JP2007169238A - Method for purifying 6,6'-(ethylenedioxy)di-2-naphthoic acid - Google Patents
Method for purifying 6,6'-(ethylenedioxy)di-2-naphthoic acid Download PDFInfo
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縮合重合体の原料である6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸の精製方法、および該精製方法により得られるアルカリ金属塩の含有量が少ない6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸に関する。 A method for purifying 6,6 '-(ethylenedioxy) di-2-naphthoic acid, which is a raw material of the condensation polymer, and 6,6'-(ethylenedioxydiene) containing a small amount of alkali metal salt obtained by the purification method Oxy) di-2-naphthoic acid.
従来から種々の芳香族ジカルボン酸が知られており、ポリエステル、ポリアミドのなどの如き縮合重合体の原料として広く利用されている。例えばテレフタル酸はポリエチレンテレフタレート、ポリテトラエチレンテレフタレート、ポリパラフェニレンテレフタルアミド等の原料として工業的に使用されている。その他イソフタル酸もポリマー用原料として広く利用されている。またナフタレンジカルボン酸を原料としたポリエステルであるポリエチレンナフタレートはポリエチレンテレフタレートに比べ機械的、熱的に更に高性能である事は知られている。 Conventionally, various aromatic dicarboxylic acids are known and widely used as raw materials for condensation polymers such as polyesters and polyamides. For example, terephthalic acid is industrially used as a raw material for polyethylene terephthalate, polytetraethylene terephthalate, polyparaphenylene terephthalamide and the like. Other isophthalic acids are also widely used as raw materials for polymers. Polyethylene naphthalate, which is a polyester made from naphthalenedicarboxylic acid, is known to have higher mechanical and thermal performance than polyethylene terephthalate.
特許文献１にはポリエチレンテレフタレート、ポリエチレンナフタレートよりも更に高性能のポリエステル原料となり得る新規なジカルボン酸である6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸の精製方法に関する記述がある。
6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸を原料とする縮重合体が優れた物性、例えば機械的、熱的物性などを有する事が記載されている。
Patent Document 1 describes a method for purifying 6,6 ′-(ethylenedioxy) di-2-naphthoic acid, which is a novel dicarboxylic acid that can be a higher-performance polyester raw material than polyethylene terephthalate and polyethylene naphthalate. .
It is described that a condensation polymer made from 6,6 ′-(ethylenedioxy) di-2-naphthoic acid has excellent physical properties such as mechanical and thermal properties.
また特許文献２には6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸の製造法について記載されている。製造法は6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸のアルカリ金属塩を合成後、鉱酸や酸性ガスの添加により酸析を行うが、この処方で酸析を行なうとアルカリ金属成分が多量に残存する。このようなアルカリ金属がモノマー中に残存するとポリマーの色相の悪影響を与えるばかりか、熱的特性、機械特性に悪い影響を与える。さらに酸析後の6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸中には、2-ヒドロキシ-6-ナフトエ酸由来の不純物を含有している。 Patent Document 2 describes a method for producing 6,6 ′-(ethylenedioxy) di-2-naphthoic acid. The production method involves synthesizing an alkali metal salt of 6,6 '-(ethylenedioxy) di-2-naphthoic acid and then acidifying it by adding mineral acid or acid gas. A large amount of metal component remains. If such an alkali metal remains in the monomer, it not only adversely affects the hue of the polymer but also adversely affects the thermal and mechanical properties. Furthermore, 6,6 ′-(ethylenedioxy) di-2-naphthoic acid after acid precipitation contains impurities derived from 2-hydroxy-6-naphthoic acid.
本発明の目的は縮合重合体の原料である6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸の精製方法、およびアルカリ金属塩の含有量が少ない6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸を提供することにある。 The object of the present invention is to purify 6,6 ′-(ethylenedioxy) di-2-naphthoic acid, which is a raw material of a condensation polymer, and 6,6 ′-(ethylenedioxy) having a low alkali metal salt content. ) To provide di-2-naphthoic acid.
本発明は6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸ジアルカリ金属塩を水と水溶性有機溶媒との混合溶媒、または水溶性有機溶媒の存在下に酸析することを特徴とする6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸の精製方法である。
本発明により粗6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸中の不純物を効果的に除去できるばかりでなく、アルカリ金属塩の少ない6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸を提供する。
The present invention is characterized in that 6,6 ′-(ethylenedioxy) di-2-naphthoic acid dialkali metal salt is subjected to acid precipitation in a mixed solvent of water and a water-soluble organic solvent, or in the presence of a water-soluble organic solvent. This is a method for purifying 6,6 ′-(ethylenedioxy) di-2-naphthoic acid.
According to the present invention, not only impurities in crude 6,6 ′-(ethylenedioxy) di-2-naphthoic acid can be effectively removed, but also 6,6 ′-(ethylenedioxy) di- Provides 2-naphthoic acid.
本発明によれば6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸アルカリ金属塩を水溶性有機溶媒の存在下酸析することにより6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸中の着色物質、重金属、および反応中間体を効率的に除去できるばかりでなく、濾過性の優れた、結晶粒径の均一な精製6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸が得られる。本発明で得られた6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸を用いることより色相や熱的特性、機械特性に優れた重縮合体を得ることができる。 According to the present invention, 6,6- (ethylenedioxy) -di-2 is obtained by acidifying 6,6- (ethylenedioxy) -di-2-naphthoic acid alkali metal salt in the presence of a water-soluble organic solvent. -Refining 6,6- (ethylenedioxy) -di-2 not only can efficiently remove colored substances, heavy metals and reaction intermediates in naphthoic acid, but also has excellent filterability and crystal grain size -Naphthoic acid is obtained. By using the 6,6 ′-(ethylenedioxy) di-2-naphthoic acid obtained in the present invention, a polycondensate excellent in hue, thermal properties and mechanical properties can be obtained.
2-ヒドロキシ-6-ナフトエ酸のアルカリ金属塩と１，２−ジハロゲン化エタンとを反応させ下記式（Ｉ）
（式中、Mはアルカリ金属、Rはアルカリ金属または水素原子である）
で示される粗6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸モノアルカリ金属塩および/または6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸のジアルカリ金属塩を製造し、次いで概金属塩を酸と反応させることにより粗6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸を製造する事ができる。
By reacting an alkali metal salt of 2-hydroxy-6-naphthoic acid with 1,2-dihalogenated ethane, the following formula (I)
(In the formula, M is an alkali metal and R is an alkali metal or a hydrogen atom)
A crude 6,6 ′-(ethylenedioxy) di-2-naphthoic acid monoalkali metal salt and / or a 6,6- (ethylenedioxy) -di-2-naphthoic acid dialkali metal salt represented by the formula: Subsequently, crude 6,6 ′-(ethylenedioxy) di-2-naphthoic acid can be produced by reacting an approximately metal salt with an acid.
本発明に於いてアルカリ金属としてはナトリウム、カリウムが好ましく、特にカリウムが生成物の溶媒に対する溶解度が高くなるので好ましい。また１，２−ジハロゲン化エタンとしては１，２−ジクロロエタン、１，２−ジブロモエタンが好ましい。また該１，２−ジハロゲン化エタンの使用割合は前記２−ヒドロキシー６−ナフトエ酸のアルカリ金属塩1モルに対し、０．４ないし、１．５モル程である。理論量は０．５モルであるが副反応によって消費されるので理論量よりも多くしてもよい。２−ヒドロキシー６−ナフトエ酸のアルカリ金属塩と１，２−ジハロゲン化エタンとの反応は溶媒中で行なうのが好ましく、かかる溶媒としては水が特に好ましいが、その他、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等のアミド類、テトラヒドロフラン、ジオキサン等のエーテル類、メタノール、エタノール、プロパノール等のアルコール類、アセトン、メチルイソブチルケトン等のケトン類、エチレングリコール、プロピレングリコール等のグリコール類、アセトニトリル等のニトリル類が使用できる。 In the present invention, sodium and potassium are preferable as the alkali metal, and potassium is particularly preferable because the solubility of the product in the solvent is increased. The 1,2-dihalogenated ethane is preferably 1,2-dichloroethane or 1,2-dibromoethane. The proportion of 1,2-dihalogenated ethane used is about 0.4 to 1.5 moles per mole of the alkali metal salt of 2-hydroxy-6-naphthoic acid. The theoretical amount is 0.5 mol, but may be larger than the theoretical amount because it is consumed by side reactions. The reaction between the alkali metal salt of 2-hydroxy-6-naphthoic acid and 1,2-dihalogenated ethane is preferably carried out in a solvent. As such a solvent, water is particularly preferred, but N, N-dimethylformamide, Amides such as N, N-dimethylacetamide, ethers such as tetrahydrofuran and dioxane, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl isobutyl ketone, glycols such as ethylene glycol and propylene glycol, acetonitrile Nitriles such as can be used.
反応温度は、好ましくは50〜250℃、特に好ましくは60〜200℃であり、反応は常圧〜加圧下で実施できる。本発明では、ヨウ素カリウム等の触媒、銅などの安定剤を添加剤として用いてよく、また2-ヒドロキシ-6-ナフトエ酸またはそのモノアルカリ金属塩を反応系に存在させてもよい。必要により相間移動反応系で行なってもよく、この場合には、水-芳香族炭化水素系、水-ハロゲン化炭化水素系等を溶媒として用い、クラウンエーテル類、クリプタンド類、４級アンモニウム塩等を相間移動触媒として用いる方法が挙げられる。 The reaction temperature is preferably 50 to 250 ° C., particularly preferably 60 to 200 ° C., and the reaction can be carried out under normal pressure to increased pressure. In the present invention, a catalyst such as potassium iodine and a stabilizer such as copper may be used as additives, and 2-hydroxy-6-naphthoic acid or a monoalkali metal salt thereof may be present in the reaction system. If necessary, a phase transfer reaction system may be used. In this case, water-aromatic hydrocarbon system, water-halogenated hydrocarbon system, etc. are used as a solvent, crown ethers, cryptands, quaternary ammonium salts, etc. Can be used as a phase transfer catalyst.
上記芳香族炭化水素としてはベンゼン、キシレン、トルエンなどが挙げられる。またハロゲン化炭化水素としてはジクロロメタン、ジクロロエタン、クロロホルムなどが例示される。 Examples of the aromatic hydrocarbon include benzene, xylene, toluene and the like. Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform and the like.
かかる方法により6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸モノアルカリ金属塩、および/または6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸ジアルカリ金属塩が生成する。反応溶媒として水を用いた場合には、該生成物が6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸モノカリウム、6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸モノナトリウムおよび、6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸ジナトリウムの場合には溶解度が極めて低く反応系からろ過によって単離でき、また6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸ジカリウムの場合には一時溶解するが冷却する事によって析出するので単離する事ができる。反応系ではこのようにして得た6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸アルカリ金属塩を酸と反応せしめる。 Such a method produces 6,6- (ethylenedioxy) -di-2-naphthoic acid monoalkali metal salt and / or 6,6- (ethylenedioxy) -di-2-naphthoic acid dialkali metal salt. When water is used as the reaction solvent, the product is monopotassium 6,6- (ethylenedioxy) -di-2-naphthoate, 6,6- (ethylenedioxy) -di-2-naphthoic acid. In the case of monosodium and 6,6- (ethylenedioxy) -di-2-naphthoate disodium, the solubility is very low and it can be isolated from the reaction system by filtration, and 6,6- (ethylenedioxy)- In the case of dipotassium di-2-naphthoate, it dissolves temporarily but precipitates when cooled, so it can be isolated. In the reaction system, the 6,6- (ethylenedioxy) -di-2-naphthoic acid alkali metal salt thus obtained is reacted with an acid.
また反応物の異物除去および着色成分の除去を行なう場合には6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸のジアルカリ金属塩にして一旦溶解し、ろ過および活性炭処理などを施す事が好ましい。 6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸ジカリウムは6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸モノカリウムにさらにアルカリ成分を添加する事で容易に得る事が出来、溶解性も高い事から特に好ましい。このようにジアルカリ金属塩とする際の温度は室温でも構わないが一般には加熱下で行うことが好ましい。ジアルカリ金属塩溶解度が向上し釜効率が良くなる。この加熱処理は通常０．５〜５時間で行い不溶物がある時は濾別して除く。上記のようにして得られる水溶液中の6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸のジアルカリ金属塩の濃度は、通常０．２〜 ３０重量％である。 In addition, when removing foreign substances from the reactants and removing colored components, dissolve it as a dialkali metal salt of 6,6- (ethylenedioxy) -di-2-naphthoic acid, and filter, treat with activated carbon, etc. Is preferred. Dipotassium 6,6- (ethylenedioxy) -di-2-naphthoate can be easily obtained by adding an alkali component to monopotassium 6,6- (ethylenedioxy) -di-2-naphthoate. It is particularly preferable because of its high solubility. Thus, although the temperature at the time of setting it as a dialkali metal salt may be room temperature, generally it is preferable to carry out under heating. The dialkali metal salt solubility is improved and the pot efficiency is improved. This heat treatment is usually carried out for 0.5 to 5 hours, and when there is insoluble matter, it is filtered off. The concentration of the dialkali metal salt of 6,6- (ethylenedioxy) -di-2-naphthoic acid in the aqueous solution obtained as described above is usually 0.2 to 30% by weight.
6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸ジアルカリ金属塩は水と有機溶媒との混合溶媒系による酸析により精製6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸を容易に得ることはできるが、酸析に先立って活性炭処理を行うことにより、さらに高純度のものを得ることができるので好ましく用いる事ができる。 6,6- (Ethylenedioxy) -di-2-naphthoic acid dialkali metal salt is purified by acid precipitation in a mixed solvent system of water and organic solvent. 6,6- (Ethylenedioxy) -di-2-naphthoic acid Can be easily obtained, but it can be preferably used because it can be obtained with a higher purity by treating with activated carbon prior to acid precipitation.
活性炭処理法は流通式又は回分式で行う。例えば流通式の場合には粒状の活性炭をカラムに充填しアップフロ−又はダウンフロ−で6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸ジアルカリ金属塩水溶液を流通させる。処理温度は室温〜６０℃で行うが通常は室温で充分である。回分式の場合には水溶液中の6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸ジアルカリ金属塩に対して１〜１０重量％程度の粉末活性炭を加え１〜５時間撹拌下処理する。活性炭処理は強塩基で処理するよりも中性付近のほうが処理効果が大きい。活性炭種には特に制限は無くどんな種類のものでも使用できる。 The activated carbon treatment method is carried out by a distribution method or a batch method. For example, in the case of a circulation type, granular activated carbon is packed in a column and a 6,6- (ethylenedioxy) -di-2-naphthoic acid dialkali metal salt aqueous solution is circulated by up-flow or down-flow. The treatment temperature is from room temperature to 60 ° C., but room temperature is usually sufficient. In the case of a batch system, about 1 to 10% by weight of powdered activated carbon is added to the 6,6- (ethylenedioxy) -di-2-naphthoic acid dialkali metal salt in an aqueous solution, and the mixture is stirred for 1 to 5 hours. . The activated carbon treatment is more effective in the vicinity of neutrality than the treatment with a strong base. There are no particular restrictions on the type of activated carbon, and any type can be used.
6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸アルカリ金属塩の酸析は水と水溶性有機溶媒との混合溶媒、または水溶性有機溶媒の存在下に行う。通常は、6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸アルカリ金属塩水溶液と水溶性有機溶媒を混合して行う。水溶性有機溶媒としては水に対する溶解度の大きなものが好ましく、具体的には２０℃における水への溶解度が１００ｇ／１００ｇ・Ｈ2Ｏ以上の有機溶媒、例えば、メタノ−ル、エタノ−ル、２−プロパノ−ル等のアルコ−ル類、アセトン、メチルエチルケトン等のケトン類、その他ジメチルスルホキシド、アセトニトリル等を用いることができる。これらの有機溶媒は単独で用いても、又は混合して用いても良い。 The acid precipitation of 6,6- (ethylenedioxy) -di-2-naphthoic acid alkali metal salt is carried out in the presence of a mixed solvent of water and a water-soluble organic solvent or a water-soluble organic solvent. Usually, 6,6- (ethylenedioxy) -di-2-naphthoic acid alkali metal salt aqueous solution and a water-soluble organic solvent are mixed. As the water-soluble organic solvent, those having high solubility in water are preferable. Specifically, organic solvents having a solubility in water at 20 ° C. of 100 g / 100 g · H 2 O or more, such as methanol, ethanol, 2 -Alcohols such as propanol, ketones such as acetone and methyl ethyl ketone, dimethyl sulfoxide, acetonitrile and the like can be used. These organic solvents may be used alone or in combination.
水溶液中の6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸アルカリ金属塩の濃度は、通常０．２〜 ３０重量％である。有機溶媒の量は6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸アルカリ金属塩の水溶液中での濃度及び塩の種類により異なるが、水溶液中の水１００ｇに対し５０ｇ〜２００ｇ程度用いる。使用する有機溶媒の量が少なすぎると本発明の効果が充分に現れない。このようにし6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸アルカリ金属塩を有機溶媒と水の混合溶媒に分散または溶解させておき、撹拌下に酸を加え酸析して6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸の結晶を得る。酸は塩酸、硫酸等の鉱酸や亜硫酸ガス等の酸性ガスを用いるが通常は硫酸等の鉱酸を水で希釈して使用する。希釈濃度は任意であり本発明の効果にはほとんど問題ないが、通常は、例えば、硫酸であれば１〜５０重量％程度のものを使用する。酸の添加は反応液のｐＨが２付近になるまで加える。添加速度は添加量にもよるが、通常は０．０１〜１０時間で、酸添加後も攪拌を３〜３０分間そのまま続ける。酸析の温度は室温から有機溶媒の沸点程度で行うが、加圧下沸点以上の高温で行うこともできる。生成した6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸の結晶は、濾別後、十分水洗し乾燥する。得られる6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸の結晶粒径は、通常、１〜５００μｍとなる。
さらに水溶性有機溶媒存在下に酸析を行なう事により２−ヒドロキシー６−ナフトエ酸由来の不純物を容易に除去できるだけでなくろ過性も改善する。
The concentration of 6,6- (ethylenedioxy) -di-2-naphthoic acid alkali metal salt in the aqueous solution is usually 0.2 to 30% by weight. The amount of the organic solvent varies depending on the concentration of the 6,6- (ethylenedioxy) -di-2-naphthoic acid alkali metal salt in the aqueous solution and the kind of the salt, but it is used in an amount of about 50 to 200 g with respect to 100 g of water in the aqueous solution. . If the amount of the organic solvent used is too small, the effect of the present invention will not be sufficiently exhibited. In this way, 6,6- (ethylenedioxy) -di-2-naphthoic acid alkali metal salt was dispersed or dissolved in a mixed solvent of an organic solvent and water, and acid was added with stirring to cause acid precipitation. Crystals of 6- (ethylenedioxy) -di-2-naphthoic acid are obtained. As the acid, a mineral acid such as hydrochloric acid or sulfuric acid, or an acidic gas such as sulfurous acid gas is used. Usually, a mineral acid such as sulfuric acid is diluted with water. The dilution concentration is arbitrary, and there is almost no problem with the effect of the present invention, but usually, for example, about 1 to 50% by weight of sulfuric acid is used. The acid is added until the pH of the reaction solution reaches about 2. Although the addition rate depends on the addition amount, it is usually 0.01 to 10 hours, and stirring is continued for 3 to 30 minutes after the acid addition. The acid precipitation temperature is from room temperature to about the boiling point of the organic solvent, but can also be carried out at a high temperature above the boiling point under pressure. The produced 6,6- (ethylenedioxy) -di-2-naphthoic acid crystals are separated by filtration, sufficiently washed with water and dried. The crystal grain size of the obtained 6,6- (ethylenedioxy) -di-2-naphthoic acid is usually 1 to 500 μm.
Furthermore, by performing acid precipitation in the presence of a water-soluble organic solvent, not only impurities derived from 2-hydroxy-6-naphthoic acid can be easily removed but also filterability is improved.
本発明の精製方法よりアルカリ金属塩の含有量が１〜５００ｐｐｍの6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸を得ることができる。好ましくはアルカリ金属塩の含有量が１〜２００ｐｐｍであると縮合重合体の原料として好ましく、より好ましくは１〜１００ppmの範囲である。本発明で得られた6,6'-(エチレンジオキシ)ジ-2-ナフトエ酸より色相や熱的特性、機械特性に優れた重縮合体を得ることができる。 From the purification method of the present invention, 6,6 ′-(ethylenedioxy) di-2-naphthoic acid having an alkali metal salt content of 1 to 500 ppm can be obtained. Preferably, the content of the alkali metal salt is 1 to 200 ppm as a raw material for the condensation polymer, and more preferably in the range of 1 to 100 ppm. A polycondensate excellent in hue, thermal properties and mechanical properties can be obtained from 6,6 ′-(ethylenedioxy) di-2-naphthoic acid obtained in the present invention.
以下に実施例及び比較例を挙げ本発明をより具体的に説明する。２−ヒドロキシー６−ナフトエ酸はアルドリッチ(株)から、ジクロロエタン、水酸化カリウム、エタノールは和光純薬工業から入手した。アルカリ成分は原子吸光法（日立製作所製偏光ゼーマン原子吸光光度計Z5000）により定量分析を行った。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. 2-Hydroxy-6-naphthoic acid was obtained from Aldrich, and dichloroethane, potassium hydroxide, and ethanol were obtained from Wako Pure Chemical Industries. The alkali component was quantitatively analyzed by an atomic absorption method (polarized Zeeman atomic absorption photometer Z5000 manufactured by Hitachi, Ltd.).
[実施例１]
10Lの攪拌付きオートクレーブに２−ヒドロキシー６−ナフトエ酸1000重量部、水酸化カリウム597重量部、ジクロロエタン263重量部、水5000重量部を仕込み窒素置換後、窒素圧0.3Mpaを掛け攪拌下120℃〜130℃で反応した。反応後冷却・ろ過することにより6,6’-(エチレンジオキシ)ジ-2-ナフトエ酸モノカリウム塩を主成分とする固体を得た。この生成物の乾燥重量380重量部であった。この生成物を5Lのセパラブルフラスコに入れ、ついで水酸化カリウム46重量部、水5400重量部を加え100℃で加熱した。塩が完全に溶解したところで熱ろ過してエタノール５４００重量部を加えた後、硫酸を加え温度75℃で酸析を行った。酸析後、析出した固体をろ過し水洗し減圧乾燥した。乾燥後の乾燥重量は290重量部であった。6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸結晶の最小粒径は５μｍでろ過は容易であった。このものの元素分析結果は下記の通り6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸に一致した。また6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸中の残留アルカリ成分は19ppmであった。
[Example 1]
A 10 L autoclave with stirring was charged with 1000 parts by weight of 2-hydroxy-6-naphthoic acid, 597 parts by weight of potassium hydroxide, 263 parts by weight of dichloroethane, and 5000 parts by weight of water. Reacted at 130 ° C. After the reaction, the mixture was cooled and filtered to obtain a solid mainly composed of 6,6 ′-(ethylenedioxy) di-2-naphthoic acid monopotassium salt. The dry weight of this product was 380 parts by weight. This product was put into a 5 L separable flask, and then 46 parts by weight of potassium hydroxide and 5400 parts by weight of water were added and heated at 100 ° C. When the salt was completely dissolved, it was filtered hot and 5400 parts by weight of ethanol was added. Then, sulfuric acid was added and acid precipitation was carried out at a temperature of 75 ° C. After acid precipitation, the precipitated solid was filtered, washed with water, and dried under reduced pressure. The dry weight after drying was 290 parts by weight. The minimum particle size of 6,6- (ethylenedioxy) -di-2-naphthoic acid crystals was 5 μm and filtration was easy. The elemental analysis result of this product was consistent with 6,6- (ethylenedioxy) -di-2-naphthoic acid as follows. The residual alkali component in 6,6- (ethylenedioxy) -di-2-naphthoic acid was 19 ppm.
[実施例２]
10Lの攪拌付きオートクレーブに２−ヒドロキシー６−ナフトエ酸1000重量部、水酸化ナトリウム597重量部、ジクロロエタン263 重量部、水5000重量部を仕込み、窒素置換後、窒素圧0.3Mpaを掛け攪拌下120℃〜130℃で反応した。反応後、冷却・ろ過することにより6,6’-(エチレンジオキシ)ジ-2-ナフトエ酸ジナトリウム塩を主成分とする固体を得た。この生成物の乾燥重量は557重量部であった。この固体に水3000重量部、メタノール3000重量部、硫酸１３５重量部を加え温度65℃で酸析を行った。酸析後、析出した固体をろ過し水洗し減圧乾燥した。6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸結晶の最小粒径は７μｍでろ過は容易であった。また6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸中の残留アルカリ成分は100ppmであった。
[Example 2]
A 10 L autoclave with stirring was charged with 1000 parts by weight of 2-hydroxy-6-naphthoic acid, 597 parts by weight of sodium hydroxide, 263 parts by weight of dichloroethane, and 5000 parts by weight of water. Reacted at ~ 130 ° C. After the reaction, the mixture was cooled and filtered to obtain a solid mainly composed of 6,6 ′-(ethylenedioxy) di-2-naphthoic acid disodium salt. The dry weight of this product was 557 parts by weight. To this solid, 3000 parts by weight of water, 3000 parts by weight of methanol, and 135 parts by weight of sulfuric acid were added, and acid precipitation was performed at a temperature of 65 ° C. After acid precipitation, the precipitated solid was filtered, washed with water, and dried under reduced pressure. The minimum particle size of 6,6- (ethylenedioxy) -di-2-naphthoic acid crystals was 7 μm and filtration was easy. The residual alkali component in 6,6- (ethylenedioxy) -di-2-naphthoic acid was 100 ppm.
[実施例３]
実施例２で酸析に使用する溶媒について、水3000重量部、メタノール3000重量部の混合溶液からから水3000重量部、アセトン3000重量部に変え室温で酸析を行なった。その結果6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸結晶の最小粒径は６μｍでろ過は同様に容易であった。また残留アルカリ成分量は80ppmであった。
[Example 3]
The solvent used for acid precipitation in Example 2 was changed from a mixed solution of 3000 parts by weight of water and 3000 parts by weight of methanol to 3000 parts by weight of water and 3000 parts by weight of acetone, and was subjected to acid precipitation at room temperature. As a result, the minimum particle size of 6,6- (ethylenedioxy) -di-2-naphthoic acid crystals was 6 μm and filtration was equally easy. The residual alkali component amount was 80 ppm.
[比較例１]
実施例２において使用する溶媒を、水3000重量部、メタノール3000重量部の混合溶液から水6000重量部に変え同様に酸析を行った。その結果6,6-(エチレンジオキシ)-ジ-2-ナフトエ酸の最小粒径は２μｍ以下であり、ろ過は時間がかかり、また残留アルカリ成分量は2ｗｔ%と非常に多い値であった。
[Comparative Example 1]
The solvent used in Example 2 was changed from a mixed solution of 3000 parts by weight of water and 3000 parts by weight of methanol to 6000 parts by weight of water, and acid precipitation was performed in the same manner. As a result, the minimum particle size of 6,6- (ethylenedioxy) -di-2-naphthoic acid was 2 μm or less, the filtration took time, and the amount of residual alkali component was very high at 2 wt%. .
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007169237A (en) * | 2005-12-26 | 2007-07-05 | Teijin Ltd | Method for purifying 6,6'-(ethylenedioxy)di-2-naphthoic acid |
| JP2008001603A (en) * | 2006-06-20 | 2008-01-10 | Teijin Ltd | Method for preparing 6,6'-(alkylenedioxy)di-2-naphthoic acid |
| JP2009120540A (en) * | 2007-11-15 | 2009-06-04 | Ueno Fine Chem Ind Ltd | Method for purifying 6,6'-(ethylenedioxy)bis-2-naphthoic acid |
| JP2009120539A (en) * | 2007-11-15 | 2009-06-04 | Ueno Fine Chem Ind Ltd | Method for producing 6,6'-(ethylenedioxy)bis-2-naphthoic acid |
| JP2009120541A (en) * | 2007-11-15 | 2009-06-04 | Ueno Fine Chem Ind Ltd | Method for purifying 6,6'-(ethylenedioxy)bis-2-naththoic acid |
| JP2009137867A (en) * | 2007-12-05 | 2009-06-25 | Ueno Fine Chem Ind Ltd | Method for purifying 6,6'-(ethylenedioxy)bis-2-naphthoic acid |
| JP2009137866A (en) * | 2007-12-05 | 2009-06-25 | Ueno Fine Chem Ind Ltd | Method for producing 6,6'-(ethylenedioxy)bis-2-naphthoic acid |
| JP2009155230A (en) * | 2007-12-25 | 2009-07-16 | Ueno Fine Chem Ind Ltd | Method for producing recycled 6-hydroxy-2-naphthoic acid |
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| JP2009137866A (en) * | 2007-12-05 | 2009-06-25 | Ueno Fine Chem Ind Ltd | Method for producing 6,6'-(ethylenedioxy)bis-2-naphthoic acid |
| JP2009155230A (en) * | 2007-12-25 | 2009-07-16 | Ueno Fine Chem Ind Ltd | Method for producing recycled 6-hydroxy-2-naphthoic acid |
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