JPH0421654A - Preparation of highly pure 3,3',4,4'-biphenyltetracarboxylic acid or its dianhydride - Google Patents
Preparation of highly pure 3,3',4,4'-biphenyltetracarboxylic acid or its dianhydrideInfo
- Publication number
- JPH0421654A JPH0421654A JP12555490A JP12555490A JPH0421654A JP H0421654 A JPH0421654 A JP H0421654A JP 12555490 A JP12555490 A JP 12555490A JP 12555490 A JP12555490 A JP 12555490A JP H0421654 A JPH0421654 A JP H0421654A
- Authority
- JP
- Japan
- Prior art keywords
- water
- crude
- bpta
- organic solvent
- acid
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 title claims abstract 7
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 15
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 3
- 229920001721 polyimide Polymers 0.000 abstract description 3
- 239000009719 polyimide resin Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 4
- RCZJVHXVCSKDKB-UHFFFAOYSA-N tert-butyl 2-[[1-(2-amino-1,3-thiazol-4-yl)-2-(1,3-benzothiazol-2-ylsulfanyl)-2-oxoethylidene]amino]oxy-2-methylpropanoate Chemical compound N=1C2=CC=CC=C2SC=1SC(=O)C(=NOC(C)(C)C(=O)OC(C)(C)C)C1=CSC(N)=N1 RCZJVHXVCSKDKB-UHFFFAOYSA-N 0.000 description 35
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- -1 alkali metal salt Chemical class 0.000 description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 208000005156 Dehydration Diseases 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- XGLOSUOCAVHAQP-UHFFFAOYSA-J C1(=C(C(=C(C(=C1)C(=O)[O-])C(=O)[O-])C(=O)[O-])C(=O)[O-])C1=CC=CC=C1.[Na+].[Na+].[Na+].[Na+] Chemical compound C1(=C(C(=C(C(=C1)C(=O)[O-])C(=O)[O-])C(=O)[O-])C(=O)[O-])C1=CC=CC=C1.[Na+].[Na+].[Na+].[Na+] XGLOSUOCAVHAQP-UHFFFAOYSA-J 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- LWXGAQHPDMUTQE-UHFFFAOYSA-L disodium;4-chlorophthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(Cl)C=C1C([O-])=O LWXGAQHPDMUTQE-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、耐熱性の高いポリイミド樹脂等の原料である
高純度の３．３ ’、４．４ ’−ビフェニルテトラカ
ルボン酸（以下、ＢＰＴＡと略する）及び３．３ ’、
４．４ ’−ビフェニルテトラカルボン酸二無水物（以
下、ＢＰＤＡと略す）を得る方法に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to highly purified 3.3', 4.4'-biphenyltetracarboxylic acid (hereinafter referred to as BPTA), which is a raw material for highly heat-resistant polyimide resin, etc. ) and 3.3',
The present invention relates to a method for obtaining 4.4'-biphenyltetracarboxylic dianhydride (hereinafter abbreviated as BPDA).
（従来の技術）
従来、ＢＰＤＡは耐熱性の高いポリイミド樹脂等の原料
として注目され、年々高純度のものが要求されるように
なった。(Prior Art) BPDA has traditionally attracted attention as a raw material for highly heat-resistant polyimide resins, etc., and higher purity has been demanded year by year.
一般に、ＢＰＤＡの製造方法には種々の提案がなされて
いる。その主な方法としては、例えば、オルトフタル酸
ジアルキルエステルの脱水素二量化反応によって得られ
る主生成物である３、３“４．４Ｉ−ビフェニルテトラ
カルボン酸テトラエステルを加水分解し、得られるＢＰ
ＴＡを脱水反応させて製造する方法がある。この方法に
より最終的に得られるＢＰＤＡは未反応の原料、副生成
物、触媒等の無機物及びそのイオンなどの種々の不純物
の一部が混入するため、純度が必ずしも高くならない。Generally, various proposals have been made for methods of manufacturing BPDA. The main method is, for example, by hydrolyzing 3,3"4,4I-biphenyltetracarboxylic acid tetraester, which is the main product obtained by the dehydrogenation dimerization reaction of orthophthalic acid dialkyl ester, to obtain BP.
There is a method of producing TA by subjecting it to a dehydration reaction. The BPDA finally obtained by this method does not necessarily have high purity because it is partially contaminated with various impurities such as unreacted raw materials, by-products, inorganic substances such as catalysts, and their ions.
また、４−ハロゲノオルトフタル酸アルカリ金属塩を、
水酸化アルカリと共に溶解させている水溶液中に金属パ
ラジウムを担体に担持させた触媒及びメタノール等の助
触媒を存在させ、その溶液を加熱させる三量化反応によ
ってＢＰＴＡを得る方法がある。この方法は、反応後、
反応液をろ過し、パラジウム系触媒を除去し、ろ液に酸
を加えてＢＰＴＡを析出させ、加熱し、熱ろ過するとＢ
ＰＴＡを結晶として分離することができる。更にこれを
乾燥して粗ＢＰＴＡを得る。この粗ＢＰＴＡの中には前
者の例と同様に種々の不純物が含まれる。その不純物と
は原料に起因するフタル酸、アルカリ塩類、アルカリ出
金属塩類、あるいはその他の金属塩等である。In addition, 4-halogenorthophthalic acid alkali metal salt,
There is a method of obtaining BPTA by a trimerization reaction in which a catalyst in which metal palladium is supported on a carrier and a co-catalyst such as methanol are present in an aqueous solution dissolved together with an alkali hydroxide, and the solution is heated. In this method, after the reaction,
The reaction solution is filtered, the palladium-based catalyst is removed, an acid is added to the filtrate to precipitate BPTA, and by heating and hot filtration, B
PTA can be separated as crystals. This is further dried to obtain crude BPTA. This crude BPTA contains various impurities as in the former example. The impurities include phthalic acid, alkali salts, alkaline metal salts, and other metal salts originating from the raw materials.
また、４−ハロゲノオルトフタル酸ジアルキルをニッケ
ル触媒、助触媒等の存在下で三量化反応によってＢＰＴ
Ａが得られる方法等がある。これら従来の方法で得られ
た粗ＢＰＴＡの純度は８５〜９０％であることが一般的
である。In addition, dialkyl 4-halogenorthophthalate can be converted into BPT by trimerization reaction in the presence of a nickel catalyst, cocatalyst, etc.
There are ways to obtain A. The purity of crude BPTA obtained by these conventional methods is generally 85 to 90%.
従来、この粗ＢＰＴＡの脱水反応により純度の高いＢＰ
ＤＡを得る方法には、無水酢酸のような脂肪族の酸無水
物等の存在下で脱水する方法、また粗ＢＰＴＡまたは粗
ＢＰＤＡを加熱昇華してその蒸気を冷却してＢＰＤＡを
得る方法（特開昭６１−２４９９７７号、特開昭６２−
２５７９３４号）が知られている。Conventionally, high purity BP was obtained through the dehydration reaction of this crude BPTA.
Methods for obtaining DA include a method of dehydration in the presence of an aliphatic acid anhydride such as acetic anhydride, and a method of heating and sublimating crude BPTA or crude BPDA and cooling the vapor to obtain BPDA (especially 1986-249977, JP-A-62-
No. 257934) is known.
前者は粗ＢＰＴＡを多量の無水酢酸のような脂肪族の酸
無水物と共に還流、脱水してＢＰＤＡにすると共に、同
時に溶解度の差によって不純物の無水フタル酸等を溶解
除去してＢＰＤＡの純度を高める方法である。しかしな
がら、刺激臭の強い無水酢酸等を取り扱うために取り扱
い方が不便であるとともに大量の無水酢酸等を消費する
ためＢＰＤＡのコストが高くなる。In the former, crude BPTA is refluxed and dehydrated with a large amount of aliphatic acid anhydride such as acetic anhydride to form BPDA, and at the same time, due to the difference in solubility, impurities such as phthalic anhydride are dissolved and removed to increase the purity of BPDA. It's a method. However, since acetic anhydride, which has a strong pungent odor, is handled, it is inconvenient to handle, and a large amount of acetic anhydride, etc. is consumed, which increases the cost of BPDA.
また、後者は加熱により脱水と昇華精製を行うものであ
る。しかしながら、大規模な装置を必要とするためにＢ
ＰＤＡのコストが高くなる。またフタル酸、無水フタル
酸等も同時に昇華するのでこの精製には特別の工夫を要
する。Moreover, the latter performs dehydration and sublimation purification by heating. However, because it requires large-scale equipment, B.
The cost of PDAs increases. Furthermore, since phthalic acid, phthalic anhydride, etc. are also sublimed at the same time, special measures are required for purification.
さらに最も経済的で安全で特別な装置を必要としない方
法として、ＢＰＴＡの水洗を繰り返して精製し、続いて
精製ＢＰＤＡを得る方法が考えられる。ＢＰＴＡは水に
対する溶解度が低く、実質上不溶である。従って、多量
の水または温水で洗浄することによって無機物、フタル
酸等の不純物を除去することが可能であるが、実際には
粗ＢＰＴＡに水を直接添加するとスラリー状となり、ス
ラリーのろ過が極めて困難であるという問題がある。こ
のスラリーにおけるＢＰＴＡの粒子は非常に細かくなり
、水洗を繰り返せば、さらに微粒子となり、また粘性も
あがるため、ろ過による分離が困難となる。つまり、水
洗処理による精製は、実用的なりＰＴＡの精製法ではな
く、高純度ＢＰＤＡを得る工程になり得ない。Furthermore, as the most economical and safe method that does not require special equipment, it is possible to purify BPTA by repeatedly washing it with water, and then obtain purified BPDA. BPTA has low solubility in water and is virtually insoluble. Therefore, it is possible to remove impurities such as inorganic substances and phthalic acid by washing with a large amount of water or hot water, but in reality, when water is directly added to crude BPTA, it becomes slurry-like, and it is extremely difficult to filter the slurry. There is a problem that. The particles of BPTA in this slurry become very fine, and if water washing is repeated, the particles become even finer and the viscosity increases, making it difficult to separate by filtration. In other words, purification by water washing is not a practical method for purifying PTA and cannot be a process for obtaining high purity BPDA.
（発明が解決しようとする課題）
本発明は粗ＢＰＴＡを簡便で経済的な工程で精製し、高
純度ＢＰＴＡまたはＢＰＤＡを得る製造方法を提案する
ものである。(Problems to be Solved by the Invention) The present invention proposes a manufacturing method for obtaining highly purified BPTA or BPDA by refining crude BPTA through a simple and economical process.
（課題を解決するための手段）
本発明は粗ＢＰＴＡを、水を含む有機溶剤で洗浄処理、
または有機溶剤で洗浄処理した後、水で洗浄処理するこ
とによって不純物を溶解せしめる工程により高純度ＢＰ
ＴＡまたはＢＰＤＡを製造する方法である。(Means for Solving the Problems) The present invention involves cleaning crude BPTA with an organic solvent containing water,
Alternatively, high purity BP can be obtained through a process of cleaning with an organic solvent and then with water to dissolve impurities.
This is a method for producing TA or BPDA.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の高純度ＢＰＴＡを製造する方法は、粗ＢＰＴＡ
を有機溶剤に懸濁して不純物を溶解せしめ、ろ過するこ
とによりＢＰＴＡを精製するものである。例えば４−ハ
ロゲノオルトフタル酸アルカリ金属塩のパラジウム触媒
による三量化反応で得られる粗ＢＰＴＡは、触媒分離後
の反応液を酸析し、得られる沈澱を分離し、さらに水で
の洗浄工程を経て得られる。この粗ＢＰＴＡは、未反応
の原料、フタル酸等の原料不純物、反応副生成物、アル
カリ土類金属
一部が混入するため、純度が必ずしも高くならない。ま
た、この粗ＢＰＴＡは単に、水または熱湯水洗浄処理に
よって精製しようとすると、粒子が極めて微細であるた
め、ろ過が困難である。つまり、片栗粉を水に溶かした
様なスラリー状となり、取り扱いが、困難で水洗処理に
より、精製することは実用的でない。さらに、この粗Ｂ
ＰＴＡを時間と労力をかけて水洗を続けてもなお、水に
難溶性の物質が残り、製品を例えば、高分子原料として
用いた場合、十分な物性が得られないことがある。The method for producing high-purity BPTA of the present invention includes crude BPTA
BPTA is purified by suspending it in an organic solvent to dissolve impurities and filtering it. For example, crude BPTA obtained by a palladium-catalyzed trimerization reaction of an alkali metal salt of 4-halogenorthophthalate is obtained by precipitating the reaction solution after catalyst separation with acid, separating the resulting precipitate, and further washing with water. can get. This crude BPTA does not necessarily have high purity because it contains unreacted raw materials, raw material impurities such as phthalic acid, reaction by-products, and some alkaline earth metals. Moreover, if this crude BPTA is purified simply by washing with water or hot water, it will be difficult to filter because the particles are extremely fine. In other words, it becomes a slurry like potato starch dissolved in water, which is difficult to handle and impractical to purify by washing with water. Furthermore, this rough B
Even if PTA is continuously washed with water, taking time and effort, substances that are poorly soluble in water still remain, and when the product is used, for example, as a raw material for a polymer, sufficient physical properties may not be obtained.
従って、粗ＢＰＴＡを有機溶剤で洗浄することが必要で
あり、これにより高純度ＢＰＴＡまたはＢＰＤＡが得ら
れる。有機溶剤中、粗ＢＰＴＡを懸濁した液は、比較的
容易にろ過することができ、前記の問題も解決される。Therefore, it is necessary to wash the crude BPTA with an organic solvent, thereby obtaining high purity BPTA or BPDA. A suspension of crude BPTA in an organic solvent can be filtered relatively easily, and the above problem is also solved.
しかし、イオン性不純物が特に多い粗ＢＰＴＡでは有機
溶剤のみの洗浄工程だけでは十分除去することができな
いので、用いる有機溶剤に水を混ぜるか、または有機溶
剤洗浄工程の次に、水洗工程を続ける。前者の場合は、
有機溶剤が半量あればほとんどろ過には影響せず、後者
の場合は、一回有機溶剤で洗浄したＢＰＴＡは次に水に
懸濁して、ろ過することが比較的容易となる。However, crude BPTA, which has a particularly large amount of ionic impurities, cannot be sufficiently removed by a washing step using only an organic solvent, so either water is mixed with the organic solvent used, or a water washing step is continued after the organic solvent washing step. In the former case,
If the amount of organic solvent is half, it will hardly affect filtration, and in the latter case, BPTA washed once with an organic solvent will be suspended in water and filtered relatively easily.
ここで用いる有機溶剤は一般に用いる溶剤ならほとんど
用いることができるが、比較的安価なもので沸点の比較
的低いものが好ましい。しかし、アルコール系溶剤、特
にメタノールは、ＢＰＴ’Ａと反応してエステルが生成
しやすいので好ましくない。好ましい溶剤としては、ベ
ンゼン、トルエン、アセトン、クロロホルム、酢酸エチ
ルなどがあげられる。特に取り扱い上、水との混和性等
を考えるとアセトンが最も好ましい。As the organic solvent used here, most commonly used solvents can be used, but it is preferable to use one that is relatively inexpensive and has a relatively low boiling point. However, alcoholic solvents, particularly methanol, are not preferred because they tend to react with BPT'A and form esters. Preferred solvents include benzene, toluene, acetone, chloroform, and ethyl acetate. In particular, acetone is most preferred in terms of handling and miscibility with water.
有機溶剤による精製工程を経て、得られるＢＰＴＡから
、通常行われる、加熱脱水処理により高純度ＢＰＤＡが
得られる。こうして得られるＢＰＤＡは、通常の目的に
は十分使用される純度を有し、ＢＰＤＡの純度としては
９９．５％以上に達する。有機溶剤による洗浄に続いて
水洗処理工程を行えば、更に高純度のＢＰＤＡとなり、
ＢＰＤＡの純度としては９９．８％以上、金属イオン及
びハロゲンイオンはｉｐｐｍ以下となり、高信頼性の要
求される製品（例えば半導体）用材料の原料としての使
用に充分耐え得るものとなる。High purity BPDA can be obtained from the BPTA obtained through a purification process using an organic solvent through a commonly performed heating dehydration treatment. The BPDA thus obtained has a purity sufficient for general purposes, reaching a purity of 99.5% or more. If a water washing treatment step is performed following washing with an organic solvent, even higher purity BPDA can be obtained.
The purity of BPDA is 99.8% or more, and the metal ions and halogen ions are less than ippm, making it sufficiently durable for use as a raw material for products (for example, semiconductors) that require high reliability.
（実 施 例）
以下に本発明を実施例を挙げて説明する。なお、実施例
中の部とは重量部を表わす。(Examples) The present invention will be described below with reference to Examples. In addition, parts in the examples represent parts by weight.
実施例１
（１）ビフェニルテトラカルボン酸の調整攪拌機及び加
熱装置を備えた反応機に、４−クロロフタル酸ナトリウ
ムの二量化反応で得られた３ 、３ ’，４ 、４ ’
ービフェニルテトラヵルボン酸ナトリウムの水溶液（Ｂ
ＰＴＡ５．４％、フタル酸４、２％を含む）６９部を仕
込み、攪拌上濃塩酸１４部を添加し、酸析後、加熱し、
熱ろ過した。Example 1 (1) Preparation of biphenyltetracarboxylic acid 3,3',4,4' obtained by the dimerization reaction of sodium 4-chlorophthalate was placed in a reactor equipped with a stirrer and a heating device.
-Aqueous solution of sodium biphenyltetracarboxylate (B
69 parts (containing 5.4% PTA and 4.2% phthalic acid) were charged, 14 parts of concentrated hydrochloric acid was added after stirring, and after acid precipitation, heated.
Hot filtered.
得られた白色ケーキ７．２部を水３６部とともに再び反
応機に仕込み、攪拌上加熱し、熱ろ過した。7.2 parts of the obtained white cake was charged into the reactor again together with 36 parts of water, heated with stirring, and filtered hot.
得られた白色ケーキ４．７部を、１２０℃で５時間熱風
乾燥して、白色粒状の粗３，３”、４ 、４ ’ビフェ
ニルテトラカルボン酸２．６部を得た。このものの純度
は９５％で、フタル酸は２％含まれていた。4.7 parts of the obtained white cake was dried with hot air at 120°C for 5 hours to obtain 2.6 parts of white granular coarse 3,3'',4,4' biphenyltetracarboxylic acid.The purity of this product was as follows: 95% and contained 2% phthalate.
（２）精製処理及び脱水反応
上記粗ＢＰＴＡを攪拌機及び加熱装置を備えた反応機に
アセトン１０部とともに仕込み、３０分攪拌した後ろ過
して、白色ケーキを得る。これを水２６部とともに撹拌
下で加熱し、冷却後ろ過してＢＰＴＡの白色ケーキ３．
８部１２０℃で５時間熱風乾燥し、純度９９．８％以上
のＢＰＴＡの白色粉末を得た。このＢＰＤＡを微粉砕し
て、排気口に冷却トラップを付けた加熱装置に入れ吸弓
しながら２２０″Ｃで３時間加熱脱水して、白色粉末状
の精製ＢＰＤＡ２．１部を得た。このものの純度は９９
．８％以上で、無水フタル酸は含まれていなかった。ま
た、イオン含有量はナトリウムイオン、塩素イオンとも
にｉｐｌ）ｍ以下であった。(2) Purification treatment and dehydration reaction The above crude BPTA was charged together with 10 parts of acetone into a reactor equipped with a stirrer and a heating device, stirred for 30 minutes, and then filtered to obtain a white cake. This was heated under stirring with 26 parts of water, cooled and filtered to form a white cake of BPTA.3.
Eight parts were dried with hot air at 120° C. for 5 hours to obtain a white powder of BPTA with a purity of 99.8% or higher. This BPDA was finely pulverized, placed in a heating device with a cooling trap attached to the exhaust port, and heated and dehydrated at 220''C for 3 hours while using a suction tube to obtain 2.1 parts of purified BPDA in the form of a white powder. Purity is 99
．． It was over 8% and did not contain phthalic anhydride. Further, the ion content was less than ipl)m for both sodium ions and chloride ions.
実施例２
（１）ビフェニルテトラカルボン酸の調整実施例１にお
けるビフェニルテトラカルボン酸の調整と同様にして製
造した粗３．３ ’、４．４ ’ビフェニルテトラカル
ボン酸２８部を得た。このものの純度は９６％で、フタ
ル酸は１％含まれていた。Example 2 (1) Preparation of biphenyltetracarboxylic acid 28 parts of crude 3.3', 4.4' biphenyltetracarboxylic acid produced in the same manner as in the preparation of biphenyltetracarboxylic acid in Example 1 was obtained. This product had a purity of 96% and contained 1% phthalic acid.
（２）精製処理及び脱水反応
上記粗ＢＰＴＡを攪拌機及び加熱装置を備えた反応機に
アセトン：水（１： １）２０部とともに仕込み、３０
分攪拌したのち、ろ過して、白色ケーキを得る。得られ
た白色ケーキ４部を１２０″Ｃで５時間熱風乾燥し、純
度９９．８％以上のＢＰＴＡの白色粉末を得た。以下、
実施例１と同様にして、加熱脱水して、白色粉末状の精
製ＢＰＤＡ２．３部を得た。このものの純度は９９．８
％以上で無水フタル酸は含まれていなかった。また、イ
オン含有量は、ナトリウムイオン、塩素イオンともにｉ
ｐｐｍ以下であった。(2) Purification treatment and dehydration reaction The above crude BPTA was charged into a reactor equipped with a stirrer and a heating device together with 20 parts of acetone:water (1:1).
After stirring for several minutes, it is filtered to obtain a white cake. Four parts of the obtained white cake was dried with hot air at 120''C for 5 hours to obtain a white powder of BPTA with a purity of 99.8% or more.
The mixture was heated and dehydrated in the same manner as in Example 1 to obtain 2.3 parts of purified BPDA in the form of white powder. The purity of this product is 99.8
% or more, no phthalic anhydride was contained. In addition, the ion content is i for both sodium ions and chloride ions.
It was less than ppm.
比較例１
く昇華法による精製〉
下部に加熱装置、上部に冷却装置の板吠冷却面、頂部に
ガス排気口をそれぞれ有する密閉形反応器に実施例工の
粗ＢＰＴＡ１部を仕込み、減圧上加熱した。４０ｍｍＨ
ｇで２００°Ｃで２時間加熱して、ＢＰＤＡとしたのち
、２０ｍｍＨｇ１３００℃で１時間加熱した。冷却面に
析出した黄色味を帯びた結晶のＢＰＤＡｏ、９部を回収
した。このものの純度は９９．２％で無水フタル酸０．
５％が含まれていた。Comparative Example 1 Purification by sublimation method> One part of the crude BPTA of the example process was charged into a closed reactor having a heating device at the bottom, a cooling surface of a cooling device at the top, and a gas exhaust port at the top, and heated under reduced pressure. did. 40mmH
g for 2 hours at 200°C to form BPDA, and then heated at 20mmHg and 1300°C for 1 hour. 9 parts of yellowish crystal BPDAo precipitated on the cooling surface was recovered. The purity of this product is 99.2% and phthalic anhydride 0.
It contained 5%.
（発明の効果）
本発明により、簡便かつ経済的に高純度ＢＰＴＡ及びＢ
ＰＤＡを製造することが可能になった。(Effect of the invention) The present invention allows high purity BPTA and B to be easily and economically produced.
It has become possible to manufacture PDAs.
特許出願人 日本カーリット株式会社Patent applicant Nippon Carlit Co., Ltd.
Claims (4)
酸を、水を含む有機溶剤で洗浄処理し、不純物を除去せ
しめることを特徴とする高純度３，３’，４，４’−ビ
フェニルテトラカルボン酸の製造方法。1. High-purity 3,3',4,4'-biphenyltetra, which is characterized by washing crude 3,3',4,4'-biphenyltetracarboxylic acid with an organic solvent containing water to remove impurities. Method for producing carboxylic acid.
酸を、有機溶剤で洗浄した後、水で洗浄処理し、不純物
を除去せしめることを特徴とする高純度３，３’，４，
４’−ビフェニルテトラカルボン酸の製造方法。2. High purity 3,3',4,4'-biphenyltetracarboxylic acid is washed with an organic solvent and then washed with water to remove impurities.
Method for producing 4'-biphenyltetracarboxylic acid.
酸を、水を含む有機溶剤で洗浄処理し、不純物を除去せ
しめる工程と、得られた固体を加熱処理する工程とから
なることを特徴とする高純度３，３’，４，４’−ビフ
ェニルテトラカルボン酸二無水物の製造方法。3. It is characterized by comprising the steps of washing crude 3,3',4,4'-biphenyltetracarboxylic acid with an organic solvent containing water to remove impurities, and heat-treating the obtained solid. A method for producing high purity 3,3',4,4'-biphenyltetracarboxylic dianhydride.
酸を、有機溶剤で洗浄した後、水で洗浄処理し、不純物
を除去せしめる工程と、得られた固体を加熱処理する工
程とからなることを特徴とする高純度３，３’，４，４
’−ビフェニルテトラカルボン酸二無水物の製造方法。4. It consists of a step of washing crude 3,3',4,4'-biphenyltetracarboxylic acid with an organic solvent and then washing with water to remove impurities, and a step of heat-treating the obtained solid. High purity 3,3',4,4 characterized by
A method for producing '-biphenyltetracarboxylic dianhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12555490A JPH0421654A (en) | 1990-05-17 | 1990-05-17 | Preparation of highly pure 3,3',4,4'-biphenyltetracarboxylic acid or its dianhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12555490A JPH0421654A (en) | 1990-05-17 | 1990-05-17 | Preparation of highly pure 3,3',4,4'-biphenyltetracarboxylic acid or its dianhydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0421654A true JPH0421654A (en) | 1992-01-24 |
Family
ID=14913077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12555490A Pending JPH0421654A (en) | 1990-05-17 | 1990-05-17 | Preparation of highly pure 3,3',4,4'-biphenyltetracarboxylic acid or its dianhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0421654A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999041222A1 (en) * | 1998-02-16 | 1999-08-19 | Bromine Compounds Ltd. | Process for the purification of polycarboxylic aromatic acids |
| JP2012131767A (en) * | 2010-12-02 | 2012-07-12 | Ube Industries Ltd | Purification method of 2,3,3',4'-biphenyl tetracarboxylic acid dianhydride powder, powder, and polyimide using the same |
| CN114507130A (en) * | 2022-02-09 | 2022-05-17 | 河北海力香料股份有限公司 | Purification method of 3,3',4,4' -biphenyltetracarboxylic acid |
-
1990
- 1990-05-17 JP JP12555490A patent/JPH0421654A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999041222A1 (en) * | 1998-02-16 | 1999-08-19 | Bromine Compounds Ltd. | Process for the purification of polycarboxylic aromatic acids |
| JP2012131767A (en) * | 2010-12-02 | 2012-07-12 | Ube Industries Ltd | Purification method of 2,3,3',4'-biphenyl tetracarboxylic acid dianhydride powder, powder, and polyimide using the same |
| CN114507130A (en) * | 2022-02-09 | 2022-05-17 | 河北海力香料股份有限公司 | Purification method of 3,3',4,4' -biphenyltetracarboxylic acid |
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