KR101846111B1 - Preparation Method of 1, 3, 6-Hexanetricarbonitrile - Google Patents
Preparation Method of 1, 3, 6-Hexanetricarbonitrile Download PDFInfo
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Abstract
본 발명은 새로운 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile) 제조방법을 개시한다. 전통적인 공정과 완전히 다른 제조방법인 것 이외에도, 나트륨이 존재하는 조건 하에 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)를 제조할 때 존재하는 안전 문제를 극복하여 공정을 더욱 안전하게 하였고, 대규모 공업생산 수요를 실현하였다. 또한 본 발명의 제조방법은 생산성이 높고, 원재료를 쉽게 얻으며 반응 제어가 간단하고 제품 순도가 높은 등의 장점을 구비한다.The present invention discloses a process for the preparation of novel 1,3,6-hexanetricarbonitrile. In addition to being a completely different manufacturing process from the traditional process, overcoming the safety problems existing when 1,3,6-hexanetricarbonitrile is prepared under the presence of sodium, And realized large-scale industrial production demand. Further, the production method of the present invention has advantages such as high productivity, easy raw material acquisition, simple reaction control, and high product purity.
Description
본 발명은 화합물 제조의 기술영역에 속하며, 구체적으로 1,3,6-헥산트리카르보니트릴(1, 3, 6-Hexanetricarbonitrile)의 제조방법에 관한 것이다.The present invention belongs to the technical field of the preparation of compounds, and more particularly to a process for the preparation of 1,3,6-hexanetricarbonitrile.
1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)은 주로 유기합성 중간체, 높은 비등점 용제, 전해액 첨가제로 사용된다. 현재 전기자동차와 전기자전거가 발전함에 따라 리튬이온 배터리 에너지 밀도가 수요를 만족시킬 수 없다. 고전압을 발전시키는 것은 향후 연구방향 중 하나이다. 전통적인 탄산에스테르(carbonic ester) 전해액은 4, 5V 전압 이하에서 분해되고, 전해액의 지속적인 분해는 배터리 성능에 심각한 영향을 줄 수 있으며, 전해액 중 전해액 첨가제를 첨가하여 배터리의 성능을 높이는 것이 매우 시급하다. 1,3,6-Hexanetricarbonitrile is mainly used as an organic synthesis intermediate, a high boiling point solvent, and an electrolyte additive. As electric vehicles and electric bicycles are developed, the lithium ion battery energy density can not satisfy the demand. Developing high voltage is one of the future research directions. Conventional carbonic ester electrolytes are decomposed below a voltage of 4 and 5 V, and continuous decomposition of the electrolyte can seriously affect the performance of the battery. It is very urgent to increase the performance of the battery by adding an electrolyte additive in the electrolyte.
러시아응용화학잡지(Journal of Applied Chemistry of the USSR，1972，2683-2684)는 나트륨의 존재 하에 2-아미노-시클로펜텐-1-니트릴(2-Amino-1-Cyclopentene-1-nitrile)과 아크릴로니트릴(Acrylonitrile)에서 1,3,6-헥산트리카르보니트릴(1，3，6-Hexanetricarbonitrile)을 제작하는 방법을 개시하였다. 그러나 나트륨의 사용은 공정의 안전성이 높지 않고 원료 2-아미노-시클로펜텐-1-니트릴(2-Amino-1-Cyclopenten-1-nitrile)를 쉽게 얻을 수 없고 공업화가 어려운 문제를 초래하였다. 그래서 공업화 생산이 가능한 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법 연구는 우리가 끊임없이 추구하는 목표가 되었다. (2-Amino-1-cyclopentene-1-nitrile) and acryloyl-1-nitryl in the presence of sodium Discloses a method for producing 1,3,6-hexanetricarbonitrile in acrylonitrile. However, the use of sodium has not resulted in high safety of the process and can not easily obtain the raw material 2-amino-1-cyclopentene-1-nitrile and has caused difficulties in industrialization. Thus, research into the production of 1,3,6-hexanetricarbonitrile, which is capable of producing industrialization, has become a constantly pursuing goal.
본 발명은 종래 기술 중 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile) 제조 방법이 공업화가 어렵고 제조한 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 순도가 낮으며 백색도가 떨어지는 기술적인 문제를 해결하기 위한 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법을 제공하는 것이다. 그래서 생산성이 높고, 원재료를 쉽게 얻으며, 반응 제어가 간단하고, 제품 순도가 높은 효과를 거둘 수 있다.The present invention relates to a process for preparing 1,3,6-hexanetricarbonitrile in the prior art, wherein 1,3,6-hexanetricarbonitrile (1,3,6-hexanetricarbonitrile) (1,3,6-hexanetricarbonitrile) for solving the technical problem of low purity and low whiteness of hexanetricarbonitrile (1,3,6-hexanetricarbonitrile). Thus, the productivity is high, the raw material is easily obtained, the reaction control is simple, and the product purity is high.
본 발명이 그 목적을 실현하기 위해 사용하는 기술방안은 다음과 같다.The technical scheme used by the present invention to realize the object is as follows.
1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법은 아래 단계를 포함한다.The process for preparing 1,3,6-hexanetricarbonitrile includes the following steps.
A. 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)의 제조：1, 4-디옥산(1,4-Dioxane)을 반응 용제로 하여, 1,6-디클로로-헥센(1,6-dichloro-2-hexene)과 NaCN를 1, 4-디옥산(1,4-Dioxane)에 놓고 40-101℃에서 치환반응을 진행하여 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)을 얻는다.A. Preparation of 1,6-dicyano-2-hexene Using 1,4-dioxane as a reaction solvent, 1,6-dicyano-2-hexene -Dicyano-2-hexene and NaCN were placed in 1,4-dioxane and the reaction was carried out at 40 to 101 ° C to obtain 1,6-dicyano-2- Hexene (1,6-dicyano-2-hexene).
B. 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조：단계 A에서 제조한 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)과 HCI 메틸알코올 용액을 40-60℃에서 4-6h 동안 반응한 후 NaCN를 첨가하여 40-101℃에서 치환반응을 진행하여 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)을 얻는다.B. Preparation of 1,3,6-hexanetricarbonitrile: To a solution of 1,6-dicyano-2-hexene prepared in Step A, And HCI methyl alcohol solution were reacted at 40-60 ° C for 4-6h, NaCN was added and the reaction was carried out at 40-101 ° C to obtain 1,3,6-hexanetricarbonitrile ).
단계A와 단계B의 치환반응의 반응시간은 2-7h이다.The reaction time of the substitution reaction of Step A and Step B is 2-7 h.
단계A 중 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene)과 NaCN의 몰비는 1：（2-3）이다.The molar ratio of 1,6-dichloro-2-hexene to NaCN in step A is 1: (2-3).
단계B 중 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)과 HCl 메틸알코올 용액이 반응하여 얻은 산물과 NaCN의 몰비는 1：（1-2）이다. In step B, the molar ratio of the product obtained by reacting 1,6-dicyano-2-hexene with the HCl methyl alcohol solution is 1: (1-2).
단계A 중 촉매제를 첨가하였으며 상기 촉매제는 CuCl, Cu2O, CuBr의 1종에서 선택한다. A catalyst is added in step A and the catalyst is selected from one of CuCl, Cu 2 O, and CuBr.
1mol의 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene)에서 사용하는 반응 용제 ：1, 4-디옥산(1,4-Dioxane)의 양은 200-800ml이다.The amount of 1,4-dioxane used as a reaction solvent in 1 mol of 1,6-dichloro-2-hexene is 200-800 ml.
1mol의 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene)에서 사용하는 촉매제의 양은 0.5g이다. The amount of catalyst used in 1 mol of 1,6-dichloro-2-hexene is 0.5 g.
단계B 중 1mol의 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene)에서 사용하는 HCl의 메틸알코올 용액의 양은 90g이다.The amount of the methyl alcohol solution of HCl used in 1 mol of 1,6-dichloro-2-hexene in Step B is 90 g.
본 발명의 유익한 효과: 본 발명은 새로운 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법을 제공하였으며, 전통적인 공정과 완전히 다른 제조방법인 것 이외에도, 나트륨이 존재하는 조건 하에 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)를 제조할 때 존재하는 안전 문제를 극복하여 공정을 더욱 안전하게 하였고, 대규모 공업생산 수요를 실현하였다. 또한 본 발명의 제조방법은 생산성이 높고, 원재료를 쉽게 얻으며 반응 제어가 간단하고 제품 순도가 높은 등의 장점을 구비하였다. 본 발명에서 제조하는 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)은 양극 표면에서 막을 형성하여 과도 금속 이온이 고전압 하에서 전해액 분해를 촉매하는 것을 차단하여 배터리 성능을 높일 수 있다. Advantageous Effects of the Invention: The present invention provides a process for the preparation of novel 1,3,6-hexanetricarbonitrile, which, apart from being a completely different preparation process from the traditional process, (1,3,6-Hexanetricarbonitrile) under the conditions that make the process more safe and overcome the safety problems existing in the production of large-scale industrial production. Further, the production method of the present invention has advantages such as high productivity, easy raw material acquisition, simple reaction control, and high product purity. 1,3,6-Hexanetricarbonitrile (1,3,6-hexanetricarbonitrile) produced by the present invention forms a film on the surface of the anode to prevent the transient metal ions from catalyzing decomposition of the electrolyte under a high voltage, have.
도 1은 1% 1,2-디플루오르-1,3-프로펜 설폰(1，2-difluoro-1,3-propane sulfone)를 첨가한 배터리와 기초 전해액 첨가제를 첨가한 배터리를 65℃에서 50바퀴 순환한 전후 EIS그림이다.1 is a graph showing a comparison between a battery containing 1% 1,2-difluoro-1,3-propane sulfone and a battery containing a basic electrolyte additive at 65 DEG C It is an EIS figure before and after the wheel circulation.
본 발명은 종래 기술 중 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile) 제조 방법이 공업화가 어렵고 제조한 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile) 순도가 낮으며 백색도가 떨어지는 기술적인 문제를 해결하기 위해 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법을 제공한 것이다. 그래서 생산성이 높고, 원재료를 쉽게 얻으며, 반응 제어가 간단하고, 제품 순도가 높은 효과를 거둘 수 있다. 그 중 본 방법 제조 중에서 사용하는 HCI 메틸알코올 용액은 시장에서 살 수 있다. HCI 기체를 메틸알코올 용액 중에 용해시켜 포화용액을 형성한다. 아래는 구체적인 실시예를 통해 본 발명을 더욱 설명하였다. The present invention relates to a process for preparing 1,3,6-hexanetricarbonitrile in the prior art, wherein 1,3,6-hexanetricarbonitrile (1,3,6-hexanetricarbonitrile) Hexanetricarbonitrile) is a process for preparing 1,3,6-hexanetricarbonitrile to solve the technical problem of low purity and low whiteness. Thus, the productivity is high, the raw material is easily obtained, the reaction control is simple, and the product purity is high. Among them, the HCI methyl alcohol solution used in the method production can be bought in the market. The HCI gas is dissolved in the methyl alcohol solution to form a saturated solution. The present invention is further illustrated by the following specific examples.
실시예1Example 1
1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법은 아래 단계를 포함한다.The process for preparing 1,3,6-hexanetricarbonitrile includes the following steps.
A. 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)의 제조：1, 4-디옥산(1,4-Dioxane)을 반응 용제로 하여, 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene)과 0.5g CuCl와 2mol NaCN를 1, 4-디옥산(1,4-Dioxane)에 놓고 40℃에서 치환반응을 2h 동안 진행하여 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)을 얻는다.A. Preparation of 1,6-dicyano-2-hexene Using 1,4-dioxane as a reaction solvent, 1,6-dicyano-2-hexene 2-hexene, 0.5 g CuCl and 2 mol NaCN were placed in 1,4-dioxane and the reaction was allowed to proceed at 40 ° C for 2 h. 6-dicyano-2-hexene is obtained.
B. 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조：단계A에서 제조한 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)와 90g HCl 메틸알코올 용액을 40℃에서 4h 동안 반응한 후 NaCN를 첨가하여 40℃에서 치환반응을 2h 동안 진행하여 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)을 얻는다. 계산 수율은 52.1%이고, 검측 제품의 순도는 99.55%, 제품 색 번호 APHA는 15, 제품 수분은 16PPM이다.B. Preparation of 1,3,6-hexanetricarbonitrile: To a solution of 1,6-dicyano-2-hexene prepared in Step A, And a 90g HCl methyl alcohol solution were reacted at 40 ° C for 4 hours, NaCN was added and the substitution reaction was carried out at 40 ° C for 2 hours to obtain 1,3,6-hexanetricarbonitrile . The calculated yield is 52.1%, the purity of the tested product is 99.55%, the product color number is 15, and the product moisture is 16PPM.
실시예2Example 2
1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법은 아래 단계를 포함한다.The process for preparing 1,3,6-hexanetricarbonitrile includes the following steps.
A. 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)의 제조：：1, 4-디옥산(1,4-Dioxane)을 반응 용제로 하여, 1mol 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene), 0.5g Cu2O과 2.5g NaCN을 1, 4-디옥산(1,4-Dioxane)에 놓고 80℃에서 치환반응을 5h 동안 진행하여 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)을 얻는다.A. Preparation of 1,6-dicyano-2-hexene Using 1, 4-dioxane as a reaction solvent, 1 mol of 1,6-dicyano- - 1, 6-dichloro-2-hexene, 0.5 g Cu 2 O and 2.5 g NaCN were placed in 1,4-dioxane and the substitution reaction was carried out at 80 ° C. for 5 h To obtain 1,6-dicyano-2-hexene.
B. 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조：단계A에서 제조한 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)와 90g HCl 메틸알코올 용액을 50℃에서 5h 동안 반응한 후 NaCN를 첨가하여 80℃에서 치환반응을 5h 동안 진행하여 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)을 얻는다. 계산 수율은 61.2%이고, 검측 제품의 순도는 99.63%, 제품 색 번호 APHA는 13, 제품 수분은 18PPM이다.B. Preparation of 1,3,6-hexanetricarbonitrile: To a solution of 1,6-dicyano-2-hexene prepared in Step A, And a 90g HCl methyl alcohol solution are reacted at 50 ° C for 5 hours, NaCN is added and the substitution reaction is carried out at 80 ° C for 5 hours to obtain 1,3,6-hexanetricarbonitrile . The calculated yield is 61.2%, the purity of the tested product is 99.63%, the product color number APHA is 13, and the product moisture is 18PPM.
실시예3Example 3
1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법은 아래 단계를 포함한다.The process for preparing 1,3,6-hexanetricarbonitrile includes the following steps.
A. 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)의 제조：1, 4-디옥산(1,4-Dioxane)을 반응 용제로 하여, 1mol 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene), 0.5g CuBr과 2.3mol NaCN을 1, 4-디옥산(1,4-Dioxane)에 놓고 101℃에서 치환반응을 7h 동안 진행하여 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)을 얻는다.A. Preparation of 1,6-dicyano-2-hexene Using 1, 4-dioxane as a reaction solvent, 1 mol of 1,6-dicyano- Dichloro-2-hexene, 0.5 g CuBr and 2.3 mol NaCN were placed in 1,4-dioxane and the reaction was allowed to proceed at 101 ° C for 7 h 1,6-dicyano-2-hexene is obtained.
B. 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조：단계A에서 제조한 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)와 90g HCl 메틸알코올 용액을 60℃에서 6h 동안 반응한 후 NaCN를 첨가하여 101℃에서 치환반응을 7h 동안 진행하여 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)을 얻는다. 계산 수율은 57.5%이고, 검측 제품의 순도는 99.54%, 제품 색 번호 APHA는 17, 제품 수분은 16PPM이다.B. Preparation of 1,3,6-hexanetricarbonitrile: To a solution of 1,6-dicyano-2-hexene prepared in Step A, And 90g HCl methyl alcohol solution were reacted at 60 ° C for 6 hours, NaCN was added, and the substitution reaction was carried out at 101 ° C for 7 hours to obtain 1,3,6-hexanetricarbonitrile . The calculated yield is 57.5%, the purity of the tested product is 99.54%, the product color number APHA is 17, and the product moisture is 16PPM.
실시예4Example 4
1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법은 아래 단계를 포함한다.The process for preparing 1,3,6-hexanetricarbonitrile includes the following steps.
A. 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)의 제조：1, 4-디옥산(1,4-Dioxane)을 반응 용제로 하여, 1mol 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene), 0.5g Cu2O과 3mol NaCN을 1, 4-디옥산(1,4-Dioxane)에 놓고 60℃에서 치환반응을 3.5h 동안 진행하여 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)을 얻는다.A. Preparation of 1,6-dicyano-2-hexene Using 1, 4-dioxane as a reaction solvent, 1 mol of 1,6-dicyano- Dichloro-2-hexene, 0.5 g Cu 2 O and 3 mol NaCN were placed in 1,4-dioxane and the substitution reaction was carried out at 60 ° C for 3.5 h To obtain 1,6-dicyano-2-hexene.
B. 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조：단계A에서 제조한 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)과 90g HCl 메틸알코올 용액을 45℃에서 4.5h 동안 반응한 후 NaCN를 첨가하여 60℃에서 치환반응을 3.5h 동안 진행하여 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)을 얻는다. 계산 수율은 54.7%이고, 검측 제품의 순도는 99.58%, 제품 색 번호 APHA는 14, 제품 수분은 17PPM이다.B. Preparation of 1,3,6-hexanetricarbonitrile: To a solution of 1,6-dicyano-2-hexene prepared in Step A, And 90g HCl methyl alcohol solution were reacted at 45 ° C for 4.5 hours, and NaCN was added thereto. Subsequently, the substitution reaction was carried out at 60 ° C for 3.5 hours to obtain 1,3,6-hexanetricarbonitrile, . The calculated yield is 54.7%, the purity of the tested product is 99.58%, the product color number APHA is 14, and the product moisture is 17PPM.
실시예5Example 5
1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법은 아래 단계를 포함한다.The process for preparing 1,3,6-hexanetricarbonitrile includes the following steps.
A. 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)의 제조：1, 4-디옥산(1,4-Dioxane)을 반응 용제로 하여, 1mol 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene), 0.5g CuBr과 2.7mol NaCN을 1, 4-디옥산(1,4-Dioxane)에 놓고 92℃에서 치환반응을 6h 동안 진행하여 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)을 얻는다.A. Preparation of 1,6-dicyano-2-hexene Using 1, 4-dioxane as a reaction solvent, 1 mol of 1,6-dicyano- Dichloro-2-hexene, 0.5 g of CuBr and 2.7 mol of NaCN were placed in 1,4-dioxane and the reaction was allowed to proceed for 6 h at 92 ° C. 1,6-dicyano-2-hexene is obtained.
B. 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조：단계A에서 제조한 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)과 90g HCl 메틸알코올 용액을 55℃에서 5.5h 동안 반응한 후 NaCN를 첨가하여 92℃에서 치환반응을 6h 동안 진행하여 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)을 얻는다. 계산 수율은 59.3%이고, 검측 제품의 순도는 99.83%, 제품 색 번호 APHA는 10, 제품 수분은 17PPM이다.B. Preparation of 1,3,6-hexanetricarbonitrile: To a solution of 1,6-dicyano-2-hexene prepared in Step A, And 90g HCl methyl alcohol solution were reacted at 55 ° C for 5.5h, NaCN was added and the substitution reaction was carried out at 92 ° C for 6h to obtain 1,3,6-hexanetricarbonitrile . The calculated yield is 59.3%, the purity of the tested product is 99.83%, the product color number APHA is 10, and the product moisture is 17PPM.
1%의 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile) 첨가제를 첨가한 배터리와 기초 전해액을 첨가한 배터리를 각각 65℃에서 50바퀴를 순환시킨 후 비교한다. 그중 배터리의 양극이 5V LiNi0 .5Mn1 .5O4이고, 음극은 실리콘 카본 음극이다. 기초 전해액을 첨가한 배터리의 전해액은 DC/EMC=1/3，LiPF6：1.1M，FEC SN이다. 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile) 첨가제를 첨가한 배터리의 전해액은 DC/EMC=1/3，LiPF6：1.1M，FEC 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)이다. 비교 결과는 도 1을 참조한다. A battery containing 1% of 1,3,6-hexanetricarbonitrile (1,3,6-hexanetricarbonitrile) and a battery containing basic electrolyte are circulated at 65 ° C for 50 cycles and then compared. And of which the anode of the battery 5V LiNi 0 .5 Mn 1 .5 O 4, the negative electrode is a silicon carbon cathode. The electrolyte of the battery to which basic electrolyte is added is DC / EMC = 1/3, LiPF6: 1.1M, FEC SN. The electrolyte of the battery to which the 1,3,6-hexanetricarbonitrile additive was added was DC / EMC = 1/3, LiPF6: 1.1M, FEC 1,3,6-hexanetricarbonitrile 1,3,6-hexanetricarbonitrile. See FIG. 1 for comparison results.
도 1을 참조하면, 5V의 전압에서 1%를 첨가한 본 발명의 배터리는 고온 65℃에서 50바퀴 순환시킨 후 용량은 80% 이상을 유지하며, 기초 전해액을 첨가한 배터리는 고온 65℃에서 50바퀴를 순환시킨 후 용량은 단지 61%가 남은 것을 볼 수 있다. 이것은 본 발명의 첨가제 고온 순환 성능이 탁월하며, 배터리 용량 유지율이 더욱 높다는 것을 설명해 준다.Referring to FIG. 1, the battery of the present invention to which 1% is added at a voltage of 5 V is maintained at a rate of 80% or more after circulating 50 times at a high temperature of 65 ° C. After circulating the wheel, only 61% of the capacity remains. This explains that the additive high-temperature circulation performance of the present invention is excellent, and the battery capacity retention rate is higher.
Claims (8)
A. 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)의 제조：1, 4-디옥산(1,4-Dioxane)을 반응 용제로 하여, 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene)과 NaCN를 1, 4-디옥산(1,4-Dioxane)에 놓고 40-101℃에서 치환반응을 진행하여 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)을 얻는 단계A; 및
B. 단계A에서 제조한 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)과 HCI 메틸알코올 용액을 40-60℃에서 4-6h 동안 반응한 후 NaCN를 첨가하여 40-101℃에서 치환반응을 진행하여 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)을 얻는 단계B를 포함하는 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법.As a method for producing 1,3,6-hexanetricarbonitrile,
A. Preparation of 1,6-dicyano-2-hexene Using 1,4-dioxane as a reaction solvent, 1,6-dicyano-2-hexene Dichloro-2-hexene and NaCN were placed in 1,4-dioxane, and the reaction was carried out at 40-101 ° C to obtain 1,6-dicyano- Step A to obtain 2-hexene (1,6-dicyano-2-hexene); And
B. Reaction of 1,6-dicyano-2-hexene and HCI methyl alcohol solution prepared in step A at 40-60 ° C for 4-6 h followed by addition of NaCN 1,3,6-hexanetricarbonitrile (1,3,6-hexanetricarbonitrile) containing step B, which undergoes a substitution reaction at 40-101 DEG C to obtain 1,3,6-hexanetricarbonitrile , 6-hexanetricarbonitrile).
상기 단계A의 치환반응의 반응시간 및 상기 단계B의 치환반응의 반응시간은 각각 2-7h임을 그 특징으로 하는 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법.The method according to claim 1,
Wherein the reaction time of the substitution reaction in Step A and the reaction time of the substitution reaction in Step B are respectively 2-7 h, and the production of 1,3,6-hexanetricarbonitrile Way.
상기 단계A 중 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene)과 NaCN의 몰비는 1: (2-3)임을 그 특징으로 하는 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법.The method according to claim 1,
Wherein the molar ratio of 1,6-dichloro-2-hexene to NaCN in step A is 1: (2-3), and 1,3,6-hexanetricarbonyl (1,3,6-hexanetricarbonitrile).
상기 단계B 중 1,6-디시아노-2-헥센(1,6-dicyano-2-hexene)와 HCI 메틸알코올 용액이 반응하여 얻은 산물과 NaCN의 몰비는 1: (1-2)임을 그 특징으로 하는 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법.The method according to claim 1,
The product obtained by reacting 1,6-dicyano-2-hexene with HCI methyl alcohol solution in step B above and the NaCN molar ratio is 1: (1-2) (1, 3, 6-hexanetricarbonitrile).
상기 단계A 중 촉매제를 첨가하며, 상기 촉매제는 CuCl, Cu2O, CuBr 중에서 선택되는 적어도 어느 하나인 것을 그 특징으로 하는 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법.The method according to claim 1,
(1, 3 , 6-hexanetricarbonitrile), which is characterized in that at least one catalyst selected from the group consisting of CuCl, Cu 2 O and CuBr is added, ≪ / RTI >
상기 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene)의 1mol에 사용하는 반응 용제 4-디옥산(1,4-Dioxane1)의 양은 200-800ml임을 그 특징으로 하는 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법.The method according to claim 1,
The amount of the reaction solvent 4-dioxane used in 1 mol of the 1,6-dichloro-2-hexene is 200-800 ml. , 3,6-hexanetricarbonitrile.
상기 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene) 1mol에서 사용하는 촉매제의 양은 0.5g임을 그 특징으로 하는 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법.6. The method of claim 5,
1,3,6-hexanetricarbonitrile (1,3, 6-dichloro-2-hexene), which is characterized in that the amount of the catalyst used in 1 mol of 1,6-dichloro-2- 6-hexanetricarbonitrile).
단계B 중 1mol의 1,6-디클로로-2-헥센(1,6-dichloro-2-hexene)에서 사용하는 HCI 메틸알코올 용액의 양은 90g임을 그 특징으로 하는 1,3,6-헥산트리카르보니트릴(1,3,6-Hexanetricarbonitrile)의 제조방법.The method according to claim 1,
The amount of the HCI methyl alcohol solution used in 1 mol of 1,6-dichloro-2-hexene in Step B is 90 g, and 1,3,6-hexanetricarbonitrile (1,3,6-hexanetricarbonitrile).
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| CN105037203B (en) | 2015-08-27 | 2017-08-29 | 石家庄圣泰化工有限公司 | The preparation method of the nitrile of 1,3,6 hexane three |
| CN105481719B (en) * | 2015-12-24 | 2018-02-02 | 天津广顺化学科技有限公司 | The preparation method of the nitrile of 1,3,4,6-hexane four |
| CN112825372A (en) * | 2019-11-20 | 2021-05-21 | 珠海冠宇电池股份有限公司 | Electrolyte and electrochemical device containing same |
| CN112825373B (en) * | 2019-11-20 | 2022-06-14 | 珠海冠宇电池股份有限公司 | Non-aqueous electrolyte and lithium secondary battery comprising same |
| CN111129590A (en) * | 2019-12-23 | 2020-05-08 | 东莞市杉杉电池材料有限公司 | High-voltage lithium ion battery non-aqueous electrolyte and high-voltage lithium ion battery |
| CN111517986B (en) * | 2020-06-12 | 2023-09-26 | 上海如鲲新材料股份有限公司 | Novel method for preparing aliphatic tri-nitrile and aliphatic tri-nitrile prepared by novel method |
| CN114621116B (en) * | 2022-01-28 | 2023-08-22 | 苏州亚科科技股份有限公司 | Preparation method of 1,3, 6-hexanetrinitrile |
| CN116947695B (en) * | 2023-09-19 | 2023-12-26 | 上海如鲲新材料股份有限公司 | Preparation method and application of 1,3, 6-hexanetrinitrile |
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| JP2003183239A (en) | 2001-12-21 | 2003-07-03 | Asahi Kasei Corp | Low-colored trinitrile mixture and method for producing the same |
| CN104387291A (en) | 2014-11-07 | 2015-03-04 | 苏州亚科化学试剂股份有限公司 | Preparation method of 1,3,6-hexanetricarbonitrile |
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| US3190909A (en) * | 1961-11-06 | 1965-06-22 | Toyo Koatsu Ind Inc | Preparation of alpha, omegadicyanoolefins |
| DE10032881A1 (en) * | 2000-07-06 | 2002-01-17 | Bayer Ag | Process for the preparation of 1,3,6-hexane tricarbonitrile |
| CN105037203B (en) | 2015-08-27 | 2017-08-29 | 石家庄圣泰化工有限公司 | The preparation method of the nitrile of 1,3,6 hexane three |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003183239A (en) | 2001-12-21 | 2003-07-03 | Asahi Kasei Corp | Low-colored trinitrile mixture and method for producing the same |
| CN104387291A (en) | 2014-11-07 | 2015-03-04 | 苏州亚科化学试剂股份有限公司 | Preparation method of 1,3,6-hexanetricarbonitrile |
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| CN105037203B (en) | 2017-08-29 |
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