KR100605052B1 - Purification Method Of 2,6-Naphthalenedicarboxylic Acid - Google Patents
Purification Method Of 2,6-Naphthalenedicarboxylic Acid Download PDFInfo
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Abstract
본 발명은 2,6-디메틸나프탈렌을 브롬/코발트/망간 촉매하에서 산화반응시켜 제조된 2,6-나프탈렌디카르복실산의 정제 방법에 관한 것으로, 보다 상세하게는The present invention relates to a method for purifying 2,6-naphthalenedicarboxylic acid prepared by oxidizing 2,6-dimethylnaphthalene under a bromine / cobalt / manganese catalyst.
1) 불순물 함유 2,6-나프탈렌디카르복실산을 디메틸포름아마이드, 디메틸아세트아마이드 및 디메틸설폭사이드로 구성된 군에서 선택된 1 종의 화합물에 용해하고 석출하는 단계;1) dissolving and precipitating impurity-containing 2,6-naphthalenedicarboxylic acid in one compound selected from the group consisting of dimethylformamide, dimethylacetamide and dimethylsulfoxide;
2) 1)단계의 석출물을 지방족 아민 수용액에 용해하고 철, 코발트, 니켈, 팔라듐 및 백금으로 구성된 군에서 선택된 1 종의 금속이 담지된 카본 촉매하에 수소화 처리하는 단계; 및2) dissolving the precipitate of step 1) in an aqueous aliphatic amine solution and subjecting to hydrogenation under a carbon catalyst carrying one metal selected from the group consisting of iron, cobalt, nickel, palladium and platinum; And
3) 2)단계의 생성물을 물, 알콜 또는 물/알콜 혼합용매로 세척하는 단계3) washing the product of step 2) with water, alcohol or water / alcohol mixed solvent
로 구성되는 2,6-나프탈렌디카르복실산의 정제 방법에 관한 것이며, 본 발명에 의하면, 고순도의 2,6-나프탈렌디카르복실산을 얻을 수 있다.The present invention relates to a method for purifying 2,6-naphthalenedicarboxylic acid comprised of the present invention, and according to the present invention, high purity 2,6-naphthalenedicarboxylic acid can be obtained.
2,6-나프탈렌디카르복실산, 디메틸포름아마이드, 지방족 아민, 팔라듐/카본 촉매, 수소화2,6-naphthalenedicarboxylic acid, dimethylformamide, aliphatic amine, palladium / carbon catalyst, hydrogenation
Description
본 발명은 2,6-디메틸나프탈렌의 산화 반응으로 생성된 2,6-나프탈렌디카르복실산의 정제 방법에 관한 것으로, 보다 상세하게는 1)산화반응으로 생성된 2,6-나프탈렌디카르복실산을 디메틸포름아마이드 등에 용해, 석출하는 단계; 2)지방족 아민 수용액에서 특정 촉매하에 수소화될 수 있는 불순물을 수소화하는 단계; 3) 특정 용매에서 잔존 불순물을 제거하는 단계를 포함하는 2,6-나프탈렌디카르복실산의 정제 방법에 관한 것이다.The present invention relates to a method for purifying 2,6-naphthalenedicarboxylic acid produced by the oxidation of 2,6-dimethylnaphthalene, and more particularly, to 1,2,6-naphthalenedicarboxyl produced by the oxidation reaction. Dissolving and precipitating an acid in dimethylformamide or the like; 2) hydrogenating impurities that can be hydrogenated under a specific catalyst in an aqueous aliphatic amine solution; 3) to a method for purifying 2,6-naphthalenedicarboxylic acid comprising removing residual impurities in a specific solvent.
2,6-나프탈렌디카르복실산은 에틸렌글리콜과 중합시켜 폴리에틸렌 나프탈레이트(PEN)를 제조하는데 사용된다.2,6-naphthalenedicarboxylic acid is used to prepare polyethylene naphthalate (PEN) by polymerization with ethylene glycol.
나프탈렌디카르복실산은 디메틸나프탈렌을 초산 용매중에서 코발트, 망간등의 중금속과 브롬화합물의 존재하에 O2를 고온, 고압으로 반응시키는 방법에 의하여 얻어진다. 그러나, 이 방법은 생성물 중에 촉매 금속인 코발트, 망간 외에 산화 반 응의 중간 생성물인 포르밀나프토산(FNA), 메틸나프토산(MNA), 분해 생성물인 트리멜리트산(TMLA), 브롬 부가된 나프탈렌디카르복실산브로마이드, 원료 디메틸나프탈렌의 불순물에서 유래한 나프토산(NA)등이 불순물로서 포함되므로, 이를 에틸렌글리콜과 바로 중합시키면, 중합 생성물인 폴리에스테르는 내열성과 연화점이 저하되며, 착색 등의 품질 저하가 발생한다. 특히, 포르밀나프토산이 특정치 이상 포함되어 있으면, 중합도는 향상되지 않고 겔화나 착색이 발생한다. 따라서, 고품질의 폴리에스테르를 얻기 위해서는 순도 99% 이상의 고순도 2,6-나프탈렌디카르복실산이 요구된다.Naphthalenedicarboxylic acid is obtained by reacting dimethylnaphthalene with O 2 at high temperature and high pressure in the presence of heavy metals such as cobalt and manganese and bromine compounds in a solvent of acetic acid. However, this method does not contain cobalt as a catalyst metal, formylnaphthoic acid (FNA), methylnaphthoic acid (MNA) as an intermediate in the oxidation reaction in addition to the catalytic metal, trimellitic acid (TMLA) as bromine added naphthalene in the product. Since dicarboxylic acid bromide and naphthoic acid (NA) derived from the impurity of the raw material dimethyl naphthalene are included as impurities, when it is directly polymerized with ethylene glycol, the polyester product as a polymerization product has low heat resistance and softening point, Quality degradation occurs. In particular, when formyl naphthoic acid is contained at a specific value or more, the degree of polymerization does not improve and gelation or coloring occurs. Therefore, high purity 2,6-naphthalenedicarboxylic acid with a purity of 99% or higher is required to obtain high quality polyester.
유기물의 정제에는 일반적으로 증류, 재결정 등이 사용되지만, 2,6-나프탈렌디카르복실산은 300℃이상의 고온에서 분해되므로 증류법을 사용할 수 없고, 일반적인 용매에 난용성이므로 단순한 재결정법을 사용할 수 없다. 따라서, 대체 방법으로 나프탈렌디카르복실산을 메틸알콜 등의 알콜류와 반응시켜 일단 나프탈렌디카르복실산 에스테르로 전환한 후 증류 또는 재결정 등을 행하는 정제 방법 등이 행하여지고 있으나, 그 과정이 복잡하고 비경제적인 단점이 있다.Distillation, recrystallization and the like are generally used for purification of organic materials. However, since 2,6-naphthalenedicarboxylic acid is decomposed at a high temperature of 300 ° C. or higher, distillation cannot be used, and simple recrystallization cannot be used because it is poorly soluble in a general solvent. Therefore, as an alternative method, a purification method of reacting naphthalenedicarboxylic acid with alcohols such as methyl alcohol and converting it to naphthalenedicarboxylic acid ester once and then performing distillation or recrystallization is performed, but the process is complicated and economical. There is a disadvantage.
나프탈렌디카르복실산을 용매에 용해하고, 정제하는 방법으로서 다음과 같은 방법이 제안되고 있다. As a method of dissolving naphthalenedicarboxylic acid in a solvent and purifying, the following method is proposed.
미국 특허 제 5,256,817호는 물 또는 초산 수용액을 용매로 하여 300℃이상의 고온에서 용해하고 수소첨가 반응을 이용하여 정제하는 방법을 개시하고 있는데, 이 방법은 높은 용해도를 얻기 위해 고온이 필요하고, 이로 인하여 부반응 즉 탈탄산 반응에 의한 나프토산이 생성되며, 수소 첨가 반응에 의한 테트라린디카르 복실산이 생기기 쉽다. U. S. Patent No. 5,256, 817 discloses a method of dissolving water or acetic acid in water at a high temperature of 300 ° C. or higher and purifying by using a hydrogenation reaction, which requires a high temperature to obtain high solubility. Naphthoic acid is generated by side reaction, that is, decarbonation reaction, and tetralindicarboxylic acid by hydrogenation reaction is likely to occur.
일본특허공개 소62-230747은 디메틸설폭사이드(DMSO), 디메틸포름아미드 (DMF) 등의 용매로 용해, 재결정하는 정제 방법을 개시하고 있다. 그러나, 2,6-나프탈렌디카르복실산은 상기 용매에 대한 용해도가 낮고, 불순물을 수소화시켜 제거하려 하면 용매도 함께 수소화되기 때문에 수소화 처리가 불가하며, 포르밀나프토산(FNA)의 완전한 제거도 어렵다. Japanese Patent Application Laid-Open No. 62-230747 discloses a purification method for dissolving and recrystallization with a solvent such as dimethyl sulfoxide (DMSO) or dimethylformamide (DMF). However, 2,6-naphthalenedicarboxylic acid has low solubility in the solvent, and if hydrogenated impurities are removed to remove the solvent, hydrogenation is impossible, and complete removal of formylnaphthoic acid (FNA) is difficult. .
일본특허공개 평5-32586은 피리딘류에 용해하고 재결정하는 정제방법에 관한 것인데, 2,6-나프탈렌 디카르복실산의 피리딘류에 대한 용해도의 온도 의존성이 낮기 때문에 회수율이 낮은 단점이 있다. Japanese Patent Laid-Open No. 5-32586 relates to a purification method of dissolving and recrystallizing in pyridines, but has a disadvantage in that the recovery rate is low because the temperature dependency of solubility of 2,6-naphthalene dicarboxylic acid in pyridine is low.
미국 특허 제 5,859,294호는 피리딘류와 지방족 아민류의 혼합 용매에 용해하고, 수소화 처리한 후, 재결정을 통하여 2,6-나프탈렌디카르복실산 아민염을 얻고, 아민염을 가열 분해하여 2,6-나프탈렌디카르복실산을 정제하는 방법을 개시하고 있다. 나프탈렌디카르복실산을 알칼리에 용해하여 알칼리염으로서 용해도를 향상시켜 정제하는 방법은 알칼리염을 석출시킬 때 포르밀나프토산 등의 불순물의 염도 동시에 석출되고, 다량의 알칼리 또는 산이 요구되는 단점이 있다.U.S. Patent No. 5,859,294 is dissolved in a mixed solvent of pyridines and aliphatic amines, hydrogenated, and then recrystallized to obtain 2,6-naphthalenedicarboxylic acid amine salt, and the amine salt is thermally decomposed to give 2,6- A method of purifying naphthalenedicarboxylic acid is disclosed. The method of dissolving naphthalenedicarboxylic acid in alkali to improve solubility as an alkali salt has the disadvantage of simultaneously depositing salts of impurities such as formylnaphthoic acid when the alkali salt is precipitated, and a large amount of alkali or acid is required. .
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로, 보다 용이한 2,6-나프탈렌디카르복실산의 정제 방법을 제공함을 그 목적으로 한다.The present invention has been made to solve the problems of the prior art as described above, and an object thereof is to provide an easier method for purifying 2,6-naphthalenedicarboxylic acid.
즉, 본 발명은 2,6-디메틸나프탈렌을 브롬/코발트/망간 촉매하에서 산화반응 시켜 제조된 2,6-나프탈렌디카르복실산을 정제함에 있어 먼저 2,6-나프탈렌디카르복실산을 디메틸포름아마이드 등에 용해, 석출하여 트리멜리트산 및 촉매에 의한 금속 착물을 제거하고, 지방족 아민 수용액에 용해하여 수소화 촉매하에 수소화시켜 수소화될 수 있는 불순물, 즉 포르밀나프토산 및 나프탈렌디카르복실산브로마이드의 양을 감소시킨 후, 물, 알콜, 또는 물/알콜 혼합용매로 나머지 잔존 불순물을 제거하여 고순도의 2,6-나프탈렌디카르복실산을 제조하는 방법에 관한 것이다.
That is, in the present invention, in purifying 2,6-naphthalenedicarboxylic acid prepared by oxidizing 2,6-dimethylnaphthalene under a bromine / cobalt / manganese catalyst, 2,6-naphthalenedicarboxylic acid is first converted into dimethylform. The amount of impurities that can be hydrogenated, ie, formylnaphthoic acid and naphthalenedicarboxylic acid bromide, dissolved and precipitated in an amide or the like to remove trimellitic acid and the metal complex by the catalyst, dissolved in an aqueous aliphatic amine solution and hydrogenated under a hydrogenation catalyst. After reduction of the present invention, the present invention relates to a method for preparing high purity 2,6-naphthalenedicarboxylic acid by removing residual impurities with water, alcohol, or a water / alcohol mixed solvent.
이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 The present invention
1) 불순물 함유 2,6-나프탈렌디카르복실산을 디메틸포름아마이드, 디메틸아세트아마이드 및 디메틸설폭사이드로 구성된 군에서 선택된 1 종의 화합물에 용해하고 석출하는 단계;1) dissolving and precipitating impurity-containing 2,6-naphthalenedicarboxylic acid in one compound selected from the group consisting of dimethylformamide, dimethylacetamide and dimethylsulfoxide;
2) 1)단계의 석출물을 지방족 아민 수용액에 용해하고 철, 코발트, 니켈, 팔라듐 및 백금으로 구성된 군에서 선택된 1 종의 금속이 담지된 카본 촉매하에 수소화 처리하는 단계; 및2) dissolving the precipitate of step 1) in an aqueous aliphatic amine solution and subjecting to hydrogenation under a carbon catalyst carrying one metal selected from the group consisting of iron, cobalt, nickel, palladium and platinum; And
3) 2)단계의 생성물을 물, 알콜 또는 물/알콜 혼합용매로 세척하는 단계3) washing the product of step 2) with water, alcohol or water / alcohol mixed solvent
로 구성된 2,6-나프탈렌디카르복실산의 정제 방법에 관한 것이다.It relates to a method for purifying 2,6-naphthalenedicarboxylic acid consisting of.
본 발명의 원료로 사용되는 2,6-나프탈렌디카르복실산은 브롬/코발트/망간으로 구성되는 촉매계를 이용하여 초산 용매하에서 2,6-디메틸나프탈렌과 공기를 연속적으로 공급하여 반응온도 200-250℃에서 반응시켜 얻어진다. 이 산화반응은 공지된 공정을 사용한 것으로 산화반응 원료, 조건 및 촉매조성에 관해서는 특별한 제약이 없다. 이렇게 제조된 2,6-나프탈렌디카르복실산은 일반적으로 트리멜리트산, 포르밀나프토산, 나프토산 및 촉매에 의해 형성되는 금속 착물과 브롬 유도체 등의 불순물을 함유한다.The 2,6-naphthalenedicarboxylic acid used as a raw material of the present invention is continuously supplied with 2,6-dimethylnaphthalene and air under a solvent of acetic acid using a catalyst system composed of bromine / cobalt / manganese and the reaction temperature is 200-250 ° C. It is obtained by reacting at. This oxidation reaction uses a well-known process, and there are no particular restrictions regarding the oxidation reaction raw material, conditions and catalyst composition. The 2,6-naphthalenedicarboxylic acid thus prepared generally contains impurities such as trimellitic acid, formylnaphthoic acid, naphthoic acid and metal complexes formed by a catalyst and bromine derivatives.
본 발명에 사용되는 디메틸포름아마이드 등은 트리멜리트산 및 이와 금속 촉매와의 착물을 효과적으로 제거하여 수소화 반응시 불순물의 부하를 감소시키는 역할을 한다. 디메틸아세트아마이드, 디메틸설폭사이드도 사용될 수 있으나 디메틸포름아마이드가 바람직하다.Dimethylformamide and the like used in the present invention effectively remove the trimellitic acid and the complexes thereof with the metal catalyst to reduce the load of impurities during the hydrogenation reaction. Dimethylacetamide, dimethylsulfoxide may also be used but dimethylformamide is preferred.
본 발명에 사용되는 지방족 아민류로는 메틸아민, 디메틸아민, 트리메틸아민, 디에틸아민, 트리에틸아민, 프로필아민, 디프로필아민, 이소프로필아민, 디이소프로필아민, 디부틸아민, 트리부틸아민, 디이소부틸아민, 트리이소부틸아민 등의 알킬아민류가 있으며, 바람직하게는 취급 및 보관이 간편한 에틸아민류, 보다 바람직하게는 트리에틸아민이 있다. Aliphatic amines used in the present invention include methylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, dibutylamine, tributylamine, Alkylamines, such as diisobutylamine and triisobutylamine, are preferable, Preferably there are ethylamines which are easy to handle and store, More preferably, triethylamine.
본 발명의 수소화 반응시 2,6-나프탈렌디카르복실산은 상기에 언급된 지방족 아민에 용해시킨다. 사용되는 지방족 아민의 2,6-나프탈렌디카르복실산에 대한 중량비는 제한적이지는 않지만, 수소화 처리시의 반응 온도에서 2,6-나프탈렌디카르 복실산의 10% 이상을 용해시킬 수 있는 양의 지방족 아민이 필요하다. In the hydrogenation reaction of the present invention, 2,6-naphthalenedicarboxylic acid is dissolved in the aliphatic amines mentioned above. The weight ratio of the aliphatic amines used to the 2,6-naphthalenedicarboxylic acid is not limited, but in an amount capable of dissolving at least 10% of the 2,6-naphthalenedicarboxylic acid at the reaction temperature during the hydrogenation treatment. Aliphatic amines are needed.
본 발명의 수소화용 촉매는 금속이 담지된 활성탄이다. 담지된 금속의 예는 철, 코발트, 니켈, 팔라듐, 백금 등이며, 바람직하게는 팔라듐 또는 백금이다. 금속의 함량은 0.1∼1 중량% 이며, 바람직하게는 0.3∼0.7 중량%이다. The catalyst for hydrogenation of the present invention is activated carbon carrying a metal. Examples of the supported metal are iron, cobalt, nickel, palladium, platinum, and the like, preferably palladium or platinum. The content of the metal is 0.1 to 1% by weight, preferably 0.3 to 0.7% by weight.
수소화 반응은 2,6-나프탈렌디카르복실산을 지방족 아민에 용해시키고 상기의 수소화 촉매하에서 0.1∼3시간, 바람직하게는 0.5∼2시간 행한다. 수소화 반응시 온도는 100∼300℃, 바람직하게는 150∼250℃이며 수소 분압은 0.1∼50 bar, 바람직하게는 1∼30 bar 이다. 온도가 250℃ 초과이면 나프탈렌 고리가 수소화되어 테트랄린 계열의 불순물이 생성되며, 150℃ 미만이면 수소화 가능한 불순물들이 충분히 제거되지 않을 수 있다. 상기 반응에 의해 포르밀나프토산 및 나프탈렌디카르복시산브로마이드 등의 불순물이 수소화되어 제거되거나 제거되기 쉬운 불순물로 전환된다.The hydrogenation reaction is performed by dissolving 2,6-naphthalenedicarboxylic acid in an aliphatic amine and performing 0.1 to 3 hours, preferably 0.5 to 2 hours, under the hydrogenation catalyst. The temperature during the hydrogenation reaction is 100 to 300 ° C., preferably 150 to 250 ° C., and the hydrogen partial pressure is 0.1 to 50 bar, preferably 1 to 30 bar. If the temperature is greater than 250 ℃ naphthalene ring is hydrogenated to produce a tetralin-based impurities, if less than 150 ℃ hydrogenated impurities may not be sufficiently removed. By the reaction, impurities such as formylnaphthoic acid and naphthalenedicarboxylic acid bromide are hydrogenated and converted into impurities that are easily removed or removed.
수소화 반응 후 2,6-나프탈렌디카르복실산을 -10∼100℃, 바람직하게는 0∼80℃로 냉각하면 2,6-나프탈렌디카르복실산 아민염으로 재결정되며 이를 필터로 여과한다. After the hydrogenation reaction, the 2,6-naphthalenedicarboxylic acid is cooled to -10 to 100 ° C, preferably 0 to 80 ° C, and recrystallized from 2,6-naphthalenedicarboxylic acid amine salt, which is filtered through a filter.
이렇게 얻어진 2,6-나프탈렌디카르복실산 아민염을 사용된 아민의 비점 이상인 100∼300℃로 가열한다. 온도가 300℃ 초과이면, 2,6-나프탈렌디카르복실산이 분해되거나 착색되며, 100℃ 미만이면, 분해 속도가 감소하여 비경제적이다. 또한, 2,6-나프탈렌디카르복실산의 착색방지를 위하여 감압하에서 가열하는 것이 바람직하다. 가열에 의해 2,6-나프탈렌디카르복실산 아민염은 분해되고, 기체상으로 생성 되는 아민은 냉각하여 거의 전량을 회수할 수 있다.Thus obtained 2,6-naphthalenedicarboxylic acid amine salt is heated to 100-300 degreeC which is more than the boiling point of the amine used. If the temperature is above 300 ° C., 2,6-naphthalenedicarboxylic acid is decomposed or colored, and if it is below 100 ° C., the rate of decomposition decreases and is uneconomical. In addition, it is preferable to heat under reduced pressure in order to prevent the coloring of 2,6-naphthalenedicarboxylic acid. The 2,6-naphthalenedicarboxylic acid amine salt is decomposed by heating, and the amine produced in the gas phase can be cooled to recover almost the entire amount.
본 발명에서 얻어진 2,6-나프탈렌디카르복실산은 마지막으로 물, 알콜 또는 물/알콜 혼합용매로 세척하여 나머지 잔존 불순물을 제거한다. 물을 단독용매로 사용하는 경우보다 물/알콜 혼합용매를 사용하는 것이 바람직하다. 이때, 혼합 용매의 혼합비는 질량 기준으로 물에 대한 알콜의 비가 3/7 이상, 바람직하게는 1이상이다. 사용가능한 알콜은 메탄올, 에탄올, 프로탄올, 부탄올 등이며, 바람직하게는 에탄올이다.The 2,6-naphthalenedicarboxylic acid obtained in the present invention is finally washed with water, alcohol or water / alcohol mixed solvent to remove remaining residual impurities. It is preferable to use a water / alcohol mixed solvent than when water is used as the sole solvent. At this time, the mixing ratio of the mixed solvent is 3/7 or more, preferably 1 or more ratio of alcohol to water on a mass basis. Alcohols that can be used are methanol, ethanol, protanol, butanol and the like, preferably ethanol.
상기와 같이 얻어진 2,6-나프탈렌디카르복실산은 매우 고순도이며 폴리에틸렌 나프탈레이트 제조를 위한 원료로 사용할 수 있다.The 2,6-naphthalenedicarboxylic acid obtained as described above is very high purity and can be used as a raw material for producing polyethylene naphthalate.
이하, 실시예와 비교예를 통하여 본 발명을 보다 상세하게 설명하고자 하나, 실시예는 본 발명의 보호범위를 제한하는 것으로 해석되어서는 아니된다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, which should not be construed as limiting the protection scope of the present invention.
정제의 대상이 된 2,6-나프탈렌디카르복실산의 제조과정을 다음 참고예에서 설명한다.The procedure for producing 2,6-naphthalenedicarboxylic acid, which is the subject of purification, will be described in the following reference example.
<참고예> : 2,6-나프탈렌디카르복실산의 제조Reference Example Preparation of 2,6-naphthalenedicarboxylic Acid
환류콘덴서, 교반기, 가열기, 산소의 도입부를 갖춘 1ℓ의 티타늄 반응용기에 다음 표 1과 같이 촉매와 용매를 투입하였다. A catalyst and a solvent were added to a 1 L titanium reaction vessel equipped with a reflux condenser, a stirrer, a heater, and an introduction portion of oxygen as shown in Table 1 below.
반응온도를 200℃로, 반응 압력은 18㎏중/㎠로 조절한 후 교반기를 700rpm으로 설정하고, 디메틸나프탈렌을 18g/hr로 공급하며 1시간 동안 반응을 진행시켰다. 반응이 종결된 후에도 계속하여 산소를 30분간 추가적으로 공급하였다. 이후, 60℃까지 냉각한 후 슬러리 형태의 생성 물질을 회수하고 이에 생성물질의 3배 질량의 초산을 가하고 20분간 교반한 후 여과에 의해 고상을 분리해내고 건조하였다. 상기 과정으로 제조된 2,6-나프탈렌디카르복실산의 조성은 표2에 나타내었다.The reaction temperature was adjusted to 200 ° C., the reaction pressure was adjusted to 18 kg / cm 2, the stirrer was set to 700 rpm, and dimethyl naphthalene was supplied at 18 g / hr for 1 hour. After the reaction was terminated, oxygen was further supplied for 30 minutes. Thereafter, after cooling to 60 ℃ to recover the product in the form of slurry, acetic acid of three times the mass of the product was added thereto, stirred for 20 minutes, the solid phase was separated by filtration and dried. The composition of 2,6-naphthalenedicarboxylic acid prepared by the above procedure is shown in Table 2.
<실시예 1><Example 1>
표 1의 참고예의 성분으로 구성된 아직 정제되지 아니한 상태의 2,6-나프탈렌디카르복실산 50g을 디메틸포름아마이드 500g과 혼합하고 80℃에서 30분간 교반 후 냉각, 여과하여 전처리를 수행하였다. 상기 과정으로 얻어진 2,6-나프탈렌디카르복실산과 트리에틸아민 200g을 0.5중량%의 팔라듐이 담지된 활성탄 촉매가 들어있는 1ℓ의 티타늄 반응용기에 투입하고 반응기 내로 H2를 투입하여 20 bar로 유지하면서 200℃에서 1시간 동안 수소화 반응을 실시하였다. 반응 종결 후 상온으로 냉각하여 2,6-나프탈렌디카르복실산 아민염을 석출시키고 여과한 후, 감압하에서 150℃로 3시간 유지하여 2,6-나프탈렌디카르복실산을 얻었다. 상기 과정으로 얻어진 2,6-나프탈렌디카르복실산은 마지막으로 물의 질량에 대한 에탄올의 질량의 비가 5인 물/에탄올 혼합용매 250g에 상온에서 30분간 교반하여 세척한 후 여과·건조하였다. 결과는 표 2에 나타내었다.50 g of unpurified 2,6-naphthalenedicarboxylic acid consisting of the components of the reference example of Table 1 was mixed with 500 g of dimethylformamide, stirred at 80 ° C. for 30 minutes, cooled, and filtered to perform pretreatment. 200 g of 2,6-naphthalenedicarboxylic acid and triethylamine obtained in the above process were added to a 1 L titanium reaction vessel containing an activated carbon catalyst containing 0.5 wt% of palladium, and H 2 was added to the reactor and maintained at 20 bar. Hydrogenation was carried out for 1 hour at 200 ℃. After the completion of the reaction, the mixture was cooled to room temperature to precipitate 2,6-naphthalenedicarboxylic acid amine salt, filtered, and then maintained at 150 ° C. under reduced pressure for 3 hours to obtain 2,6-naphthalenedicarboxylic acid. The 2,6-naphthalenedicarboxylic acid obtained by the above process was finally washed with 250 g of a water / ethanol mixed solvent having a ratio of the mass of ethanol to the mass of water of 5 at room temperature for 30 minutes, followed by filtration and drying. The results are shown in Table 2.
<실시예 2><Example 2>
전처리 과정에서 용매로 디메틸포름아마이드 대신 디메틸아세트아마이드를 사용한 것을 제외하고는 모든 조건을 실시예 1과 동일하게 수행하였다. 결과는 표 2에 나타내었다.All conditions were carried out in the same manner as in Example 1 except that dimethylacetamide was used instead of dimethylformamide as a solvent in the pretreatment process. The results are shown in Table 2.
<실시예 3><Example 3>
수소화 반응시 용매로 트리에틸아민 대신 메틸아민을 사용한 것을 제외하고는 모든 조건을 실시예 1과 동일하계 수행하였다. 결과는 표 2에 나타내었다.All conditions were carried out in the same manner as in Example 1 except that methylamine was used instead of triethylamine as a solvent in the hydrogenation reaction. The results are shown in Table 2.
<실시예 4><Example 4>
마지막 정제시 물/에탄올 혼합용매 대신 물을 단독으로 사용한 것을 제외하고는 모든 조건을 실시예 1과 동일하게 수행하였다. 결과는 표 2에 나타내었다.All conditions were performed in the same manner as in Example 1 except that water was used alone instead of the water / ethanol mixed solvent in the final purification. The results are shown in Table 2.
<비교예 1>Comparative Example 1
디메틸포름아마이드를 용매로 하여 전처리하는 단계를 생략하는 것을 제외하고는 그 이외의 모든 과정과 조건은 실시예 1과 동일하게 수행하였다. 결과는 표 2에 나타내었다.All other procedures and conditions were carried out in the same manner as in Example 1 except for omitting the pretreatment with dimethylformamide as a solvent. The results are shown in Table 2.
<비교예 2>Comparative Example 2
수소화 반응 후 물/에탄올 혼합용매로 세척하는 단계를 생락하는 것을 제외하고는 그 이외의 모든 과정과 조건은 실시예 1과 동일하게 수행하였다. 결과는 표 2에 나타내었다.All other procedures and conditions were carried out in the same manner as in Example 1 except for the step of washing with a water / ethanol mixed solvent after the hydrogenation reaction. The results are shown in Table 2.
2,6-NDA : 2,6-나프탈렌디카르복실산2,6-NDA: 2,6-naphthalenedicarboxylic acid
TMLA : 트리멜리트산TMLA: trimellitic acid
2,6-FNA : 2,6-포르밀나프토산2,6-FNA: 2,6-formylnaphthoic acid
2-NA : 2-나프토산2-NA: 2-naphthoic acid
2,6-MNA : 2,6-메틸나프토산2,6-MNA: 2,6-methylnaphthoic acid
Br-2,6-NDA : 브로모-2,6-나프탈렌디카르복실산Br-2,6-NDA: Bromo-2,6-naphthalenedicarboxylic acid
본 발명에 의하면, 비교적 용이하게 2,6-나프탈렌디카르복실산을 폴리에틸렌나프탈레이트의 원료로 사용할 수 있을 정도의 고순도로 정제할 수 있다.
Advantageous Effects of Invention According to the present invention, 2,6-naphthalenedicarboxylic acid can be purified with high purity enough to be used as a raw material of polyethylene naphthalate.
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| JPH06279355A (en) * | 1993-03-26 | 1994-10-04 | Sekiyu Sangyo Kasseika Center | Production of 2,6-naphthalene-dicarboxylic acid |
| JPH0971553A (en) * | 1995-09-07 | 1997-03-18 | Mitsubishi Gas Chem Co Inc | Purification of naphthalenedicarboxylic acid |
| US5859294A (en) * | 1996-02-05 | 1999-01-12 | Mitsubishi Gas Chemical Corporation, Inc. | Process for the production of high-purity naphthalenedicarboxylic acid |
-
2002
- 2002-02-21 KR KR1020020009196A patent/KR100605052B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62230747A (en) * | 1986-03-31 | 1987-10-09 | Kureha Chem Ind Co Ltd | Purification of 2,6-naphthalenedicarboxylic acid |
| JPH06279355A (en) * | 1993-03-26 | 1994-10-04 | Sekiyu Sangyo Kasseika Center | Production of 2,6-naphthalene-dicarboxylic acid |
| JPH0971553A (en) * | 1995-09-07 | 1997-03-18 | Mitsubishi Gas Chem Co Inc | Purification of naphthalenedicarboxylic acid |
| US5859294A (en) * | 1996-02-05 | 1999-01-12 | Mitsubishi Gas Chemical Corporation, Inc. | Process for the production of high-purity naphthalenedicarboxylic acid |
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