vinylnorbornene reaction mixture monocalciumphosphate formula (II)

in which X denotes a halogen atom, with dehydrohalogenation agent at an elevated temperature in the environment of an organic solvent, characterized in that the organic solvent used, the ethylene carbonate resulting.

The tetrahydrofuran used in the implementation of the known method, in the method proposed in accordance with the invention, substituted ethylene carbonate resulting in the solvent during the reaction dehydrohalogenating. This allows you to reduce the presence in the reaction mixture of compounds that impede the flow of the process, and thus to simplify the treatment of the reaction mixture. Moreover, in the method in accordance with the invention have significantly higher output is a product, than in the known method. When applying for certain purposes, for example, as a solvent for non-aqueous electrolytes in lithium-ion batteries, the need for allocation of ethylene carbonate resulting, in the reaction mixture, no, because, on the contrary, in fact, for this purpose you must use vinylenecarbonate/efilecabinet mixture of this type.

Experiments show that vinylenecarbonate highly sensitive to temperature and at temperatures above 60°able to decompose within a few hours, and at temperatures above 80°With - even for a few minutes. However, at elevated temperatures the reactions of elimination usually are achieving increased product yield. In accordance with the invention it was found that the reaction of dehydrohalogenating can successfully take place at a temperature in the range of 40-80°C, preferably at about 60°C. In this case, the reaction can be completed within 1-4 hours, preferably for about 2 hours under such reaction conditions, the yield of crude vinylnorbornene usually exceeds 80%.

In the implementation proposed in accordance with the invention method, you can use a regular dehydrohalogenation agents, such as solutions of hydroxides of alkali metals, amines, and calamity or heterocyclic nitrogen compounds. Preferred trialkylamines, particularly preferred triethylamine.

The method in accordance with the invention is particularly successfully carried out in the presence of monoclonalantibody used as monocalciumphosphate the above formula (II).

Moreover, when conducting the reaction in accordance with the invention to prevent decomposition reactions are especially effective atmosphere of protective gas. Examples of suitable protective gases are nitrogen and inert gases such as argon. Thus, the use of the stabilizer, which usually add to vinylnorbornene obtained as the reaction product becomes optional.

For completeness and uniformity of the reaction, it is expedient, in addition, to ensure efficient mixing of the reaction components.

Monohalomethanes used as starting compounds in accordance with the invention, are known compounds which can be obtained, for example, photochemical gorodilova of ethylene carbonate resulting or gorodilova initiated azoisobutyronitrile (AIBN), using, for example, sulfurylchloride. The residual amount of AIBN or sulfurylchloride in monocalciumphosphate considered acceptable. When implementing the method in accordance with izobreteny is m such residual amounts of sulfurylchloride can be removed, for example, using the corresponding excess agent dehydrohalogenating, such as triethylamine.

While in the implementation of this method processes the received raw vinylnorbornene conduct simple distillation, in this case, as it was set during the creation of the present invention may reduce product yield. Thus, in accordance with the invention, it is preferable application of the processing method which is guaranteed impact on vinylenecarbonate appropriate temperature evaporation within the minimum possible period of time. This is achieved, for example, by distillation under vacuum in a film evaporator at a bath temperature of about 100°and under the pressure of about 5 mbar. This allows you to get vinylenecarbonate directly from the reaction product of dehydrohalogenation in the form of colorless product with a yield of at least about 75%. It is known the use of vinylnorbornene as a nonaqueous solvent for an electrolytic batteries, in particular lithium-ion batteries (JP 05-085138, JP 08-096852, EP 0582410). Also in the prior art it is known the use of vinylnorbornene as the monomer for based on homopolymers or copolymers (SU 413807, US 4098771, EP 0110281). In the patent US 5274039 described using vinylnorbornene as opponent to obtain compositions for coatings.

Vinylenecarbonate obtained by implementing the method in accordance with the invention, can be used for various purposes, for example as an additive for lithium-ion batteries, in particular as a solvent for non-aqueous electrolyte, as a component of materials, surface coatings or as a monomer for polyvinylcarbazole. During polymerization to obtain this last it is possible to synthesize high molecular weight colorless polymers by subsequent hydrolysis which it is possible to obtain water-soluble polymers.

The invention is illustrate in more detail the examples below.

Example 1

250-ml chetyrehpolnye the reaction apparatus with a double jacket, equipped with accurate glass stirrer, an electric motor for the agitator, coiled refrigerator, drip funnel and reaches the liquid phase, temperature, rinsed with argon. Further, when continuous purging with argon download 0,420 mol of chlorochromate and 84 ml of anhydrous ethylene carbonate resulting. Using laboratory heating bath the temperature of the contents was raised to 57,6°C. Then through an addition funnel over 25 min with stirring, added dropwise 0,630 mole of triethylamine. During this period the temperature of the contents is supported within 56-59°C. When the addition of triethylamine complete, the reaction mixture is stirred at about 60°C for 1 h then in a rotary evaporator at a bath temperature of 40°and under a residual pressure of 150 mbar distilled off excess triethylamine. The number of vinylnorbornene contained in raw vinylnorbornene mixture is 77.2% of theoretical.

Comparative example 1

Vinylenecarbonate get in the way described in SOC., 77, 3789-3793 (1955). To this end, the argon purge the reaction apparatus described in example 1. Then, while blowing argon download 0,280 mol of chlorochromate and 33.4 ml of ultra-pure tert-butyl methyl ether and use of laboratory heating bath the mixture is heated to 37.8°C. Then through an addition funnel over 50 min with stirring, added dropwise 0,350 mole of triethylamine. During this period the temperature of the contents maintained within the range of 37-40°C. After that the reaction mixture with stirring and maintained at about 40°C for 50 minutes Number of vinylnorbornene contained in raw vinylnorbornene mixture is only 26.6% of theoretical.

Example 2

Raw vinylnorbornene mixture obtained in example 1, is treated by distillation under vacuum film evaporator (internal diameter 40 mm, length of the rotor 25 cm). The bath temperature is approx the RNC 100° C, and the residual pressure is approximately 5 mbar. When the feed rate of approximately 3 ml/min after about 70 min in the form of oils are transparent, slightly yellowish distillate. The yield of purified vinylnorbornene is 73,3%.

1. The method of obtaining vinylnorbornene mixture, characterized in that monohalomethanes formula (II)

where X denotes a halogen atom interacts with dehydrohalogenation agent at a temperature in the range of 40-80°C, preferably at 60°With, in the environment of an organic solvent, and the organic solvent used ethylene carbonate resulting.

2. The method according to claim 1, characterized in that the reaction is carried out within 1-4 hours, preferably about 2 hours

3. The method according to claim 1, characterized in that as dehydrohalogenating agent use Amin.

4. The method according to any one of claims 1 to 3, characterized in that as dehydrohalogenating agent use trialkylamine, preferably triethylamine.

5. The method according to any one of claims 1 to 4, characterized in that as monocalciumphosphate use monochlorotoluene.

6. The method according to any one of claims 1 to 5, characterized in that the reaction is performed in a protective gas atmosphere.

7. Raw vinylnorbornene mixture obtained by the method according to claim 1, the additive for retieving batteries as a component material of the surface coating or as a monomer for polyvinylcarbazole.



 

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