WO2017031871A1

WO2017031871A1 - Method for preparing 1,3,6-hexanetricarbonitrile

Info

Publication number: WO2017031871A1
Application number: PCT/CN2015/097346
Authority: WO
Inventors: 刘鹏; 田丽霞; 梅银平
Original assignee: 石家庄圣泰化工有限公司
Priority date: 2015-08-27
Filing date: 2015-12-15
Publication date: 2017-03-02
Also published as: CN105037203A; CN105037203B; KR101846111B1; KR20170035828A

Abstract

Provided is a method for preparing 1,3,6-hexanetricarbonitrile, comprising the following steps: A. preparation of 1,6-dicyano-2-butylene; and B. preparation of the 1,3,6-hexanetricarbonitrile. Provided is a new method for preparing 1,3,6-hexanetricarbonitrile. In addition to being a preparation method which is completely different from a traditional process, the preparation method also overcomes the safety problem present in the preparation of the 1,3,6-hexanetricarbonitrile in the presence of sodium, thus enabling the process to be safer, and at the same time, also achieving the requirements of large-scale industrial production. In addition, the preparation method of the present invention also has the advantages such as a high yield, easily available raw materials, a simple reaction control, and a high product purity.

Description

Method for preparing 1,3,6-hexane tricarbonitrile

Technical field

The invention belongs to the technical field of compound preparation, and in particular relates to a preparation method of 1,3,6-hexanetrinitrile.

Background technique

1,3,6-hexanetrinitrile is mainly used as an organic synthesis intermediate, a high boiling point solvent, and an electrolyte additive. At present, with the development of pure electric vehicles and electric bicycles, the energy density of lithium ion batteries can no longer meet the demand. Developing high voltage is one of the future research directions. The traditional carbonate electrolyte will decompose above 4,5V. The continuous decomposition of the electrolyte will seriously affect the performance of the battery. It is urgent to add electrolyte additives to the electrolyte to improve the performance of the battery.

The Journal of Applied Chemistry of the USSR, 1972, 2683-2684 discloses the preparation of 1,3,6- from 2-amino-1-cyclopentene-1-carbonitrile and acrylonitrile in the presence of sodium. The method of hexane tricarbonitrile, but the use of sodium leads to low safety of the process, and the raw material 2-amino-1-cyclopentene-1-nitrile is not easily obtained, and industrialization is difficult. Therefore, research on a method for the preparation of industrially produced 1,3,6-hexanetrinitrile is our constant pursuit.

Summary of the invention

The invention solves the technical problem that the method for preparing 1,3,6-hexanetrinitrile in the prior art is difficult to industrialize, and the preparation of 1,3,6-hexanetrizonitrile has low purity and poor whiteness, and provides a kind of 1 The preparation method of 3,6-hexane tricarbonitrile has the advantages of high internship yield, easy availability of raw materials, simple reaction control and high product purity.

The technical solution adopted by the present invention for achieving the purpose is:

A method for preparing 1,3,6-hexanetricarbonitrile comprises the following steps:

Preparation of A, 1,6-dicarbonitrile-2-butene: 1, 4-dichloro-2-butene and NaCN at 1,4-1,4-dioxane as a reaction solvent In the dioxane, the substitution reaction is carried out at 40-101 ° C to obtain 1,6-dicarbonitrile-2-butene;

Preparation of B,1,3,6-hexanetricarbonitrile: The 1,6-dicarbonitrile-2-butene prepared in the step A is reacted with a HCl methanol solution at 40-60 ° C for 4-6 h, and then The substitution reaction was carried out by adding NaCN at 40 to 101 ° C to obtain 1,3,6-hexanetricarbonitrile.

The reaction time of the substitution reaction in Step A and Step B was 2-7 h.

The molar ratio of 1,6-dichloro-2-butene to NaCN in step A is 1: (2-3).

The molar ratio of the product obtained by the reaction of 1,6-dicarbonitrile-2-butene with HCl in methanol in step B is 1: (1-2).

Further, a catalyst is added in the step A, and the catalyst is selected from one of CuCl, Cu ₂ O, and CuBr.

The amount of the reaction solvent 1,4-dioxane used for 1 mol of 1,6-dichloro-2-butene is 200-800 ml.

The amount of the catalyst used for 1 mol of 1,6-dichloro-2-butene was 0.5 g.

The amount of 1 mol of 1,6-dichloro-2-butene used in step B in methanol was 90 g.

The invention has the beneficial effects that the present invention provides a novel preparation method of 1,3,6-hexanetrinitrile, which overcomes the existence condition of sodium in addition to the completely different preparation method from the conventional process. The safety problem of the preparation of 1,3,6-hexanetricarbonitrile makes the process safer, and also realizes the need for large-scale industrial production. In addition, the preparation method of the invention has high yield and easy raw materials. It has the advantages of simple reaction control and high product purity. At the same time, the 1,3,6-hexanetriazonitrile prepared by the invention can form a film on the surface of the positive electrode, and the transition metal ions are blocked to catalyze the decomposition of the electrolyte at a high voltage, thereby improving the battery performance.

DRAWINGS

1 is an EIS diagram of a battery to which 1% 1,2-difluoro-1,3-propane sultone was added and a battery to which a base electrolyte additive was added, respectively, at a temperature of 65 ° C for 50 weeks.

detailed description

The invention solves the technical problem that the method for preparing 1,3,6-hexanetrinitrile in the prior art is difficult to industrialize, and the preparation of 1,3,6-hexanetrizonitrile has low purity and poor whiteness, and provides a kind of 1 The preparation method of 3,6-hexanetricarbonitrile can achieve high yield, easy availability of raw materials, simple reaction control and high purity of the product, wherein the HCl methanol solution used in the preparation of the method can be purchased on the market. This is to dissolve the HCl gas into a methanol solution to form a saturated solution. The present invention will be further described below in conjunction with specific examples.

Example 1

Preparation of A,1,6-dicarbonitrile-2-butene: 1 mol of 1,6-dichloro-2-butene, 0.5 g of CuCl and 2 mol of NaCN were prepared using 1,4-dioxane as a reaction solvent. The substitution reaction was carried out in 1,4-dioxane at 40 ° C for 2 h to obtain 1,6-dicarbonitrile-2-butene;

Preparation of B,1,3,6-hexanetricarbonitrile: The 1,6-dicarbonitrile-2-butene prepared in Step A was reacted with 90 g of HCl in methanol at 40 ° C for 4 h, then NaCN was added thereto at 40 The substitution reaction was carried out at ° C for 2 h to obtain 1,3,6-hexanetrizonitrile, the calculated yield was 52.1%, the purity of the test product was 99.55%, the product color number was APHA, and the product moisture was 16 PPM.

Example 2

Preparation of A, 1,6-dicarbonitrile-2-butene: using 1,4-dioxane as a reaction solvent, 1 mol of 1,6-dichloro-2-butene, 0.5 g of Cu ₂ O and 2.5 mol of NaCN was placed in 1,4-dioxane, and the substitution reaction was carried out at 80 ° C for 5 h to obtain 1,6-dicarbonitrile-2-butene;

Preparation of B,1,3,6-hexanetricarbonitrile: The 1,6-dicarbonitrile-2-butene prepared in Step A was reacted with 90 g of HCl in methanol at 50 ° C for 5 h, then NaCN was added thereto at 80 The substitution reaction was carried out at ° C for 5 h to obtain 1,3,6-hexanetrizonitrile, the calculated yield was 61.2%, the purity of the test product was 99.63%, the product color number was APHA, and the product moisture was 18 PPM.

Example 3

Preparation of A, 1,6-dicarbonitrile-2-butene: using 1,4-dioxane as a reaction solvent, 1 mol of 1,6-dichloro-2-butene, 0.5 g of CuBr and 2.3 mol of NaCN Put in 1,4-dioxane, and carry out a substitution reaction at 101 ° C for 7 h to obtain 1,6-dicarbonitrile-2-butene;

Preparation of B,1,3,6-hexanetricarbonitrile: The 1,6-dicarbonitrile-2-butene prepared in the step A was reacted with 90 g of a HCl methanol solution at 60 ° C for 6 h, and then NaCN was added thereto at 101. The substitution reaction was carried out at ° C for 7 h to obtain 1,3,6-hexanetricarbonitrile, the calculated yield was 57.5%, the purity of the test product was 99.54%, the product color number was APHA, and the product moisture was 16 PPM.

Example 4

Preparation of A, 1,6-dicarbonitrile-2-butene: using 1,4-dioxane as a reaction solvent, 1 mol of 1,6-dichloro-2-butene, 0.5 g of Cu ₂ O And 3 mol of NaCN was placed in 1,4-dioxane, and the substitution reaction was carried out at 60 ° C for 3.5 h to obtain 1,6-dicarbonitrile-2-butene;

Preparation of B,1,3,6-hexanetricarbonitrile: The 1,6-dicarbonitrile-2-butene prepared in step A was reacted with 90 g of HCl in methanol at 45 ° C for 4.5 h, then NaCN was added thereto. 60 ° C The substitution reaction was carried out for 3.5 hours to obtain 1,3,6-hexanetricarbonitrile, and the calculated yield was 54.7%. The purity of the test product was 99.58%, the product color number was APHA, and the product moisture was 17 PPM.

Example 5

Preparation of A, 1,6-dicarbonitrile-2-butene: using 1,4-dioxane as a reaction solvent, 1 mol of 1,6-dichloro-2-butene, 0.5 g of CuBr and 2.7 mol NaCN was placed in 1,4-dioxane, and the substitution reaction was carried out at 92 ° C for 6 h to obtain 1,6-dicarbonitrile-2-butene;

Preparation of B,1,3,6-hexanetricarbonitrile: The 1,6-dicarbonitrile-2-butene prepared in the step A was reacted with 90 g of a HCl methanol solution at 55 ° C for 5.5 h, and then NaCN was added thereto. The substitution reaction was carried out at 92 ° C for 6 h to obtain 1,3,6-hexanetricarbonitrile, the calculated yield was 59.3%, the purity of the test product was 99.83%, the product color number was APHA, and the product moisture was 17 PPM.

The battery to which the 1% 1,3,6-hexane tricarbonitrile additive was added and the battery to which the base electrolyte was added were respectively circulated at 65 ° C for 50 weeks, and the comparison was carried out, wherein the positive electrode of the battery was 5 V LiNi _0.5 Mn _1.5 O ₄ , the negative electrode is a silicon carbon negative electrode; the electrolyte of the battery with the base electrolyte is DC/EMC=1/3, LiPF6: 1.1M, FEC SN; battery electrolysis with 1,3,6-hexane trinitrile additive The liquid was DC/EMC=1/3, LiPF6: 1.1 M, FEC 1,3,6-hexanetrizonitrile, and the comparison results are shown in Fig. 1.

As can be seen from Fig. 1, at a voltage of 5 V, the battery to which 1% of the present invention is added is kept at a high temperature of 65 ° C for 50 weeks, the capacity is maintained at 80% or more, and the battery to which the base electrolyte is added is circulated at a high temperature of 65 ° C. After 50 weeks, the capacity was only 61%, indicating that the additive of the present invention has superior high-temperature cycle performance and higher battery capacity retention rate.

Claims

A method for preparing 1,3,6-hexanetricarbonitrile, comprising the steps of:

The method for preparing 1,3,6-hexanetrinitrile according to claim 1, wherein the reaction time in the substitution reaction in the step A and the step B is 2-7 h.

The method for preparing 1,3,6-hexanetrinitrile according to claim 1, wherein the molar ratio of 1,6-dichloro-2-butene to NaCN in step A is 1: ( 2-3).

The method for preparing 1,3,6-hexanetrinitrile according to claim 1, wherein the product obtained by reacting 1,6-dicyano-2-butene with HCl in methanol in step B is The molar ratio of NaCN is 1: (1-2).

The method for preparing 1,3,6-hexanetricarbonitrile according to claim 1, wherein a catalyst is further added to the step A, and the catalyst is selected from the group consisting of CuCl, Cu ₂ O and CuBr. Kind.

The method for preparing 1,3,6-hexanetrinitrile according to claim 1, wherein 1 mol of the reaction solvent for 1,6-dichloro-2-butene is 1,4-dioxane The amount of the alkane is 200-800 ml.

The process for producing 1,3,6-hexanetricarbonitrile according to claim 1, wherein the amount of the catalyst used for 1 mol of 1,6-dichloro-2-butene is 0.5 g.

A method for preparing 1,3,6-hexanetrinitrile according to claim 1, characterized in that The amount of 1 mol of 1,6-dichloro-2-butene used in step B in MeOH methanol was 90 g.