JP2005314296A - Anhydrous product crystal produced by heating of bisphenyltetracarboxylic acid - Google Patents
Anhydrous product crystal produced by heating of bisphenyltetracarboxylic acid Download PDFInfo
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本発明は、ビフェニルテトラカルボン酸加熱無水化生成物結晶に関し、詳しくは、ビフェニルテトラカルボン酸二無水物を主成分とし、着色の少ない、ビフェニルテトラカルボン酸加熱無水化生成物結晶に関する。 The present invention relates to a biphenyltetracarboxylic acid heat-dehydrated product crystal, and more particularly, to a biphenyltetracarboxylic acid heat-dehydrated product crystal composed mainly of biphenyltetracarboxylic dianhydride and less colored.
ビフェニルテトラカルボン酸二無水物（以下「ＢＰＤＡ」と称することがある）は、耐熱性樹脂として注目されている芳香族ポリイミド樹脂の製造用原料として有用な化合物である。ＢＰＤＡを原料とする芳香族ポリイミド樹脂の製造方法としては、ＢＰＤＡと芳香族ジアミン類との重合反応による方法、ＢＰＤＡと芳香族ジアミンを常温付近の低温で重合して得られるポリアミック酸を閉環イミド化する方法などが挙げられる。 Biphenyltetracarboxylic dianhydride (hereinafter sometimes referred to as “BPDA”) is a useful compound as a raw material for producing an aromatic polyimide resin that has attracted attention as a heat-resistant resin. As a method for producing an aromatic polyimide resin using BPDA as a raw material, a method using a polymerization reaction between BPDA and an aromatic diamine, a polyamic acid obtained by polymerizing BPDA and an aromatic diamine at a low temperature around room temperature, and ring-closing imidization The method of doing is mentioned.
ＢＰＤＡの製造は、一般的にビフェニルテトラカルボン酸（以下「ＢＴＣ」と称する）を脱水閉環することによって行われている。一方、ＢＴＣの製造方法としては、例えば以下の（ｉ）、（i i）に記載の方法がある。 BPDA is generally produced by dehydrating and ring-closing biphenyltetracarboxylic acid (hereinafter referred to as “BTC”). On the other hand, as a method for producing BTC, for example, there are methods described in (i) and (ii) below.
（ｉ）O−フタル酸ジメチルの脱水素二量化反応で得られたビフェニルテトラカルボン酸テトラメチルを、Ｐｄ触媒の存在下で、水性媒体中で加水分解する方法。 (I) A method of hydrolyzing tetramethyl biphenyltetracarboxylate obtained by dehydrogenation dimerization reaction of dimethyl O-phthalate in an aqueous medium in the presence of a Pd catalyst.
（i i）無水フタル酸をハロゲン化して得られる４−ハロフタル酸を、水性媒体中、アルカリ・還元剤・Ｐｄ触媒の存在下、脱ハロゲン二量化し、ビフェニルテトラカルボン酸テトラアルカリ金属塩水溶液を得、これを鉱酸で中和する方法。 (Ii) 4-halophthalic acid obtained by halogenating phthalic anhydride is dehalogenated in an aqueous medium in the presence of an alkali, a reducing agent, and a Pd catalyst to obtain a biphenyltetracarboxylic acid tetraalkali metal salt aqueous solution. The method of neutralizing this with a mineral acid.
上記の様な方法により製造されたＢＴＣは、適当な方法、例えば、無溶媒中で減圧下に加熱する方法、無水酢酸などのＢＴＣを実質的に溶解しない液状媒体中にて加熱する方法などにより脱水反応され、ＢＰＤＡが製造される。なお、上記（i i）の方法を経由するＢＰＤＡ及び芳香族ポリイミド樹脂の製造ルートを化学式で示せば次の通りである。 The BTC produced by the above method can be obtained by an appropriate method, for example, a method of heating under reduced pressure in a solvent-free manner, a method of heating in a liquid medium that does not substantially dissolve BTC such as acetic anhydride, and the like. It is dehydrated to produce BPDA. The production route of BPDA and aromatic polyimide resin via the above method (ii) can be represented by the following chemical formula.
上述の従来法においては、各工程の反応条件を適当に制御することにより、高純度ＢＰＤＡ結晶が得られるが、この場合にも生成する結晶には若干の着色が免がれなかった。この着色はＢＰＤＡを使用して芳香族ポリイミド樹脂を製造する際、その樹脂製品の着色要因の一つと考えられており、着色の少ないＢＰＤＡが望まれている。 In the above-described conventional method, high-purity BPDA crystals can be obtained by appropriately controlling the reaction conditions in each step. However, in this case as well, some coloration is inevitable. This coloring is considered to be one of the coloring factors of the resin product when an aromatic polyimide resin is produced using BPDA, and BPDA with little coloring is desired.
ＢＰＤＡの着色を低下させる方法として、ＢＴＣを減圧下、１５０〜２３０℃の温度に加熱して脱水反応を行なわせた後、生成したＢＰＤＡを３０ｍｍＨｇ以下の減圧下、２５０〜４００℃の温度に引き続き加熱して揮発させ、次いで、その揮発したＢＰＤＡの蒸気を冷却して精製結晶として回収する方法が提案されている（例えば特許文献１参照）。 As a method of reducing the coloration of BPDA, after dehydration reaction was performed by heating BTC to a temperature of 150 to 230 ° C. under reduced pressure, the resulting BPDA was continuously heated to a temperature of 250 to 400 ° C. under a reduced pressure of 30 mmHg or less. There has been proposed a method of volatilizing by heating and then recovering the vaporized BPDA as purified crystals by cooling (see, for example, Patent Document 1).
また、高融点有機化合物を溶融・蒸発させ、次いで、冷却して高融点有機化合物を精製するに当たり、当該高融点有機化合物蒸発時の蒸気の線速を制御することにより、当該高融点有機化合物中に含有される不溶性微粒体量を低減させる方法（即ち、高純度ＢＰＤＡを得る方法）が提案されている（例えば特許文献２参照）。 Further, when the high melting point organic compound is melted and evaporated and then cooled to purify the high melting point organic compound, by controlling the linear velocity of the vapor when the high melting point organic compound is evaporated, There has been proposed a method for reducing the amount of insoluble fine particles contained in (ie, a method for obtaining high-purity BPDA) (see, for example, Patent Document 2).
しかしながら、上記の様な方法で得られるＢＰＤＡであっても、高透明度、着色抑制への要求が更に厳しくなっている近年の芳香族ポリイミド樹脂原料としては未だ不十分であり、より着色を抑制し、且つ、不純物の少ない高純度ＢＰＤＡが切望されている。 However, even BPDA obtained by the method as described above is still insufficient as a recent aromatic polyimide resin raw material where demands for high transparency and coloring suppression are becoming stricter, and coloring is further suppressed. In addition, high-purity BPDA with few impurities is desired.
その背景は次の通りである。すなわち、従来、その用途から着色が余り問題視されていなかった芳香族ポリイミド樹脂が、最近、その特徴である高寸法安定性や高耐熱性を背景に用途が広がったため、今までは着色のために使用できないと考えられていた分野への応用が検討される様になってきた。更に、ＢＰＤＡを原料とする芳香族ポリイミド樹脂が有する高耐熱性、高寸法安定性などの特徴から、精密な電子回路基盤用の部材としての用途も広がっており、不純物、特に金属の含有量の少ないＢＰＤＡが切望される様になった。 The background is as follows. In other words, the aromatic polyimide resin, which has not been regarded as a problem of coloring due to its use, has recently been used because of its high dimensional stability and high heat resistance. Application to fields that were thought to be unusable in Japan has been studied. Furthermore, due to the characteristics such as high heat resistance and high dimensional stability of aromatic polyimide resin made from BPDA, its use as a member for precise electronic circuit boards is expanding, and the content of impurities, especially metals, is increasing. Fewer BPDA's were needed.
本発明者らは、上記課題を解決するため、ＢＰＤＡを減圧下に蒸発させる際、蒸発温度、蒸発速度、蒸発時の系内の酸素濃度が、生成するＢＰＤＡの着色度に影響を与えると予想して種々検討を行った。その結果、常温のＢＰＤＡを加熱溶融して得られた溶融物を、減圧下、系内の酸素濃度を１０ｐｐｍ以下に保ちながら、３０７℃以上３３０℃以下の温度で蒸発させ、高純度ＢＰＤＡを蒸気として回収し、この蒸気を冷却して結晶化することによって、従来より着色が少なく、不純物として含有されるパラジウム（Ｐｄ）含有量の少ないＢＰＤＡを製造できることを見出した。 In order to solve the above-mentioned problems, the present inventors expect that when BPDA is evaporated under reduced pressure, the evaporation temperature, the evaporation rate, and the oxygen concentration in the system at the time of evaporation affect the coloring degree of the BPDA produced. Various studies were conducted. As a result, the melt obtained by heating and melting BPDA at room temperature was evaporated at a temperature of 307 ° C. or higher and 330 ° C. or lower under reduced pressure while maintaining the oxygen concentration in the system at 10 ppm or lower, and high purity BPDA was vaporized. It was found that BPDA can be produced by cooling and vaporizing this vapor and crystallizing it to produce a BPDA with less coloration and less palladium (Pd) content as impurities.
ところで、従来からＢＰＤＡ結晶の着色は知られており、例えば、特開昭６１−２４９９７７号公報には、得られたＢＰＤＡの着色度に関し、Ｎ−メチルピロリドンに溶解した溶液についてガードナー色数計を使用して比較測定した値の記載があるが、この方法では溶媒であるＮ−メチルピロリドンの着色の影響を受ける場合があり、測定の精度としても十分なものとは言い難い。そこで、本発明らはＢＰＤＡの着色度の測定法について鋭意検討した結果、特定条件下において、具体的には、ＢＰＤＡを特定濃度のＮａＯＨ水溶液とした際の光透過率を測定することによって、ＢＰＤＡの着色度を定量的に表すことが出来ることを見出した。 By the way, coloring of BPDA crystals has been conventionally known. For example, JP-A-61-249977 discloses a Gardner colorimeter for a solution dissolved in N-methylpyrrolidone regarding the degree of coloring of the obtained BPDA. Although there is a description of the values measured by comparison using this method, this method may be affected by the coloring of N-methylpyrrolidone as a solvent, and it is difficult to say that the accuracy of measurement is sufficient. Therefore, the present inventors have intensively studied a method for measuring the degree of coloration of BPDA. As a result, under specific conditions, specifically, by measuring the light transmittance when BPDA is used as a NaOH aqueous solution having a specific concentration, It was found that the degree of coloring of can be expressed quantitatively.
そして、前述の方法にて得られた高純度ＢＰＤＡはＮａＯＨ水溶液とした際の光透過率が極めて高い優れたものであり、次の様な特性を有していることを見い出した。すなわち、この高純度ＢＰＤＡは、濃度０．０５ｇ／ｍｌのＮａＯＨ水溶液とした際、この溶液に対する波長４００ｎｍの光透過率が９０％以上であり、更に、このＢＰＤＡのＰｄ含有量を測定すると０．２ｐｐｍ以下である。 And the high purity BPDA obtained by the above-mentioned method was found to have excellent light transmittance when it was made into an NaOH aqueous solution, and had the following characteristics. That is, when this high-purity BPDA is a NaOH aqueous solution having a concentration of 0.05 g / ml, the light transmittance at a wavelength of 400 nm with respect to this solution is 90% or more. Further, when the Pd content of this BPDA is measured, 2 ppm or less.
本発明は、上記の種々の知見に基づき完成されたものであり、その要旨は、２規定のＮａＯＨ水溶液にビフェニルテトラカルボン酸加熱無水化生成物を０．０５ｇ／ｍｌの濃度に溶解して得られた溶液に対する波長４００ｎｍの光透過率が９０％以上であることを特徴とするビフェニルテトラカルボン酸加熱無水化生成物結晶に存する。 The present invention has been completed on the basis of the above-mentioned various findings, and the gist thereof is obtained by dissolving a biphenyltetracarboxylic acid heat-dehydrated product in a 2N NaOH aqueous solution at a concentration of 0.05 g / ml. It exists in the biphenyltetracarboxylic-acid heat | fever anhydrous product crystal | crystallization characterized by the light transmittance of wavelength 400nm with respect to the obtained solution being 90% or more.
芳香族ポリイミド樹脂用原料として有用な着色の少ないビフェニルテトラカルボン酸加熱無水化生成物結晶を提供する。 Provided is a biphenyltetracarboxylic acid heat-dehydrated product crystal with little coloration that is useful as a raw material for an aromatic polyimide resin.
以下、本発明を詳細に説明する。本発明のビフェニルテトラカルボン酸加熱無水化生成物結晶は、ＢＰＤＡを主成分とし、通常、不純物としてビフェニルトリカルボン酸無水物を含有する組成物の結晶である。ビフェニルトリカルボン酸無水物の割合は、ＢＰＤＡに対し、通常０．５重量％以下、好ましくは０．３重量％以下であり、その下限は、通常０．０１〜０．１重量％である。従って、本発明のビフェニルテトラカルボン酸加熱無水化生成物結晶は、実質的成分がＢＰＤＡであることから、ＢＰＤＡと呼ぶことが出来、以下においてはその様に称することがある。なお、上記のビフェニルトリカルボン酸無水物は、ＢＴＣを脱水反応してＢＰＤＡを製造する際に副生する。 Hereinafter, the present invention will be described in detail. The biphenyltetracarboxylic acid heat-dehydrated product crystal of the present invention is a crystal of a composition containing BPDA as a main component and usually containing biphenyltricarboxylic acid anhydride as an impurity. The proportion of biphenyltricarboxylic acid anhydride is usually 0.5% by weight or less, preferably 0.3% by weight or less, based on BPDA, and its lower limit is usually 0.01 to 0.1% by weight. Accordingly, the biphenyltetracarboxylic acid heat-dehydrated product crystal of the present invention can be referred to as BPDA since the substantial component is BPDA, and may be referred to as such in the following. In addition, said biphenyl tricarboxylic acid anhydride is by-produced when dehydrating BTC and manufacturing BPDA.
本発明のビフェニルテトラカルボン酸加熱無水化生成物結晶は２規定のＮａＯＨ水溶液に０．０５ｇ／ｍｌの濃度で溶解して得られた溶液に対する波長４００ｎｍの光透過率が９０％以上であることを特徴とする。光透過率が９０％未満の場合は、淡黄色を呈し、本発明の目的を達成することが出来ない。光透過率は、好ましくは９５％以上、更に好ましくは９８％以上であり、また、Ｐｄ含有量が０．２ｐｐｍ以下であることが好ましい。 The biphenyltetracarboxylic acid heat-dehydrated product crystal of the present invention has a light transmittance at a wavelength of 400 nm of 90% or more for a solution obtained by dissolving it in a 2N NaOH aqueous solution at a concentration of 0.05 g / ml. Features. When the light transmittance is less than 90%, a light yellow color is exhibited and the object of the present invention cannot be achieved. The light transmittance is preferably 95% or more, more preferably 98% or more, and the Pd content is preferably 0.2 ppm or less.
本発明の高純度ＢＰＤＡの光透過率は次の様に測定する。先ず、２規定のＮａＯＨ水溶液に０．０５ｇ／ｍｌの濃度で溶解したサンプル溶液を調製する。次いで、内径１０ｍｍの石英セルを使用し、水を対照液とし、分光光度計（島津製作所製「ＵＶ−２６５ＦＷ型」）で測定する。上記のＮａＯＨとしては、試薬特級品を使用し、サンプル溶液の調製や対照液に使用する水は、蒸留水またはイオン交換樹脂処理水を使用する。 The light transmittance of the high purity BPDA of the present invention is measured as follows. First, a sample solution dissolved in a 2N NaOH aqueous solution at a concentration of 0.05 g / ml is prepared. Next, a quartz cell having an inner diameter of 10 mm is used, and water is used as a control solution, and measurement is performed with a spectrophotometer (“UV-265FW type” manufactured by Shimadzu Corporation). As the above-mentioned NaOH, a reagent-grade product is used, and distilled water or ion-exchange resin-treated water is used as the water used for the preparation of the sample solution and the control solution.
また、本発明の高純度ＢＰＤＡのＰｄ含有量は、 誘導結合プラズマ質量分析法（ＩＣＰ−ＭＳ）にて測定することが出来、試料の調製は次の様に行なう。試料１ｇに硫酸２ｍｌ添加後、乾式分解（炭化、灰化６００℃×３０分）し、得られた残査に塩酸を加え、塩酸を蒸発させて乾固後、硝酸で加温溶解して２５ｍｌに定容する。 The Pd content of the high purity BPDA of the present invention can be measured by inductively coupled plasma mass spectrometry (ICP-MS), and the sample is prepared as follows. After adding 2 ml of sulfuric acid to 1 g of sample, dry decomposition (carbonization, ashing 600 ° C. × 30 minutes), adding hydrochloric acid to the resulting residue, evaporating the hydrochloric acid to dryness, dissolving with warming with nitric acid, 25 ml To be constant.
本発明のビフェニルテトラカルボン酸加熱無水化生成物結晶の製造方法は任意であるが、常温のビフェニルテトラカルボン酸加熱無水化生成物（粗ＢＰＤＡ）を加熱溶融させ、具体的には３００℃迄加熱し溶融させた後、減圧下、３０７℃以上３３０℃以下の温度で蒸発させ、高純度ＢＰＤＡの蒸気を冷却し結晶化する方法が好ましい。 The method for producing the biphenyltetracarboxylic acid heat-dehydrated product crystal of the present invention is arbitrary, but the biphenyltetracarboxylic acid heat-dehydrated product (crude BPDA) at room temperature is heated and melted, and specifically heated to 300 ° C. Then, after melting and then evaporating at a temperature of 307 ° C. or higher and 330 ° C. or lower under reduced pressure, the vapor of high purity BPDA is cooled and crystallized.
溶融粗ＢＰＤＡを蒸発させる際の温度が低すぎる場合は、ＢＰＤＡの蒸発を効率的に実施することが困難となり、また、高すぎる場合は、ＢＰＤＡの着色度が増加し、透過率が低下してしまう。従って、溶融粗ＢＰＤＡを蒸発させる際の温度は、好ましくは３０７〜３２０℃、更に好ましくは３０７〜３１５℃である。 If the temperature at which the molten crude BPDA is evaporated is too low, it will be difficult to efficiently evaporate the BPDA. If it is too high, the coloration of the BPDA will increase and the transmittance will decrease. End up. Therefore, the temperature at which the molten crude BPDA is evaporated is preferably 307 to 320 ° C, more preferably 307 to 315 ° C.
溶融粗ＢＰＤＡを蒸発させる際の減圧度は、蒸発雰囲気の圧力として、通常０．５ｋＰａ以下、好ましくは０．４ｋＰａ以下、更に好ましくは０．３ｋＰａ以下である。この圧力が０．５ｋＰａを超える場合、単位時間に蒸発するＢＰＤＡの量が少なくなり、全量を蒸発するのに長時間を要するため、熱劣化してＢＰＤＡの品質や回収率が低下する。 The degree of vacuum when evaporating the molten crude BPDA is usually 0.5 kPa or less, preferably 0.4 kPa or less, more preferably 0.3 kPa or less as the pressure of the evaporation atmosphere. When this pressure exceeds 0.5 kPa, the amount of BPDA that evaporates per unit time decreases, and it takes a long time to evaporate the entire amount. Therefore, the quality and recovery rate of BPDA are deteriorated due to thermal degradation.
溶融粗ＢＰＤＡを蒸発させる際、系内の気相部に酸素が存在すると、高温下の条件下で蒸発したＢＰＤＡの一部で酸化反応が起こり、製品の着色の要因となる物質が生成されることがある。従って、系内の酸素濃度は、通常１０ｐｐｍ以下、好ましくは５ｐｐｍ以下である。 When evaporating the molten crude BPDA, if oxygen is present in the gas phase in the system, an oxidation reaction occurs in a part of the BPDA evaporated under high temperature conditions, and a substance that causes product coloring is generated. Sometimes. Therefore, the oxygen concentration in the system is usually 10 ppm or less, preferably 5 ppm or less.
ＢＰＤＡ蒸気の線速は、通常０．１〜１．０ｍ／ｓ、好ましくは０．４〜０．６ｍ／ｓである。蒸気線速が速すぎる場合は、不純物が生成物に同伴されて純度が低下する場合があり、遅すぎる場合は、溶融状態での時間が長くなり、熱による分解の割合が増加し、回収率が低下することがある。なお、本発明に於ける「ＢＰＤＡ蒸気の線速」は、当該蒸発操作における単位時間当たりの蒸発物質の量の容量換算値（ａ）を、当該蒸発操作を行う容器空間部の水平断面のうち最大面積（ｂ）で除した値、即ち（ａ）／（ｂ）を言う。 The linear velocity of the BPDA vapor is usually 0.1 to 1.0 m / s, preferably 0.4 to 0.6 m / s. If the vapor linear velocity is too high, impurities may be entrained in the product and the purity may be reduced.If it is too slow, the time in the molten state will be longer, the rate of thermal decomposition will increase, and the recovery rate May decrease. The “linear velocity of the BPDA vapor” in the present invention is the volume converted value (a) of the amount of the evaporated substance per unit time in the evaporation operation, among the horizontal cross sections of the container space portion where the evaporation operation is performed. The value divided by the maximum area (b), that is, (a) / (b).
蒸発器中で蒸発するＢＰＤＡの蒸気量は、蒸発器中の粗ＢＰＤＡの減少量、または、蒸気を冷却して得られる固化したＢＰＤＡの増加量から容易に算出することが出来る。即ち、これらの重量変化により蒸発物質のモル数が算出されるので、温度と圧力とで補正することによって、蒸発するＢＰＤＡの蒸気量を容易に換算できる。この蒸気量を、蒸発操作を行う蒸発器の空間部の水平断面のうち最大面積で除して、「蒸気の線速」を求めればよい。 The amount of vapor of BPDA evaporated in the evaporator can be easily calculated from the amount of decrease in crude BPDA in the evaporator or the amount of increase in solidified BPDA obtained by cooling the vapor. That is, since the number of moles of the evaporated substance is calculated from these weight changes, the amount of vapor of BPDA to be evaporated can be easily converted by correcting with the temperature and pressure. Dividing this amount of steam by the maximum area of the horizontal cross section of the space of the evaporator performing the evaporation operation, the “linear speed of steam” may be obtained.
揮発したＢＰＤＡの冷却温度は、通常２００℃以下、好ましくは１００℃以下である。この冷却方法は、種々の方法によることが出来るが、通常、揮発操作を行う容器、例えば、蒸発釜などの容器の気相部に直結するガス管先端に配置したドラム式回転冷却器により行うのが好ましい。ドラム式回転冷却器に付着したＢＰＤＡは、適当な掻き取り装置によって、連続的に容易に掻き取られ、フレークとして回収される。この際、着色不純物の生成抑制の観点から、系内の酸素濃度は、通常１０ｐｐｍ以下、好ましくは５ｐｐｍ以下とするのがよい。 The cooling temperature of the volatilized BPDA is usually 200 ° C. or lower, preferably 100 ° C. or lower. This cooling method can be performed by various methods, but is usually performed by a drum-type rotary cooler disposed at the front end of a gas pipe directly connected to a gas phase portion of a container for performing a volatilization operation, for example, an evaporation kettle or the like. Is preferred. The BPDA adhering to the drum type rotary cooler is easily and continuously scraped by a suitable scraping device and recovered as flakes. At this time, from the viewpoint of suppressing the generation of colored impurities, the oxygen concentration in the system is usually 10 ppm or less, preferably 5 ppm or less.
本発明に於いて、ビフェニルテトラカルボン酸加熱無水化生成物（粗ＢＰＤＡ）の製造方法は、特に制限されず、例えばＢＴＣの脱水閉環反応による方法が挙げられる。粗ＢＰＤＡは、不純物としてビフェニルトリカルボン酸無水物を含有する組成物である。 In the present invention, the production method of the biphenyltetracarboxylic acid heat-dehydrated product (crude BPDA) is not particularly limited, and examples thereof include a method by BTC dehydration ring closure reaction. Crude BPDA is a composition containing biphenyltricarboxylic anhydride as an impurity.
ＢＴＣを使用した本発明を詳述すると、ＢＴＣを、常圧または減圧下、例えば０．１〜１００ｋＰａの範囲で、１５０〜２５０℃の温度に加熱し、粗ＢＰＤＡを得る。この場合、原料のＢＴＣは、例えばＰｄ触媒を使用した前述の（ｉ）又は（i i）の方法で得られた水湿潤状態のものでも使用でき、その際には、昇温途中で付着水が、更には結晶水も蒸発によって除かれ、続いて、脱水閉環反応が起こる。これら一連の反応は、付着水、結晶水および脱水閉環反応によって生成する水を、反応系外にパージしながら行うと、反応速度が向上するので、常圧で不活性ガスを通しながら、または、減圧下で行うのが好ましい。脱水閉環反応に要する時間は、加熱速度、加熱温度、減圧度および付着水の有無などによって異なるが、通常０．５〜１０時間の範囲で選ぶことが出来る。また、使用する不活性ガスとしては、ＢＰＤＡに対して実質的に化学反応を起こさないガス例えば、窒素の他、ヘリウム、アルゴン等の希ガス類が使用できる。 The present invention using BTC will be described in detail. BTC is heated to a temperature of 150 to 250 ° C. under normal pressure or reduced pressure, for example, in the range of 0.1 to 100 kPa, to obtain a crude BPDA. In this case, the raw material BTC can be used even in a water-wet state obtained by the method (i) or (ii) described above using, for example, a Pd catalyst. Furthermore, water of crystallization is removed by evaporation, followed by a dehydration ring closure reaction. These series of reactions are carried out while purging the adhering water, crystal water and water generated by the dehydration ring closure reaction outside the reaction system, so that the reaction rate is improved, so that an inert gas is passed at normal pressure, or It is preferable to carry out under reduced pressure. The time required for the dehydration ring-closing reaction varies depending on the heating rate, heating temperature, degree of reduced pressure, and the presence or absence of adhering water, but can usually be selected in the range of 0.5 to 10 hours. In addition, as the inert gas to be used, a gas that does not substantially cause a chemical reaction with BPDA, for example, a rare gas such as helium or argon in addition to nitrogen can be used.
本発明のビフェニルテトラカルボン酸加熱無水化生成物結晶は、淡黄色の着色の少ないため、特に光学用途に使用される芳香族ポリイミド樹脂の製造原料用として好適に使用することが出来る。 Since the biphenyltetracarboxylic acid heat-dehydrated product crystal of the present invention has little pale yellow coloration, it can be suitably used particularly as a raw material for producing an aromatic polyimide resin used for optical applications.
次に、本発明を実施例により詳細に説明するが、本発明はその趣旨を超えない限り、以下の記載例に限定されるものではない。なお、以下の例において、ＢＰＤＡの光透過率およびＰｄ含有量は本文に記載した方法で測定した。 EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited to the following description examples, unless the meaning is exceeded. In the following examples, the light transmittance and Pd content of BPDA were measured by the methods described in the text.
実施例１：
ダブルヘリカルリボン翼、ジャケット、不活性ガス供給口を備えた円筒縦型の反応器に、１００重量部のＢＴＣを仕込み、攪拌しつつ、常圧下、２１５℃の温度に加熱し、２m３／ｈｒの速度で窒素ガスを流通し、生成する水をパージしながら脱水閉環反応を１０時間行った。
Example 1:
A cylindrical vertical reactor equipped with a double helical ribbon blade, a jacket, and an inert gas supply port was charged with 100 parts by weight of BTC, and heated to 215 ° C. under atmospheric pressure with stirring, to 2 m 3 / hr. The dehydration ring closure reaction was carried out for 10 hours while flowing nitrogen gas at a rate of 5 ° C and purging the generated water.
続いて、同じ容器で、攪拌しつつ、３００℃の温度に昇温し、この温度で５時間保持し、反応物を溶融させた。溶融液を容量１．６m３の蒸発釜に移送し、系内の酸素濃度を５ｐｐｍに保ちながら、温度３０７℃、圧力２３０Ｐａ、蒸気線速０．８m／秒で、ＢＰＤＡを蒸発させた。蒸発させたＢＰＤＡは、蒸発釜の気相部に直結するガス管先端に配置したドラム式回転冷却器で析出させ、冷却器に付着したＢＰＤＡの結晶は、掻き取り装置によって連続的に掻き取り、フレークとして回収した。このフレークを粉砕して、８０重量部のビフェニルテトラカルボン酸加熱無水化生成物結晶（高純度ＢＰＤＡ）を得た。得られたＢＰＤＡの波長４００ｎｍの光透過率を測定したところ、９２％であった。また、このＢＰＤＡのＰｄ含有量を測定すると０．１ｐｐｍであった。 Subsequently, while stirring in the same container, the temperature was raised to a temperature of 300 ° C. and kept at this temperature for 5 hours to melt the reaction product. The molten liquid was transferred to an evaporation kettle with a capacity of 1.6 m 3 , and BPDA was evaporated at a temperature of 307 ° C., a pressure of 230 Pa, and a vapor linear velocity of 0.8 m / sec while maintaining the oxygen concentration in the system at 5 ppm. The evaporated BPDA is deposited by a drum-type rotary cooler arranged at the gas pipe tip directly connected to the vapor phase part of the evaporation kettle, and the BPDA crystals adhering to the cooler are continuously scraped by a scraping device, Collected as flakes. The flakes were pulverized to obtain 80 parts by weight of biphenyltetracarboxylic acid heat-dehydrated product crystals (high purity BPDA). The light transmittance of the obtained BPDA at a wavelength of 400 nm was measured and found to be 92%. Further, the Pd content of this BPDA was measured and found to be 0.1 ppm.
実施例２：
実施例１において、蒸発時の温度を３０７℃、圧力４００Ｐａ、蒸気線速０．４m／秒とした以外は、実施例１と同様の操作を行いＢＰＤＡフレークを得た。得られたＢＰＤＡの光透過率は９８％であった。また、このＢＰＤＡのＰｄ含有量を測定すると０．０５ｐｐｍであった。
Example 2:
BPDA flakes were obtained in the same manner as in Example 1 except that the temperature during evaporation was 307 ° C., the pressure was 400 Pa, and the vapor linear velocity was 0.4 m / second. The resulting BPDA had a light transmittance of 98%. Further, the Pd content of this BPDA was measured and found to be 0.05 ppm.
比較例１：
実施例１において、脱水閉環反応後、蒸発操作を行わずＢＰＤＡを取り出した。得られたＢＰＤＡの透過率は７８％であり、Ｐｄ含有量は０．５ｐｐｍであった。
Comparative Example 1:
In Example 1, after the dehydration ring-closing reaction, BPDA was taken out without performing the evaporation operation. The transmittance of the obtained BPDA was 78%, and the Pd content was 0.5 ppm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012011590A1 (en) | 2010-07-22 | 2012-01-26 | 宇部興産株式会社 | Polyimide precursor, polyimide, and materials to be used in producing same |
| KR20180102209A (en) | 2010-07-22 | 2018-09-14 | 우베 고산 가부시키가이샤 | Polyimide precursor, polyimide, and materials to be used in producing same |
| KR20190007531A (en) | 2010-07-22 | 2019-01-22 | 우베 고산 가부시키가이샤 | Polyimide precursor, polyimide, and materials to be used in producing same |
| KR20190126200A (en) | 2010-07-22 | 2019-11-08 | 우베 고산 가부시키가이샤 | Polyimide precursor, polyimide, and materials to be used in producing same |
| KR20200046126A (en) | 2010-07-22 | 2020-05-06 | 우베 고산 가부시키가이샤 | Polyimide precursor, polyimide, and materials to be used in producing same |
| KR20210032015A (en) | 2010-07-22 | 2021-03-23 | 우베 고산 가부시키가이샤 | Polyimide precursor, polyimide, and materials to be used in producing same |
| JP2018193569A (en) * | 2018-09-12 | 2018-12-06 | 宇部興産株式会社 | Polyimide, and polyimide precursor |
| JP7254469B2 (en) | 2018-09-12 | 2023-04-10 | Ｕｂｅ株式会社 | Polyimide and polyimide precursor |
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