KR20140079956A - Method of refining 2-cyano-para-phenylenediamine - Google Patents

Method of refining 2-cyano-para-phenylenediamine Download PDF

Info

Publication number
KR20140079956A
KR20140079956A KR1020120149191A KR20120149191A KR20140079956A KR 20140079956 A KR20140079956 A KR 20140079956A KR 1020120149191 A KR1020120149191 A KR 1020120149191A KR 20120149191 A KR20120149191 A KR 20120149191A KR 20140079956 A KR20140079956 A KR 20140079956A
Authority
KR
South Korea
Prior art keywords
cyano
phenylenediamine
para
column
purifying
Prior art date
Application number
KR1020120149191A
Other languages
Korean (ko)
Inventor
이효진
Original Assignee
코오롱인더스트리 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to KR1020120149191A priority Critical patent/KR20140079956A/en
Publication of KR20140079956A publication Critical patent/KR20140079956A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/51—Phenylenediamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings

Abstract

A method of purifying 2-cyano-para-phenylenediamine according to the present invention is characterized by inserting 2-cyano-para-phenylenediamine into a distillation column and purifying the product to have 0.5-4 of reflux ratio under the condition having temperature of the bottom of the column is 150-250°C and temperature of the top of the column is 150-230°C. The present invention easily controls the purification of 2-cyano-para-phenylenediamine and has high yield of purified 2-cyano-para-phenylenediamine whereby mass-production is enabled. Further, the product obtained is purified 2-cyano-para-phenylenediamine having purity more than or equal to 97% which exhibits light beige or bright yellow colors based on high purification efficiency.

Description

2-시아노-파라페닐렌디아민의 정제방법{Method of refining 2-cyano-para-phenylenediamine}Method for refining 2-cyano-para-phenylenediamine < RTI ID = 0.0 >

본 발명은 2-시아노-파라페닐렌디아민의 정제방법에 관한 것으로서, 구체적으로는 정제공정의 컨트롤이 용이하며 고수득율로 대량생산이 가능하며 정제효율도 뛰어난 2-시아노-파라페닐렌디아민의 정제방법에 관한 것이다.The present invention relates to a process for purifying 2-cyano-para-phenylenediamine, and more particularly, to a process for purifying 2-cyano-paphenylenediamine which is easy to control the purification process and which can be mass- And a method for purifying the same.

방향족 아민은 아라미드 섬유의 중합 원료 중의 하나로 사용된다. 기존의 아라미드 섬유의 경우 방향족아민으로서 파라페닐렌디아민을 사용하여 중합한다. 그러나 이러한 방향족 아민의 경우 자연변색이 잘 일어나며, 특히 용해 및 용융 등 액체의 상태에서 더 빠른 속도로 변색된다.Aromatic amines are used as one of the polymerization raw materials of aramid fibers. In the case of conventional aramid fibers, p-phenylenediamine is used as the aromatic amine. However, these aromatic amines are more likely to undergo natural discoloration, particularly at higher rates in the liquid state, such as dissolution and melting.

원료로서 방향족 아민이 변색되는 것은 검은색을 띠는 불순물이 자연 생성되었기 때문이며, 이러한 불순물은 아라미드의 물성을 저하시키고 외관 품질을 악화시키는 주요한 원인이 된다. 따라서 방향족 아민을 원료물질로 사용하여 아라미드 섬유 등과 같은 최종제품을 생산하는 경우, 상기 원료물질 중에 함유된 색도원인물질을 분리, 제거해서 원료물질의 색상을 우수하게 유지시켜주는 정제공정이 매우 중요하다.The aromatic amine is discolored as a raw material because black impurities are naturally produced, and these impurities are a major cause of deteriorating the properties of the aramid and deteriorating the appearance quality. Therefore, when an aromatic amine is used as a raw material to produce an end product such as aramid fiber, it is very important to separate and remove the color-causing substance contained in the raw material so as to keep the color of the raw material excellent .

파라페닐렌디아민과 유사한 2-시아노-파라페닐렌디아민 역시 아라미드의 원료로 사용된다.2-Cyano-paphenylenediamine, similar to paraphenylenediamine, is also used as a raw material for the aramid.

구체적으로, N-메틸-2-피롤리돈 유기용매를 사용하여 2-시아노-파라페닐렌디아민, 파라페닐렌디아민 및 테레프탈로일 디클로라이드를 중합반응 시키면 황산용매를 사용하지 않고도 아라미드 섬유를 제조할 수 있는 아라미드 중합체가 얻어진다.Specifically, when 2-cyano-para-phenylenediamine, p-phenylenediamine and terephthaloyl dichloride are polymerized using an N-methyl-2-pyrrolidone organic solvent, aramid fibers An aramid polymer which can be produced is obtained.

고도로 정제된 순수한 2-시아노-파라페닐렌디아민은 색상이 밝은 베이지색 또는 밝은 노란색을 띄어 아라미드 섬유의 중합 원료로 사용하면 최종제품인 아라미드 섬유의 물성 및 색상에 나쁜 영향을 미치지 않는다.The highly refined pure 2-cyano-para-phenylenediamine diffuses light beige or light yellow and is used as a raw material for polymerization of aramid fibers, which does not adversely affect the physical properties and color of the final aramid fiber.

2-시아노-파라페닐렌디아민을 정제하는 종래 기술로는 용매추출 방법, 승화(Sublimation) 방법 등이 알려져 있다.As a conventional technique for purifying 2-cyano-para-phenylenediamine, a solvent extraction method, a sublimation method, and the like are known.

그러나 상기 용매추출 방법으로는 색상이 우수한 2-시아노-파라페닐렌디아민으로 정제할 수 없었고, 상기 승화 방법의 경우는 정제된 2-시아노-파라페닐렌디아민이 좋은 색상, 다시 말해 밝은 베이지 색상을 띄지만 승화공정의 컨트롤이 어렵고 수득율이 낮아 대량 정제에는 적용이 어려운 문제점이 있었다. 그렇기 때문에 상업적 생산을 위해서는 대량 정제가 가능한 증류(Distillation)의 방법을 적용하는 것이 필요하다.However, in the above solvent extraction method, it was impossible to purify 2-cyano-para-phenylenediamine having excellent color. In the case of the sublimation method, purified 2-cyano-paphenylenediamine has good color, But it is difficult to control the sublimation process and the yield is low so that it is difficult to apply it to mass purification. Therefore, for commercial production, it is necessary to apply distillation method capable of mass purification.

기존의 파라페닐렌디아민은 증류법이 상업화된 정제방법으로 알려져있고, 이 방법의 특징은 파라페닐렌디아민과 파라니트로아닐린과 같은 불순물 간의 비점 차이를 이용하여 파라페닐렌디아민을 정제하는 방법으로서 현재 가장 널리 사용되고 있으나, 알려진 파라페닐렌디아민의 정제공정 조건을 2-시아노-파라페닐렌디아민의 정제에 적용하면 물질 내 색도유발물질을 효과적으로 분리, 제거하기 어려운 문제점이 있었다.Conventional paraphenylenediamine is known as a purification method in which a distillation method is commercialized. This method is characterized in that paraphenylenediamine is refined by using a difference in boiling point between impurities such as paraphenylenediamine and para-nitroaniline. It has been difficult to effectively separate and remove chromophoric substances in the material when the process for purifying p-phenylenediamine is applied to the purification of 2-cyano-para-phenylenediamine.

본 발명의 과제는 2-시아노-파라페닐렌디아민내 색도유발물질을 분리, 제거하는 정제공정에 있어서, 상기 정제공정의 컨트롤이 용이하며 수득율이 높아 대량 생산이 가능하여 정제효율도 높힐 수 있는 2-시아노-파라페닐렌디아민의 정제방법을 제공하는 것이다.The object of the present invention is to provide a process for separating and removing chromophoric substances in 2-cyano-paraphenylenediamine, which is easy to control the purification process and can be mass-produced with high yield, And a method for purifying 2-cyano-para-phenylenediamine.

이와같은 과제를 달성하기 위해서, 본 발명에서는 2-시아노-파라페닐렌디아민을 증류탑에 투입하여 탑저온도가 150~250℃이고 탑정온도가 150~230℃인 조건하에서 환류비가 0.5~4가 되도록 증류하여 2-시아노-파라페닐렌디아민내 색도유발물질을 분리, 제거한다.In order to achieve the above object, the present invention provides a process for producing 2-cyano-p-phenylenediamine, which comprises introducing 2-cyano-para-phenylenediamine into a distillation column and having a reflux ratio of 0.5 to 4 under a condition of a tower low temperature of 150 to 250 ° C and a top temperature of 150 to 230 ° C Distillation so as to separate and remove the chromogenic material in 2-cyano-paphenylenediamine.

본 발명은 2-시아노-파라페닐렌디아민을 정제하는 공정 컨트롤이 용이하고, 정제된 2-시아노-파라페닐렌디아민의 수득율이 높아 대량 생산이 가능하며, 정제효율이 높아 97% 이상의 순도로 정제되어 밝은 베이지 또는 밝은 노란색을 띄는 2-시아노-파라페닐렌디아민을 얻을 수 있다.The present invention relates to a process for purifying 2-cyano-para-phenylenediamine which is easy to control the process for purifying 2-cyano-para-phenylenediamine and which can be mass-produced with high yield of purified 2-cyano-paphenylenediamine, To give a light beige or light yellow 2-cyano-para-phenylenediamine.

이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에 따른 2-시아노-파라페닐렌디아민의 제조방법은 먼저 2-시아노-파라페닐렌디아민을 증류탑에 투입한 다음, 탑저온도와 탑정온도를 각각 150~250℃와 150~230℃로 조절함과 동시에 환류비가 0.5~4가 되도록 조절하면서 증류하는 것을 특징으로 한다.The process for the preparation of 2-cyano-paphenylenediamine according to the present invention is characterized in that 2-cyano-para-phenylenediamine is first added to the distillation column and then the column low temperature and the column top temperature are respectively maintained at 150 to 250 ° C and 150 to 230 ° C And the distillation is carried out while adjusting the reflux ratio to be 0.5 to 4.

이때 상기 증류탑은 2~20단인 것이 바람직하다.At this time, the distillation tower is preferably 2 to 20 stages.

탑저온도와 탑정온도 각각이 상기 범위를 벗어나는 경우에는 정제공정의 컨트롤이 어렵게 되고 수득율도 저하되고 정제효율도 떨어져 바람직하지 못하다.When the temperature of each of the tower low temperature and the tower top temperature is out of the above range, it is difficult to control the purification process, the yield is lowered, and the purification efficiency is lowered.

또한 상기 환류비가 0.5 미만이면 낮은 비용으로 제품 수득율을 높일 수는 있으나 원하는 순도의 제품을 얻을 수가 없는 문제가 발생되고, 4를 초과하면 초고순도의 제품을 얻을 수는 있으나 에너지비가 필요이상으로 소요되어 제조원가에 영향을 주는 문제가 발생되어 바람직하지 못하다.In addition, if the reflux ratio is less than 0.5, the product yield can be increased at a low cost, but a product having a desired purity can not be obtained. If the reflux ratio is more than 4, an ultra-high purity product can be obtained. However, There is a problem that affects the manufacturing cost, which is not preferable.

본 발명으로 정제된 2-시아노-파라페닐렌디아민은 순도가 97% 이상이며 CIE 색도는 L* 60 이상 b* +20 이상으로 우수한 색상을 갖게 된다.The 2-cyano-para-phenylenediamine purified by the present invention has a purity of 97% or more and a CIE chromaticity of L * 60 or more and b * +20 or more.

이하, 실시예 및 비교실시예를 통하여 본 발명을 구체적으로 살펴본다.Hereinafter, the present invention will be described in detail with reference to examples and comparative examples.

그러나, 본 발명의 보호범위는 후술하는 실시예 만으로 한정되는 것은 아니다.However, the scope of protection of the present invention is not limited to the following embodiments.

실시예 1Example 1

2-시아노-파라페닐렌디아민을 10단 증류탑에 투입한 다음, 탑저온도 및 탑정온도를 각각 250℃ 및 200℃로 조절함과 동시에 환류비는 2로 조절하면서 증류하여 2-시아노-파라페닐렌디아민내 색도유발물질을 분리, 정제하였다.The 2-cyano-para-phenylenediamine was fed into the 10-stage distillation column, and then the tower low temperature and the column top temperature were adjusted to 250 ° C and 200 ° C, respectively, while the reflux ratio was adjusted to 2, The color inducing substance in phenylenediamine was separated and purified.

제조된 2-시아노-파라페닐렌디아민의 순도 및 CIE 색도를 평가한 결과는 표 1과 같았다.The purity and CIE chromaticity of the prepared 2-cyano-para-phenylenediamine were evaluated, and the results are shown in Table 1. [

실시예 2Example 2

2-시아노-파라페닐렌디아민을 10단 증류탑에 투입한 다음, 탑저온도 및 탑정온도를 각각 250℃ 및 160℃로 조절함과 동시에 환류비는 3.5로 조절하면서 증류하여 2-시아노-파라페닐렌디아민내 색도유발물질을 분리, 정제하였다.The 2-cyano-para-phenylenediamine was fed into a 10-stage distillation column, and then the tower low temperature and the column top temperature were adjusted to 250 ° C and 160 ° C, respectively, and the reflux ratio was adjusted to 3.5, The color inducing substance in phenylenediamine was separated and purified.

제조된 2-시아노-파라페닐렌디아민의 순도 및 CIE 색도를 평가한 결과는 표 1과 같았다.The purity and CIE chromaticity of the prepared 2-cyano-para-phenylenediamine were evaluated, and the results are shown in Table 1. [

실시예 3Example 3

2-시아노-파라페닐렌디아민을 10단 증류탑에 투입한 다음, 탑저온도 및 탑정온도를 각각 250℃ 및 230℃로 조절함과 동시에 환류비는 1.2로 조절하면서 증류하여 2-시아노-파라페닐렌디아민내 색도유발물질을 분리, 정제하였다.The 2-cyano-para-phenylenediamine was fed into the 10-stage distillation column, and the column low temperature and the column top temperature were adjusted to 250 ° C. and 230 ° C., respectively, while the reflux ratio was adjusted to 1.2, The color inducing substance in phenylenediamine was separated and purified.

제조된 2-시아노-파라페닐렌디아민의 순도 및 CIE 색도를 평가한 결과는 표 1과 같았다.The purity and CIE chromaticity of the prepared 2-cyano-para-phenylenediamine were evaluated, and the results are shown in Table 1. [

비교실시예 1Comparative Example 1

파라페닐렌디아민의 증류 조건에 따라 2-시아노-파라페닐렌디아민을 10단 증류탑에 투입한 다음, 탑저온도 및 탑정온도를 각각 180℃ 및 160℃로 조절함과 동시에 환류비는 1.5으로 조절하면서 증류하여 2-시아노-파라페닐렌디아민내 색도유발물질을 분리, 정제하였다.According to the distillation conditions of paraphenylenediamine, 2-cyano-para-phenylenediamine was fed into the 10-stage distillation tower, and then the tower low temperature and the tower top temperature were adjusted to 180 ° C. and 160 ° C., respectively, And distilled to separate and purify the chromogenic substance in 2-cyano-para-phenylenediamine.

제조된 2-시아노-파라페닐렌디아민의 순도 및 CIE 색도를 평가한 결과는 표 1과 같았다.The purity and CIE chromaticity of the prepared 2-cyano-para-phenylenediamine were evaluated, and the results are shown in Table 1. [

구분division 순도water CIE 색도CIE chromaticity L* L * b* b * 실시예 1Example 1 99.299.2 6565 +26+26 실시예 2Example 2 99.599.5 6868 +27+27 실시예 3Example 3 98.698.6 6363 +25+25 비교실시예 1Comparative Example 1 85.485.4 5555 +23+23

Claims (2)

2-시아노-파라페닐렌디아민을 증류탑에 투입하여 탑저온도가 150~250℃이고 탑정온도가 150~230℃인 조건하에서 환류비가 0.5~4가 되도록 증류하는 것을 특징으로 하는 2-시아노-파라페닐렌디아민의 정제방법.2-cyano-para-phenylenediamine is fed into a distillation column, and distillation is carried out at a reflux ratio of 0.5 to 4 under a condition of a tower low temperature of 150 to 250 ° C and a top temperature of 150 to 230 ° C. -Preparation method of paraphenylenediamine. 제1항에 있어서, 상기 증류탑은 2~20단인 것을 특징으로 하는 2-시아노-파라페닐렌디아민의 정제방법.The process according to claim 1, wherein the distillation column has 2 to 20 stages.
KR1020120149191A 2012-12-20 2012-12-20 Method of refining 2-cyano-para-phenylenediamine KR20140079956A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020120149191A KR20140079956A (en) 2012-12-20 2012-12-20 Method of refining 2-cyano-para-phenylenediamine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020120149191A KR20140079956A (en) 2012-12-20 2012-12-20 Method of refining 2-cyano-para-phenylenediamine

Publications (1)

Publication Number Publication Date
KR20140079956A true KR20140079956A (en) 2014-06-30

Family

ID=51130796

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020120149191A KR20140079956A (en) 2012-12-20 2012-12-20 Method of refining 2-cyano-para-phenylenediamine

Country Status (1)

Country Link
KR (1) KR20140079956A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907752A (en) * 1973-06-28 1975-09-23 Westinghouse Electric Corp Aromatic nitrile amide polymers
JPH0717584B2 (en) * 1986-03-08 1995-03-01 バイエル・アクチエンゲゼルシヤフト Distillation method for separating amines from aqueous amine solutions
JP2002088032A (en) * 2000-09-13 2002-03-27 Mitsubishi Gas Chem Co Inc Method for purifying xylylenediamine
JP2011026224A (en) * 2009-07-23 2011-02-10 Seiko Kagaku Kk METHOD FOR PURIFYING p-PHENYLENEDIAMINE
KR20110076346A (en) * 2009-12-29 2011-07-06 코오롱인더스트리 주식회사 Aromatic diamine, method for manufacturing the same, and method for manufacturing aramid polymer
KR20140026695A (en) * 2012-08-23 2014-03-06 코오롱인더스트리 주식회사 Method of manufacturing aramid fiber

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907752A (en) * 1973-06-28 1975-09-23 Westinghouse Electric Corp Aromatic nitrile amide polymers
JPH0717584B2 (en) * 1986-03-08 1995-03-01 バイエル・アクチエンゲゼルシヤフト Distillation method for separating amines from aqueous amine solutions
JP2002088032A (en) * 2000-09-13 2002-03-27 Mitsubishi Gas Chem Co Inc Method for purifying xylylenediamine
JP2011026224A (en) * 2009-07-23 2011-02-10 Seiko Kagaku Kk METHOD FOR PURIFYING p-PHENYLENEDIAMINE
KR20110076346A (en) * 2009-12-29 2011-07-06 코오롱인더스트리 주식회사 Aromatic diamine, method for manufacturing the same, and method for manufacturing aramid polymer
KR20140026695A (en) * 2012-08-23 2014-03-06 코오롱인더스트리 주식회사 Method of manufacturing aramid fiber

Similar Documents

Publication Publication Date Title
DE60213343D1 (en) Process for the simultaneous production of xylitol and ethanol
RU2243202C1 (en) Method for preparing anthracene and carbazole by crystallization of melt
US20150112088A1 (en) Method for preparing high purity anhydrosugar alcohols by thin film distillation
CN111499529A (en) Synthetic method of ultraviolet absorber UVA Plus
EA200801325A1 (en) METHOD OF INDUSTRIAL PRODUCTION OF HIGH-QUALITY AROMATIC POLYCARBONATE
KR20140079956A (en) Method of refining 2-cyano-para-phenylenediamine
CN112724010B (en) Production method of refined sebacic acid
PE20212093A1 (en) IMPROVED PROCEDURE FOR PRODUCING HIGH PURITY LEAD
KR101650610B1 (en) Method For Preparing Polycarbonate
US2341282A (en) Purification of methyl methacrylate
BR112020016725A2 (en) PROCESSES FOR THE PURIFICATION OF HEXAMETHYLENODYAMINE AND FOR THE PREPARATION OF HEXAMETHYLENODYAMINE
KR101611653B1 (en) Cyclic Olefin Compound and Method for Preparing the Same
KR101208050B1 (en) Method for manufacturing 1,4-cyclohexane dicarboxylic acid
KR100700623B1 (en) Process to separate azeotropic mixture using ethylene glycol
KR101686081B1 (en) Method for manufacturing high purity pyridine for electron material
EP0206789B1 (en) Crystalline hydroxyphenylpropionic acid ester and its production
KR20090094480A (en) Method for purifying the glycerin from bio-diesel plant
CN104744328A (en) Process method for producing accelerant TMTD by taking isopropanol as solvent
CN102876235A (en) Production process for decoloring and purifying capsicum oleoresin
CN110734400B (en) Process for producing isoquinoline and process for separating isoquinoline
CN100503619C (en) Method for chemically refining methyl phenyl dichloro silane through two-step ways
JP2011051905A (en) Method for purifying anhydrous sugar alcohol
TW201509500A (en) Process for the recovery of [epsilon]-caprolactam from extract water
US2829088A (en) Process of refining dimethylformamide
RU2013143308A (en) METHOD FOR PRODUCING FLUORENE BY MELT CRYSTALLIZATION

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E601 Decision to refuse application