JPH0276837A - Method for purifying 4,4'-biphenyldicarboxylic acid - Google Patents
Method for purifying 4,4'-biphenyldicarboxylic acidInfo
- Publication number
- JPH0276837A JPH0276837A JP18644288A JP18644288A JPH0276837A JP H0276837 A JPH0276837 A JP H0276837A JP 18644288 A JP18644288 A JP 18644288A JP 18644288 A JP18644288 A JP 18644288A JP H0276837 A JPH0276837 A JP H0276837A
- Authority
- JP
- Japan
- Prior art keywords
- biphenyldicarboxylic acid
- acid
- salt
- aqueous solution
- biphenyldicarboxylic
- 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.)
- Granted
Links
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 51
- 150000003839 salts Chemical class 0.000 abstract description 35
- NEQFBGHQPUXOFH-UHFFFAOYSA-L 4-(4-carboxylatophenyl)benzoate Chemical compound C1=CC(C(=O)[O-])=CC=C1C1=CC=C(C([O-])=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-L 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000005185 salting out Methods 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 150000007942 carboxylates Chemical class 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 42
- 239000013078 crystal Substances 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000000746 purification Methods 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- 239000004305 biphenyl Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical class OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical group 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- -1 biphenyldicarboxylic acid diammonium salt Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 159000000011 group IA salts Chemical class 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 159000000001 potassium salts Chemical class 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 3
- 239000007806 chemical reaction intermediate Substances 0.000 description 3
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YSYKJKJXEDDJTC-UHFFFAOYSA-N 1-acetyl-4-phenylcyclohexa-2,4-diene-1-carboxylic acid Chemical group C1=CC(C(=O)C)(C(O)=O)CC=C1C1=CC=CC=C1 YSYKJKJXEDDJTC-UHFFFAOYSA-N 0.000 description 2
- AXSORFIRFZYVQH-UHFFFAOYSA-N 1-formyl-4-phenylcyclohexa-2,4-diene-1-carboxylic acid Chemical group C(=O)C1(CC=C(C=C1)C1=CC=CC=C1)C(=O)O AXSORFIRFZYVQH-UHFFFAOYSA-N 0.000 description 2
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- CYOMKTVNSWQGGQ-UHFFFAOYSA-N [Mn].[Br] Chemical compound [Mn].[Br] CYOMKTVNSWQGGQ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 150000004074 biphenyls Chemical class 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000012487 rinsing solution Substances 0.000 description 2
- 159000000005 rubidium salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229940075581 sodium bromide Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UMSGIWAAMHRVQI-UHFFFAOYSA-N 1-ethyl-4-(4-ethylphenyl)benzene Chemical group C1=CC(CC)=CC=C1C1=CC=C(CC)C=C1 UMSGIWAAMHRVQI-UHFFFAOYSA-N 0.000 description 1
- AMBHHSBRXZAGDZ-UHFFFAOYSA-N 1-phenyl-2,3-di(propan-2-yl)benzene Chemical group CC(C)C1=CC=CC(C=2C=CC=CC=2)=C1C(C)C AMBHHSBRXZAGDZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ASYHSVJXTNYDOF-UHFFFAOYSA-L dipotassium 4-(4-carboxylatophenyl)benzoate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)C([O-])=O ASYHSVJXTNYDOF-UHFFFAOYSA-L 0.000 description 1
- RDKMRHWFTLMFDD-UHFFFAOYSA-L disodium;4-(4-carboxylatophenyl)benzoate Chemical compound [Na+].[Na+].C1=CC(C(=O)[O-])=CC=C1C1=CC=C(C([O-])=O)C=C1 RDKMRHWFTLMFDD-UHFFFAOYSA-L 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- 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、４，４′ −ビフェニルジカルボン酸の精製
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for purifying 4,4'-biphenyldicarboxylic acid.
［従来の技術］
４．４′ −ビフェニルジカルボン酸は、新規ポリマー
原料として需要が期待されている物買である。[Prior Art] 4.4'-Biphenyldicarboxylic acid is a commodity that is expected to be in demand as a raw material for new polymers.
４．４′ −ビフェニルジカルボン酸の合成法としては
、安息香酸またはその誘導体をニッケル、パラジウム等
を触媒に用いてカップリングする方法、または４．４′
−ビフェニルジカルボン酸ジ置換体を液相酸化によっ
て酸化する方法があるが、前者によって生成した粗４，
４′ −ビフェニルジカルボン酸中には安息香酸、触媒
金属などの不純物が含まれ、また、後者によって生成し
た粗４，４′ −ビフェニルジカルボン酸中には、酸
化反応中間体、触媒金属、着色物質等の不純物が含まれ
る。よって、いずれも高純度が要求されるポリマー原料
としては不適切であり、粗４，４′ −ビフェニルジ
カルボン酸の精製法の確立は重要な課題であった。4.4'-Biphenyldicarboxylic acid can be synthesized by coupling benzoic acid or its derivatives using nickel, palladium, etc. as a catalyst, or 4.4'
-There is a method of oxidizing disubstituted biphenyldicarboxylic acid by liquid phase oxidation, but the crude 4,
4'-biphenyldicarboxylic acid contains impurities such as benzoic acid and catalytic metals, and the crude 4,4'-biphenyldicarboxylic acid produced by the latter also contains oxidation reaction intermediates, catalytic metals, and colored substances. Contains impurities such as. Therefore, all of these are unsuitable as polymer raw materials that require high purity, and the establishment of a purification method for crude 4,4'-biphenyldicarboxylic acid has been an important issue.
従来、４，４′ −ビフェニルジカルボン酸を精製する
方法としては、特開昭５７−１４９．２４４号に記載さ
れているように、ジメチルスルホキシドを溶媒として再
結晶する方法、あるいは特開昭５８−８５．８４１号に
記載されているように、４，４′ −ビフェニルジカ
ルボン酸ジアルカリ塩水溶液に炭酸ガスを作用させて４
，４′ −ビフェニルジカルボン酸モノアルカリ塩を
析出、分離し、しかる後に不均化させる方法などが知ら
れている。Conventionally, methods for purifying 4,4'-biphenyldicarboxylic acid include recrystallization using dimethyl sulfoxide as a solvent, as described in JP-A-57-149.244; As described in No. 85.841, 4,4'-biphenyldicarboxylic acid dialkali salt aqueous solution is treated with carbon dioxide gas.
, 4'-biphenyldicarboxylic acid monoalkali salts are precipitated, separated, and then disproportionated.
しかしながら、前者の精製法では、ジメチルスルホキシ
ドに対する４、４′ −ビフェニルジカルボン酸の溶解
度が低く、大量のジメチルスルホキシドが必要であり、
効率の良くない分離法であった。However, in the former purification method, the solubility of 4,4'-biphenyldicarboxylic acid in dimethyl sulfoxide is low, and a large amount of dimethyl sulfoxide is required.
This was an inefficient separation method.
また、後者の精製法も、加圧圧力容器を用いた煩雑な操
作が必要であり、改善が望まれていた。Furthermore, the latter purification method also requires complicated operations using a pressurized pressure vessel, and improvements have been desired.
［発明が解決しようとする課題］
本発明は、粗４，４′ −ビフェニルジカルボン酸か
ら高収率かつ高純度で４，４′ −ビフェニルジカル
ボン酸を得ることができる精製法の提供を目的とする。[Problems to be Solved by the Invention] The purpose of the present invention is to provide a purification method capable of obtaining 4,4'-biphenyldicarboxylic acid in high yield and purity from crude 4,4'-biphenyldicarboxylic acid. do.
［課題を解決するための手段］
本発明者らは、上記精製法の確立を目的とて行ない、粗
４．４′ −ビフェニルジカルボン酸を４．４′ −
ビフェニルジカルボン酸塩の水溶液となし、次いで、該
水溶液の濃縮および／または４．４’−ビフェニルジカ
ルボン酸塩の溶解度を下げる手段により、４，４′
−ビフェニルジカルボン酸塩を析出させ分離し、しかる
後、得られた塩を酸析または加熱分解することにより高
純度の４，４′ −ビフェニルジカルボン酸が高収率で
得られことを見出し、本発明を完成した。[Means for Solving the Problems] The present inventors carried out the purification method for the purpose of establishing the above purification method, and purified crude 4.4'-biphenyl dicarboxylic acid to 4.4'-biphenyldicarboxylic acid.
4,4′-biphenyl dicarboxylate by preparing an aqueous solution of the 4,4′-biphenyl dicarboxylate salt, and then concentrating the aqueous solution and/or reducing the solubility of the 4,4′-biphenyl dicarboxylate salt.
It was discovered that high purity 4,4'-biphenyldicarboxylic acid can be obtained in high yield by precipitating and separating the -biphenyl dicarboxylic acid salt, and then acidifying or thermally decomposing the resulting salt. Completed the invention.
ここで言°う４，４′ −ビフェニルジカルボン酸塩
は、下記式（Ｉ）で示されるものである。The 4,4'-biphenyl dicarboxylate mentioned here is represented by the following formula (I).
（ただし、式中、ＸおよびＹはＬｉ、’Ｎａ、Ｋ。(However, in the formula, X and Y are Li, 'Na, K.
ＲｂまたはＮｂ２を示し、ＸとＹは同一であっても異な
ってもよい）。具体的には、４，４′ −ビフェニル
ジカルボン酸ジナトリウム塩、４，４′ −ビフェニ
ルジカルボン酸ジカリウム塩などの４，４′−ビフェニ
ルジカルボン酸ジアルカリ金属塩または４，４′ −
ビフェニルジカルボン酸ジアンモニウム塩である。また
、それらの塩の混合物でも、−方のカルボキシル基と他
方のカルボキシル基に結合するアルカリ金属またはアン
モニウムが異なる塩であっても差支えない。represents Rb or Nb2, and X and Y may be the same or different). Specifically, 4,4'-biphenyldicarboxylic acid dialkali metal salts such as 4,4'-biphenyldicarboxylic acid disodium salt, 4,4'-biphenyldicarboxylic acid dipotassium salt, or 4,4'-
It is biphenyldicarboxylic acid diammonium salt. Moreover, even if it is a mixture of these salts, the alkali metal or ammonium bonded to one carboxyl group and the other carboxyl group may be different.
本発明は、例えば下記に示す各工程より行うことができ
る。The present invention can be carried out, for example, through the steps shown below.
（１）粗４，４′ −ビフェニルジカルボン酸をアル
カリ金属および／またはアンモニウムの水酸化物または
弱酸塩の水溶液等に加えてジカルボン酸塩としたのち、
またはとすると共にジカルボン酸塩の水溶液とする工程
。(1) After adding crude 4,4'-biphenyldicarboxylic acid to an aqueous solution of an alkali metal and/or ammonium hydroxide or weak acid salt to form a dicarboxylic acid salt,
or a step of preparing an aqueous solution of the dicarboxylate.
（２）水溶液に活性炭等を加え脱色し、しかるに活性炭
を分離する工程。(2) A step of adding activated carbon or the like to the aqueous solution to decolorize it and then separating the activated carbon.
（３〉水溶液から４．４′ −ビフェニルジカルボン
酸塩を析出させる工程。(3> Step of precipitating 4.4'-biphenyl dicarboxylate from an aqueous solution.
（４）４．４’ −ビフェニルジカルボン酸塩を固液
分離し、付着母液をリンスにより除去する工程。(4) A step of separating the 4.4′-biphenyldicarboxylic acid salt into solid and liquid and removing the adhering mother liquor by rinsing.
（５）４．４’ −ビフェニルジカルボン酸塩を再び
水に溶解させる工程。(5) A step of dissolving the 4.4'-biphenyl dicarboxylate in water again.
（６）水溶液に活性炭等を加え脱色し、しかる後活性炭
を分離する工程。(6) A step of adding activated carbon or the like to the aqueous solution to decolorize it, and then separating the activated carbon.
（７）水溶液に酸を加え酸析し、４，４′ −ビフェ
ニルジカルボン酸を析出させる工程。(7) A step of adding an acid to the aqueous solution to precipitate it to precipitate 4,4'-biphenyldicarboxylic acid.
（８）４．４’ −ビフェニルジカルボン酸を固液分
離し、付着母液をリンスにより除去し、乾燥する工程。(8) A step of separating 4.4'-biphenyldicarboxylic acid into solid and liquid, removing the adhering mother liquor by rinsing, and drying.
（２）または（６）の脱色操作の工程は両方共析なって
も良いし、どちらか一方だけでも良い。In the decolorization step (2) or (6), both may be eutectoid, or only one of them may be used.
４．４′−ビフェニルジカルボン酸塩が４．４’−ビフ
ェニルジカルボン酸ジアンモニウム塩の場合は第５工程
の代りに、（５’ ）４．４’ −ビフェニルジカル
ボン酸ジアンモニウム塩を加熱分解し４，４′−ビフェ
ニルジカルボン酸を得る工程という方法も取得る。When the 4.4'-biphenyldicarboxylic acid salt is a 4.4'-biphenyldicarboxylic acid diammonium salt, instead of the fifth step, (5')4.4'-biphenyldicarboxylic acid diammonium salt is thermally decomposed. A method of obtaining 4,4'-biphenyldicarboxylic acid is also obtained.
ただし、本発明は、（１）および（３）の工程は必須で
ある。However, in the present invention, steps (1) and (3) are essential.
以下、本発明を手順に沿って詳細に説明する。Hereinafter, the present invention will be explained in detail along the procedure.
本発明において使用する粗４．４′ −ビフェニルジ
カルボン酸は、ｐ−クロロ安息香酸等をカップリングし
得られたものでもよいし、４，４′ −ジメチルビフ
ェニル、４，４′ −ジエチルビフェニル、４．４′
ジイソプロピルビフエニル、４−アルキル−４′ −ホ
ルミルビフェニル、４−アルキル−４′−アシルビフェ
ニル等の４．４′ −ジ置換ビフェニルを液相酸化す
ることにより得られたものでもよい。純度には格別の制
限はないが、８０〜９９重量％、好ましくは９０〜９８
重量％程度の粗４゜４′ −ジフェニルジカルボン酸を
原料とすることがよい。The crude 4,4'-biphenyl dicarboxylic acid used in the present invention may be one obtained by coupling p-chlorobenzoic acid, etc., or may be one obtained by coupling p-chlorobenzoic acid, etc. 4.4'
It may also be one obtained by liquid phase oxidation of 4,4'-disubstituted biphenyls such as diisopropylbiphenyl, 4-alkyl-4'-formylbiphenyl, and 4-alkyl-4'-acylbiphenyl. There are no particular restrictions on purity, but 80 to 99% by weight, preferably 90 to 98% by weight.
It is preferable to use crude 4°4'-diphenyldicarboxylic acid in an amount of about % by weight as a raw material.
このような粗４，４′ −ジフェニルジカルボン酸を
まずアルカリ塩および／またはアンモニウム塩の水溶液
となす。アルカリ塩としてはリチウム塩、ナトリウム塩
、カリウム塩およびルビジウム塩があるがナトリウム塩
およびカリウム塩が好ましい。Such crude 4,4'-diphenyldicarboxylic acid is first made into an aqueous solution of an alkali salt and/or ammonium salt. Alkaline salts include lithium salts, sodium salts, potassium salts and rubidium salts, with sodium salts and potassium salts being preferred.
アルカリ塩とするには、水酸化物、炭酸塩、炭酸水素塩
等の水溶液が用いられるが、特に水酸化物の水溶液が好
ましい。アンモニウム塩とするには、アンモニア水、炭
酸アンモニウム塩水溶液、炭酸水素アンモニウム水溶液
等が用い得るが、特にアンモニア水が好ましい。アンモ
ニウム水は、水溶液としてカルボン酸に接触させてもよ
いし、水の中にカルボン酸を入れアンモニアガスを吹込
んでもよい。アルカリおよびまたはアンモニウムの使用
量は、４，４′ −ビフェニルジカルボン酸および塩
を形成し得る不純物に対して当量以上であれば良いが、
通常、粗４，４′ −ビフェニルジカルボン酸を完全に
溶解するには１．１〜１．８杯当量用いると良い。溶解
の際、必要に応じて加熱しても差支えない。Aqueous solutions of hydroxides, carbonates, hydrogen carbonates, etc. are used to form alkaline salts, and aqueous solutions of hydroxides are particularly preferred. To prepare the ammonium salt, aqueous ammonia, aqueous ammonium carbonate salt solution, aqueous ammonium bicarbonate solution, etc. can be used, and aqueous ammonia is particularly preferred. Ammonium water may be brought into contact with carboxylic acid as an aqueous solution, or carboxylic acid may be placed in water and ammonia gas may be blown into it. The amount of alkali and/or ammonium used may be at least equivalent to 4,4'-biphenyldicarboxylic acid and impurities that can form salts.
Usually, it is recommended to use 1.1 to 1.8 equivalents to completely dissolve crude 4,4'-biphenyldicarboxylic acid. During dissolution, heating may be applied as necessary.
粗４，４′ −ビフェニルジカルボン酸がジカルボン
酸塩の水溶液となった時点で、活性炭を［４，４′ −
ビフェニルジカルボン酸に対して１〜２０重量％加え、
攪拌、固液分離することにより脱色処理を行なうことも
できる。When the crude 4,4'-biphenyl dicarboxylic acid becomes an aqueous solution of the dicarboxylate salt, activated carbon is added to [4,4'-
Adding 1 to 20% by weight based on biphenyldicarboxylic acid,
Decolorization treatment can also be carried out by stirring and solid-liquid separation.
次いで、４．４′ −ビフェニルジカルボン酸塩の水溶
液から４，４′ −ビフェニルジカルボン酸塩を析出
させる。析出させる方法とては下記のような方法が上げ
られる。すなわち、
（ａ）水溶液を冷却する。Next, 4,4'-biphenyl dicarboxylate is precipitated from the aqueous solution of 4,4'-biphenyl dicarboxylate. Examples of the precipitation method include the following methods. That is, (a) cooling the aqueous solution;
（ｂ）水溶液を濃縮する。(b) Concentrate the aqueous solution.
（ｃ）水溶液に塩を加え、塩析を行なう。(c) Add salt to the aqueous solution and perform salting out.
といった方法である。This is the method.
上記の方法は単独で用いることもできるが、組み合わせ
て用いる方がより効果的である。例えば、４．４′−ビ
フェニルジカルボン酸塩の水溶液をある程度濃縮し、室
温付近まで冷却後、塩を加えて４．４′ −ビフェニ
ルジカルボン酸塩を析出させるといった方法では、高純
度４．４′ −ビフェニルジカルボン酸が高収率で得
られる。塩析に用いる塩としては塩化物、炭酸塩、炭酸
水素塩等が良く、パ必ずしも４，４′ −ビフェニル
ジカルボン酸塩と同じカチオンとならなくとも良い。す
なわち、４．４′ −ビフェニルジカルボン酸ジカリウ
ム塩の塩析に塩化ナトリウムを用いても良い。Although the above methods can be used alone, it is more effective to use them in combination. For example, by concentrating an aqueous solution of 4.4'-biphenyl dicarboxylate to some extent, cooling it to around room temperature, and adding salt to precipitate 4.4'-biphenyl dicarboxylate, a high purity 4.4' -Biphenyldicarboxylic acid is obtained in high yield. The salt used for salting out is preferably a chloride, carbonate, hydrogen carbonate, etc., and does not necessarily have to be the same cation as the 4,4'-biphenyl dicarboxylate. That is, sodium chloride may be used for salting out the dipotassium salt of 4,4'-biphenyldicarboxylic acid.
以上のように析出した４、４′ −ビフェニルジカル
ボン酸塩を固液分離し、血漿に付着した母液を取除くた
めに冷水または塩の水溶液でリンスする。The 4,4'-biphenyldicarboxylic acid salt precipitated as described above is separated into solid and liquid, and rinsed with cold water or an aqueous salt solution to remove the mother liquor adhering to the plasma.
リンス液に使用する塩としては塩析に用いたものと同様
な塩で良い。このリンスの繰作を行なわないと、結晶に
付着した母液中の不純物の除去が困難となり、最終的得
られる４、４′ −ビフェニルジカルボン酸の純度は低
いものとなる。The salt used in the rinsing solution may be the same as that used for salting out. If this rinsing is not repeated, it will be difficult to remove impurities in the mother liquor adhering to the crystals, and the purity of the 4,4'-biphenyl dicarboxylic acid ultimately obtained will be low.
リンスの終った４、４′ −ビフェニルジカルボン酸
塩は公知の方法により、精製または分解して４゜４′
−ビフェニルジカルボン酸とする。好ましくは４，４′
−ビフェニルジカルボン酸塩は再び水に溶解させる
。この際、加熱すると、速やかに溶解し効果的である。After rinsing, the 4,4'-biphenyldicarboxylate is purified or decomposed by a known method to obtain 4゜4'
- Biphenyldicarboxylic acid. Preferably 4,4'
- The biphenyl dicarboxylate is dissolved again in water. At this time, heating is effective because it dissolves quickly.
特に４，４′ −ビフェニルジカルボン酸ジアンモニ
ウム塩の場合は、水への溶解度が他の塩に比べて低く、
加熱が必要である。この段階で脱色の必要があれば、４
，４′ −ビフェニルジカルボン酸に対し１〜２０重
呈％の活性炭を加え脱色し、活性炭を固液分離により取
除く。In particular, in the case of 4,4'-biphenyldicarboxylic acid diammonium salt, its solubility in water is low compared to other salts;
Heating is required. If bleaching is necessary at this stage,
, 4'-biphenyldicarboxylic acid in an amount of 1 to 20% by weight is added to decolorize the mixture, and the activated carbon is removed by solid-liquid separation.
次いで、塩酸、硝酸、酢酸等の４．４′ −ビフェニル
ジカルボン酸より強い酸を水溶液に加えて４゜４′−ビ
フェニルジカルボン酸を析出させる。さらに析出しな４
，４′ −ビフェニルジカルボン酸を固液分離し、水
で十分水洗し乾燥させることにより、高純度の４．４′
−ビフェニルジカルボン酸が高収率で得られる。Next, an acid stronger than 4.4'-biphenyldicarboxylic acid, such as hydrochloric acid, nitric acid, or acetic acid, is added to the aqueous solution to precipitate 4.4'-biphenyldicarboxylic acid. Even more precipitation 4
, 4'-biphenyldicarboxylic acid is solid-liquid separated, thoroughly washed with water, and dried to obtain highly pure 4.4'-biphenyldicarboxylic acid.
-Biphenyldicarboxylic acid is obtained in high yield.
４，４′−ビフェニルジカルボン酸塩が４．４’−ビフ
ェニルジカルボン酸ジアンモニウム塩の場合は、加熱分
解によっても４，４′ −ビフェニルジカルボン酸と
することができる。加熱分解の温度は２００〜４００℃
が適当である。加熱分解温度が４００°Ｃを越えると生
成した４、４′ −ビフェニルジカルボン酸中に着色
物質が存在し、２００℃未溝では分解速度が遅く工業的
でない。When the 4,4'-biphenyldicarboxylic acid salt is a diammonium salt of 4,4'-biphenyldicarboxylic acid, it can also be converted into 4,4'-biphenyldicarboxylic acid by thermal decomposition. Thermal decomposition temperature is 200-400℃
is appropriate. When the thermal decomposition temperature exceeds 400°C, colored substances are present in the 4,4'-biphenyldicarboxylic acid produced, and the decomposition rate is slow at 200°C, making it unsuitable for industrial use.
［実施例コ
以下、実施例を上げて、本発明について説明する。実施
例中の「部Ｊは重量部」、「％」は「重量％Ｊであり、
純度は高速液体クロマトグラフィでの検量線法により測
定した値である。[Example] The present invention will be described below with reference to Examples. In the examples, "part J is part by weight" and "%" is "weight % J,"
Purity is a value measured by a calibration curve method using high performance liquid chromatography.
実施例１
４．４′ −ジエチルビフェニルを原料とし、触媒と
してコバルトおよびマンガンの酢酸塩および臭化ナトリ
ウムを用い、オートクル−プを用いて酢酸溶液中で空気
酸化した生成物を炉別して固形分を熱酢酸および水で洗
浄後乾燥して純度９４．０％の粗４，４′ −ビフェ
ニルジカルボン酸を得た。Example 1 Using 4.4'-diethylbiphenyl as a raw material and using cobalt and manganese acetate and sodium bromide as catalysts, the product was air oxidized in an acetic acid solution using an autocrup, and the solid content was removed by furnace separation. After washing with hot acetic acid and water and drying, crude 4,4'-biphenyldicarboxylic acid with a purity of 94.0% was obtained.
得られた［４，４ ’ −ビフェニルジカルボン酸中
には４−アセチル−４〜カルボキシビフエニル、４−ホ
ルミル−４−カルボキシビフェニル等の反応中固体、コ
バルト、マンガン臭素等の触媒金属等が含まれ、着色物
質により粉末の状態で肌色に着色していた。The obtained [4,4'-biphenyl dicarboxylic acid contains solids during the reaction such as 4-acetyl-4-carboxybiphenyl and 4-formyl-4-carboxybiphenyl, and catalytic metals such as cobalt and manganese bromine. The powder was colored skin-colored by a coloring substance.
このｆｆ１４．４ ’ −ビフェニルジカルボン酸１
００部に５％水酸化カリウム水溶液を１４００部加え、
８０℃にて加熱溶解せしめた。この時の液の色は茶かつ
色であった。ついで、炭酸カリウム７０部を添加し、濃
縮を行なって全量を６５０部とした。This ff14.4'-biphenyldicarboxylic acid 1
Add 1400 parts of 5% potassium hydroxide aqueous solution to 00 parts,
The mixture was heated and dissolved at 80°C. The color of the liquid at this time was brown and colored. Then, 70 parts of potassium carbonate was added and concentrated to bring the total amount to 650 parts.
この濃縮液を５０℃まで除令し、更に同じ濃度で１時間
攪拌を継続して充分結晶を析出させた後沢別した。This concentrated solution was cooled down to 50° C., and stirred at the same concentration for 1 hour to sufficiently precipitate crystals, and then separated.
得られたジカリウム塩の結晶を、冷水９５部でリンス洗
浄し、ここでいったん乾燥して１０５部の結晶を得た。The obtained dipotassium salt crystals were rinsed with 95 parts of cold water and dried once to obtain 105 parts of crystals.
このときの結晶の色は淡黄色であった。この結晶に再び
熱水２，１００部を加え、攪拌下で完全に溶解せしめて
、活性炭１０部を添加し、８０℃の加熱下で３０分間攪
拌を継続後、Ｐ別により活性炭を除去し、無色透明のｒ
液を得た。The color of the crystals at this time was pale yellow. Add 2,100 parts of hot water to this crystal again and completely dissolve it under stirring, add 10 parts of activated carbon, continue stirring for 30 minutes under heating at 80 ° C., and remove the activated carbon by P. Colorless and transparent r
I got the liquid.
この液に撹拌下で５％塩酸を少量ずつｐＨが３になるま
で添加して、析出した結晶をｒ別し、水洗後乾燥して純
白の４，４′ −ビフェニルジカルボン酸の結晶７５
部を得た。この結晶の純度は９９．９％で収率は７９．
８％であった。5% hydrochloric acid was added little by little to this solution while stirring until the pH reached 3, and the precipitated crystals were separated, washed with water, and dried to give pure white crystals of 4,4'-biphenyldicarboxylic acid 75
I got the department. The purity of this crystal is 99.9% and the yield is 79.9%.
It was 8%.
実施例２
実施例１と同じ粗４，４′ −ビフェニルジカルボン酸
１００部に２９％アンモニア水３００部を加え、更に水
５，０００部を加えて攪拌下で９０℃に加熱して溶液と
した。この溶液を全量３０００部まで濃縮し、塩化カリ
ウム１００部を徐々に添加した後、攪拌を継続しながら
、２０℃まで徐冷して結晶を析出せしめＰ別した。Example 2 300 parts of 29% ammonia water was added to 100 parts of the same crude 4,4'-biphenyldicarboxylic acid as in Example 1, and 5,000 parts of water was further added and heated to 90°C with stirring to form a solution. . This solution was concentrated to a total volume of 3000 parts, and 100 parts of potassium chloride was gradually added thereto. While stirring was continued, the mixture was slowly cooled to 20°C to precipitate crystals and P was separated.
この結晶を冷水９５部ででリンス洗浄後、９０°Ｃの熱
水５，０００部を加え、攪拌しながらアンモニア水を少
量ずつ加えて、ｐＨを８．５以上に保ち、再溶解し、活
性炭１５部を添加し、更に攪拌を３０分間継続した後、
濾過により活性炭を除去した。このときの溶液の色は無
色透明であった。After rinsing the crystals with 95 parts of cold water, add 5,000 parts of 90°C hot water, add ammonia water little by little while stirring to keep the pH above 8.5, redissolve the activated carbon. After adding 15 parts and continuing stirring for an additional 30 minutes,
Activated carbon was removed by filtration. The color of the solution at this time was clear and colorless.
この液に５％塩酸を少量ずつｐＨが３になるまで添加し
て結晶を析出せしめ、Ｐ別後、水洗、乾燥して純白の４
，４′ −ビフェニルジカルボン酸の結晶を８４．１
部得た。この結晶の純度は９９．９％で収率は８９．５
％であった。5% hydrochloric acid was added little by little to this solution until the pH reached 3 to precipitate crystals, and after separating the P, they were washed with water and dried to form pure white 4
, 84.1 crystals of 4'-biphenyldicarboxylic acid
I got it. The purity of this crystal is 99.9% and the yield is 89.5
%Met.
［発明の効果］
以上述べたように、本発明は、粗４，４′ −ビフェニ
ルジカルボン酸を４，４′ −ビフェニルジカルボン
酸塩の水溶液となし、次いで、該水溶液の濃縮および／
または４，４′ −ビフェニルジカルボン゛酸塩の溶
解度を下げる手段により４，４′ −ビフェニルジカ
ルボン酸塩を析出させ分離する工程を含んでなる４、４
′ −ビフェニルジカルボン酸の精製方法であるから
、高純度の４．４′ −ビフェニルジカルボン酸を高
収率で得ることができる。[Effects of the Invention] As described above, the present invention converts crude 4,4'-biphenyldicarboxylic acid into an aqueous solution of 4,4'-biphenyldicarboxylic acid salt, and then concentrates the aqueous solution and/or
or 4,4 comprising a step of precipitating and separating 4,4'-biphenyldicarboxylic acid salt by means of lowering the solubility of 4,4'-biphenyldicarboxylic acid salt.
Since this is a method for purifying '-biphenyldicarboxylic acid, highly purified 4,4'-biphenyldicarboxylic acid can be obtained in high yield.
特許出願人 新日鐵化学株式会社代理人 弁
理士 八 １） 幹 雄（他１名）手続乎市正書
平成１年 ９月 １０
特許庁長官 吉 １１１ 文 毅 殿１、事件の
表示
昭和６３年 特許願 第１８６．４４２号２、発明の名
称
４．４′−ビフェニルジカルボン酸の精製性代表者 森
口 ｌ：
５、補正命令の日付
自発補正
明細書の「発明の詳細な説明」の欄
記載した事項以外は内容に変更ない。Patent Applicant Nippon Steel Chemical Co., Ltd. Agent Patent Attorney 8 1) Mikio (and 1 other person) Proceedings September 1999 Commissioner of the Patent Office Yoshi 111 Moon Yi 1, Indication of the case 1986 Patent Application No. 186.442 2, Title of the invention 4. Purification of 4'-biphenyldicarboxylic acid Representative Moriguchi I: 5, Date of amendment order stated in the "Detailed Description of the Invention" column of the voluntary amended specification There are no changes to the content other than the above.
訂正明細書
１、発明の名称
４．４′ −ビフェニルジカルボン酸の精製法２、特
許請求の範囲
ｔｆ１４．４ ’ −ビフェニルジカルボン酸を、下
記式（Ｉ）に示す４．４′ −ビフェニルジカルボン
酸塩の水溶液となし、次いで、該水溶液の濃縮および／
または４．４′ −ビフェニルジカルボン酸塩の溶解
度を下げる手段により４．４′ −ビフェニルジカル
ボン酸塩を析出させ分離する工程を含むことを特徴とす
る４、４′ −ビフェニルジカルボン酸の精製法。Amended specification 1, title of the invention 4. Purification method of 4'-biphenyldicarboxylic acid 2, claims tf14.4'-biphenyldicarboxylic acid is 4.4'-biphenyldicarboxylic acid represented by the following formula (I) an aqueous solution of the salt, then concentrating the aqueous solution and/or
Alternatively, a method for purifying 4,4'-biphenyldicarboxylic acid, which comprises the step of precipitating and separating 4,4'-biphenyldicarboxylic acid salt by means of lowering the solubility of 4,4'-biphenyldicarboxylic acid salt.
（ただし、式中、ＸおよびＹはＬｉ、 Ｎａ、 Ｋ。(However, in the formula, X and Y are Li, Na, and K.
ＲｂまたはＮＨ４を示し、ＸとＹは同一であっても、異
なってもよい）。represents Rb or NH4, and X and Y may be the same or different).
３、発明の詳細な説明
［産業上の利用分野］
本発明は、４．４′ −ビフェニルジカルボン酸の精
製法に関するものである。3. Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for purifying 4,4'-biphenyldicarboxylic acid.
［従来の技術］
４．４′ −ビフェニルジカルボン酸は、新規ポリマ
ー原料として需要が期待されている物質である。[Prior Art] 4.4'-biphenyldicarboxylic acid is a substance that is expected to be in demand as a new polymer raw material.
４．４′ −ビフェニルジカルボン酸の合成法として
は、安息香酸またはその誘導体をニッケル、パラジウム
等を触媒に用いてカップリングする方法、または４．４
′ −ビフェニルジ置換体を液相酸化によって酸化す
る方法があるが、前者によって生成した粗４．４′
−ビフェニルジカルボン酸中には安息香酸、触媒金属な
どの不純物が含まれ、また、後者によって生成した粗４
．４′ −ビフェニルジカルボン酸中には、酸化反応
中間体、触媒金属、着色物質等の不純物が含まれる。よ
って、いずれも高純度が要求されるポリマー原料として
は不適切であり、粗４．４′ −ビフェニルジカルボ
ン酸の精製法の確立は重要な課題であった。4.4'-Biphenyldicarboxylic acid can be synthesized by coupling benzoic acid or its derivatives using nickel, palladium, etc. as a catalyst, or 4.4
There is a method of oxidizing ′ -biphenyl disubstituted product by liquid phase oxidation, but the crude 4.4′ produced by the former method is
- Biphenyl dicarboxylic acid contains impurities such as benzoic acid and catalytic metals, and the crude 4 produced by the latter
．． 4'-biphenyldicarboxylic acid contains impurities such as oxidation reaction intermediates, catalytic metals, and colored substances. Therefore, all of these are unsuitable as polymer raw materials that require high purity, and the establishment of a method for purifying crude 4,4'-biphenyldicarboxylic acid has been an important issue.
従来、４．４ ’ −ビフェニルジカルボン酸を精製
する方法としては、特開昭５７−１４９，２４４号に記
載されているように、ジメチルスルホキシドを溶媒とし
て再結晶する方法、あるいは特開昭５８−８５．８４１
号に記載されてい・るように、４．４ ’ −ビフェ
ニルジカルボン酸ジアルカリ塩水溶液に炭酸ガスを作用
させて４．４′ −ビフェニルジカルボン酸モノアル
カリ塩を析出、分離し、しかる後に不均化させる方法な
どが知られている。Conventionally, methods for purifying 4,4'-biphenyldicarboxylic acid include recrystallization using dimethyl sulfoxide as a solvent, as described in JP-A-57-149,244; 85.841
As described in the above issue, carbon dioxide gas is applied to an aqueous solution of a dialkali salt of 4.4'-biphenyldicarboxylic acid to precipitate and separate a monoalkali salt of 4.4'-biphenyldicarboxylic acid, followed by disproportionation. There are known methods to do this.
しかしながら、前者の精製法では、ジメチルスルホキシ
ドに対する４、４′ −ビフェニルジカルボン酸の溶
解度が低く、大量のジメチルスルホキシドが必要であり
、効率の良（ない分離法であった。However, in the former purification method, the solubility of 4,4'-biphenyldicarboxylic acid in dimethyl sulfoxide is low, a large amount of dimethyl sulfoxide is required, and the separation method is not efficient.
また、後者の精製法も、加圧圧力容器を用いた煩雑な操
作が必要であり、改善が望まれていた。Furthermore, the latter purification method also requires complicated operations using a pressurized pressure vessel, and improvements have been desired.
［発明が解決しようとする課題］
本発明は、粗４．４′ −ビフェニルジカルボン酸か
ら高収率かつ高純度で４．４′ −ビフェニルジカル
ボン酸を得ることができる精製法の提供を目的とする。[Problems to be Solved by the Invention] The purpose of the present invention is to provide a purification method capable of obtaining 4.4'-biphenyldicarboxylic acid in high yield and purity from crude 4.4'-biphenyldicarboxylic acid. do.
［課題を解決するための手段］
本発明者らは、上記精製法の確立を目的とじて行ない、
粗４．４′ −ビフェニルジカルボン酸を４゜４′
−ビフェニルジカルボン酸塩の水溶液となし、次いで、
該水溶液の濃縮および／または４．４’−ビフェニルジ
カルボン酸塩の溶解度を下げる手段により、４．４′
−ビフェニルジカルボン酸塩を析出させ分離し、しか
る後、得られた塩を酸析または加熱分解することにより
高純度の４．４′ −ビフェニルジカルボン酸が高収
率で得られことを見出し、本発明を完成した。[Means for Solving the Problems] The present inventors conducted the above purification method for the purpose of establishing the above purification method,
Crude 4.4'-biphenyldicarboxylic acid to 4°4'
- an aqueous solution of biphenyldicarboxylate, then
4.4' by concentrating the aqueous solution and/or reducing the solubility of the 4.4'-biphenyldicarboxylic acid salt.
It has been discovered that high purity 4.4'-biphenyl dicarboxylic acid can be obtained in high yield by precipitating and separating the -biphenyl dicarboxylic acid salt, and then acidifying or thermally decomposing the resulting salt, and the present invention Completed the invention.
ここで言う４．４′ −ビフェニルジカルボン酸塩は
、下記式（Ｉ）で示されるものである。The 4,4'-biphenyl dicarboxylate mentioned here is represented by the following formula (I).
（ただし、式中、ＸおよびＹはＬｉ、 Ｎａ、 Ｋ。(However, in the formula, X and Y are Li, Na, and K.
ＲｂまたはＮＨ４を示し、ＸとＹは同一であっても異な
ってもよい）。具体的には、４．４ ’ −ビフェニ
ルジカルボン酸ジカリウム塩、４．４ ’ −ビフェ
ニルジカルボン酸ジカリウム塩などの４．４′−ビフェ
ニルジカルボン酸ジアルカリ金属塩または４，４′
−ビフェニルジカルボン酸ジアンモニウム塩である。ま
た、それらの塩の混合物でも、−方のカルボキシル基と
他方のカルボキシル基に結合するアルカリ金属またはア
ンモニウムが異なる塩であっても差支えない。represents Rb or NH4, and X and Y may be the same or different). Specifically, 4.4'-biphenyldicarboxylic acid dialkali metal salts such as 4.4'-biphenyldicarboxylic acid dipotassium salt, 4.4'-biphenyldicarboxylic acid dipotassium salt, or 4,4'
- biphenyldicarboxylic acid diammonium salt. Moreover, even if it is a mixture of these salts, the alkali metal or ammonium bonded to one carboxyl group and the other carboxyl group may be different.
本発明は、例えば下記に示す各工程より行うことができ
る。The present invention can be carried out, for example, through the steps shown below.
（１）粗４，４′ −ビフェニルジカルボン酸をアル
カリ金属および／またはアンモニウムの水酸化物または
弱酸塩の水溶液等に加えてジカルボン酸塩としたのち、
又はとすると共にジカルボン酸塩の水溶液とする工程。(1) After adding crude 4,4'-biphenyldicarboxylic acid to an aqueous solution of an alkali metal and/or ammonium hydroxide or weak acid salt to form a dicarboxylic acid salt,
or a step of preparing an aqueous solution of the dicarboxylate.
（２）水溶液に活性炭等を加え脱色し、しかる後に活性
炭を分離する工程。(2) A step of adding activated carbon or the like to the aqueous solution to decolorize it, and then separating the activated carbon.
（３）水溶液から４．４′ −ビフェニルジカルボン
酸塩を析出させる工程。(3) A step of precipitating 4.4'-biphenyl dicarboxylate from an aqueous solution.
（４） ４．４ ’ −ビフェニルジカルボン酸塩を
固液分離し、付着１号液をリンスにより除去する工程。(4) A step of separating the 4.4′-biphenyldicarboxylic acid salt into solid and liquid and removing the adhered No. 1 liquid by rinsing.
（５） ４．４ ’ −ビフェニルジカルボン酸塩を
再び水に溶解させる工程。(5) Step of dissolving the 4.4′-biphenyl dicarboxylate in water again.
（６）水溶液に活性炭等を加え脱色し、しかる後活性炭
を分離する工程。(6) A step of adding activated carbon or the like to the aqueous solution to decolorize it, and then separating the activated carbon.
（７）水溶液に酸を加え酸析し、４，４′ −ビフェ
ニルジカルボン酸を析出させる工程。(7) A step of adding an acid to the aqueous solution to precipitate it to precipitate 4,4'-biphenyldicarboxylic acid.
（８） ４．４ ’ −ビフェニルジカルボン酸を固
液分離し、付着母液をリンスにより除去し、乾燥する工
程。(8) A step of separating 4.4′-biphenyldicarboxylic acid into solid and liquid, removing the adhering mother liquor by rinsing, and drying.
（２）または（６）の脱色操作の工程は両方共行なって
も良いし、どちらか一方だけでも良い。Both steps (2) or (6) of the decolorization operation may be performed, or only one of them may be performed.
４．４′−ビフェニルジカルボン酸塩が４．４’−ビフ
ェニルジカルボン酸ジアンモニウム塩の場合は第５工程
以降の代りに、＜５’ ）４．４’ −ビフェニルジ
カルボン酸ジアンモニウム塩を加熱分解し４゜４′ −
ビフェニルジカルボン酸を得る工程という方法も取得る
。When the 4.4'-biphenyldicarboxylic acid salt is a 4.4'-biphenyldicarboxylic acid diammonium salt, instead of the 5th and subsequent steps, <5') 4.4'-biphenyldicarboxylic acid diammonium salt is thermally decomposed. 4゜4′ −
A method of obtaining biphenyldicarboxylic acid is also obtained.
ただし、本発明は、（１）および（３）の工程は必須で
ある。However, in the present invention, steps (1) and (3) are essential.
以下、本発明を手順に沿って詳細に説明する。Hereinafter, the present invention will be explained in detail along the procedure.
本発明において使用する粗４，４′ −ビフェニルジ
カルボン酸は、ｐ−クロロ安息香酸等をカップリングし
得られたものでもよいし、４，４′ −ジメチルビフ
ェニル、４．４ ’ −ジエチルビフェニル、４．４
′ −シイツブ旧ビルビフェニル、４−アルキル−４
′ −ホルミルビフェニル、４−アルキル−４′ −ア
シルビフェニル等の４，４′ −ジ置換ビフェニルを
液相酸化することにより得られたものでもよい。純度に
は格別の制限はないが、８０〜９９重量％、好ましくは
９０〜９８虫量％程度の粗４．４′ −ジフェニルジ
カルボン酸を原料とすることがよい。The crude 4,4'-biphenyldicarboxylic acid used in the present invention may be one obtained by coupling p-chlorobenzoic acid, etc., or may be 4,4'-dimethylbiphenyl, 4,4'-diethylbiphenyl, 4.4
' - Old bilbiphenyl, 4-alkyl-4
It may also be one obtained by liquid phase oxidation of 4,4'-disubstituted biphenyls such as '-formylbiphenyl and 4-alkyl-4'-acylbiphenyl. Although there are no particular restrictions on the purity, it is preferable to use crude 4.4'-diphenyldicarboxylic acid of about 80 to 99% by weight, preferably 90 to 98% by weight, as a raw material.
このような粗４．４′ −ジフェニルジカルボン酸を
まずアルカリ塩および／またはアンモニウム塩の水溶液
となす。アルカリ塩としてはリチウム塩、ナトリウム塩
、カリウム塩およびルビジウム塩があるがナトリウム塩
およびカリウム塩が好ましい。Such crude 4,4'-diphenyldicarboxylic acid is first made into an aqueous solution of an alkali salt and/or an ammonium salt. Alkaline salts include lithium salts, sodium salts, potassium salts and rubidium salts, with sodium salts and potassium salts being preferred.
アルカリ塩とするには、水酸化物、炭酸塩、炭酸水素塩
等の水溶液が用いられるが、特に水酸化物の水溶液が好
ましい。アンモニウム塩とするには、アンモニア水、炭
酸アンモニウム塩水溶液、炭酸水素アンモニウム水溶液
等が用い得るが、特にアンモニア水が好ましい。アンモ
ニア水は、水溶液としてカルボン酸に接触させてもよい
し、水の中にカルボン酸を入れアンモニアガスを吹込ん
でもよい。アルカリおよび／またはアンモニウムの使用
量は、４．４′ −ビフェニルジカルボン酸および塩
を形成し得る不純物に対して当量以上であれば良いが、
通常、粗４，４′ −ビフェニルジカルボン酸を完全
に溶解するには１．１〜１．８倍当量用いると良い。溶
解の際、必要に応じて加熱しても差支えない。Aqueous solutions of hydroxides, carbonates, hydrogen carbonates, etc. are used to form alkaline salts, and aqueous solutions of hydroxides are particularly preferred. To prepare the ammonium salt, aqueous ammonia, aqueous ammonium carbonate salt solution, aqueous ammonium bicarbonate solution, etc. can be used, and aqueous ammonia is particularly preferred. Ammonia water may be brought into contact with carboxylic acid as an aqueous solution, or carboxylic acid may be placed in water and ammonia gas may be blown into the water. The amount of alkali and/or ammonium used may be at least equivalent to 4,4'-biphenyldicarboxylic acid and impurities that can form salts.
Usually, it is recommended to use 1.1 to 1.8 equivalents to completely dissolve crude 4,4'-biphenyldicarboxylic acid. During dissolution, heating may be applied as necessary.
粗４，４′ −ビフェニルジカルボン酸がジカルボン
酸塩の水溶液となった時点で、活性炭を粗４．４′ −
ビフェニルジカルボン酸に対して１〜２０重量％加え、
攪拌、固液分離することにより脱色処理を行なうことも
できる。When the crude 4,4'-biphenyldicarboxylic acid becomes an aqueous solution of the dicarboxylate salt, activated carbon is added to the crude 4,4'-biphenyldicarboxylic acid.
Adding 1 to 20% by weight based on biphenyldicarboxylic acid,
Decolorization treatment can also be carried out by stirring and solid-liquid separation.
次いで、４．４ ’ −ビフェニルジカルボン酸塩の
水溶液から４．４′ −ビフェニルジカルボン酸塩を
析出させる。析出させる方法とては下記のような方法が
挙げられる。すなわち、
（ａ）水溶液を冷却する。Next, 4.4'-biphenyl dicarboxylate is precipitated from the aqueous solution of 4.4'-biphenyl dicarboxylate. Examples of the precipitation method include the following methods. That is, (a) cooling the aqueous solution;
（ｂ）水溶液を濃縮する。(b) Concentrate the aqueous solution.
（Ｃ）水溶液に塩を加え、塩析を行なう。(C) Add salt to the aqueous solution and perform salting out.
といった方法であ゛る。There is a method like this.
上記の方法は単独で用いることもできるが、組み合わせ
て用いる方がより効果的である。例えば、４．４′ −
ビフェニルジカルボン酸塩の水溶液をある程度濃縮し、
室温付近まで冷却後、塩を加えて４．４′ −ビフェ
ニルジカルボン酸塩を析出させるといった方法では、高
純度４．４′ −ビフェニルジカルボン酸が高収率で
得られる。塩析に用いる塩としては塩化物、炭酸塩、炭
酸水素塩等が良く、必ずしも４．４′ −ビフェニル
ジカルボン酸塩と同じカチオンとならなくとも良い。す
なわち、４．４′ −ビフェニルジカルボン酸ジカリウ
ム塩の塩析に塩化す！・リウムを用いても良い。Although the above methods can be used alone, it is more effective to use them in combination. For example, 4.4′ −
Concentrate the aqueous solution of biphenyl dicarboxylate to some extent,
Highly purified 4.4'-biphenyldicarboxylic acid can be obtained in high yield by a method in which 4.4'-biphenyldicarboxylic acid salt is precipitated by adding a salt after cooling to around room temperature. The salt used for salting out is preferably a chloride, carbonate, hydrogen carbonate, etc., and does not necessarily have to be the same cation as the 4,4'-biphenyl dicarboxylate. That is, 4.4'-biphenyldicarboxylic acid dipotassium salt is salted out!・Rium may be used.
以上のように析出した４、４′ −ビフェニルジカル
ボン酸塩を固液分離し、結晶に付着した母液を取除くた
めに冷水または塩の水溶液でリンスする。The 4,4'-biphenyldicarboxylic acid salt precipitated as described above is separated into solid and liquid, and rinsed with cold water or an aqueous salt solution to remove the mother liquor adhering to the crystals.
リンス液に使用する塩としては塩析に用いたものと同様
な塩で良い。このリンスの操作を行なわないと、結晶に
付着した母液中の不純物の除去が困難となり、最終的に
得られる４、４′ −ビフェニルジカルボン酸の純度
は低いものとなる。The salt used in the rinsing solution may be the same as that used for salting out. If this rinsing operation is not performed, it will be difficult to remove impurities in the mother liquor adhering to the crystals, and the purity of the 4,4'-biphenyldicarboxylic acid finally obtained will be low.
リンスの終った４、４′ −ビフェニルジカルボン酸
塩は公知の方法により、精製または分解して４゜４′
−ビフェニルジカルボン酸とする。好ましくは４．４′
−ビフェニルジカルボン酸塩は再び水に溶解させる
。この際、加熱すると、速やかに溶解し効果的である。After rinsing, the 4,4'-biphenyldicarboxylate is purified or decomposed by a known method to obtain 4゜4'
- Biphenyldicarboxylic acid. Preferably 4.4'
- The biphenyl dicarboxylate is dissolved again in water. At this time, heating is effective because it dissolves quickly.
特に４．４′ −ビフェニルジカルボン酸ジアンモニ
ウム塩の場合は、水への溶解度が他の塩に比べて低く、
加熱が必要である。この段階で脱色の必要があれば、４
．４ ’ −ビフェニルジカルボン酸に対し１〜２０
重量％の活性炭を加え脱色し、活性炭を固液分離により
取除く。In particular, in the case of 4.4′-biphenyldicarboxylic acid diammonium salt, its solubility in water is low compared to other salts;
Heating is required. If bleaching is necessary at this stage,
．． 1 to 20 for 4'-biphenyldicarboxylic acid
% by weight of activated carbon is added to decolorize, and the activated carbon is removed by solid-liquid separation.
次いで、塩酸、硝酸、酢酸等の４．４′ −ビフェニ
ルジカルボン酸より強い酸を水溶液に加えて４゜４′
−ビフェニルジカルボン酸を析出させる。さらに析出し
た４、４′ −ビフェニルジカルボン酸を固液分離し
、水で十分水洗し乾燥させることにより、高純度の４．
４′ −ビフェニルジカルボン酸が高収率で得られる
。Next, an acid stronger than 4.4'-biphenyldicarboxylic acid, such as hydrochloric acid, nitric acid, or acetic acid, is added to the aqueous solution to give 4.4'
- Precipitating biphenyldicarboxylic acid. Furthermore, the precipitated 4,4'-biphenyldicarboxylic acid is separated into solid and liquid, thoroughly washed with water, and dried to obtain highly pure 4.
4'-biphenyldicarboxylic acid is obtained in high yield.
４．４′−ビフェニルジカルボン酸塩が４．４’−ビフ
ェニルジカルボン酸ジアンモニウム塩の場合は、加熱分
解によっても４．４′ −ビフェニルジカルボン酸と
することができる。加熱分解の温度は２００〜４００℃
が適当である。加熱分解温度が４００℃を越えると生成
した４、４′ −ビフェニルジカルボン酸中に着色物
質が存在し、２００℃未満では分解速度が遅く工業的で
ない。When the 4.4'-biphenyldicarboxylic acid salt is a 4.4'-biphenyldicarboxylic acid diammonium salt, it can also be converted into 4.4'-biphenyldicarboxylic acid by thermal decomposition. Thermal decomposition temperature is 200-400℃
is appropriate. If the thermal decomposition temperature exceeds 400°C, colored substances will be present in the produced 4,4'-biphenyldicarboxylic acid, and if the thermal decomposition temperature is below 200°C, the decomposition rate will be slow and unsuitable for industrial use.
［実施例］
以下、実施例を挙げて、本発明について説明する。実施
例中の「部」は「重量部」、「％」は「重量％」であり
、純度は高速液体クロマトグラフィでの検量線法により
測定した値である。[Example] The present invention will be described below with reference to Examples. In the examples, "part" means "part by weight", "%" means "% by weight", and purity is a value measured by a calibration curve method using high performance liquid chromatography.
実施例１
４．４′ −ジエチルビフェニルを原料とし、触媒と
してコバルトおよびマンガンの酢酸塩および臭化ナトリ
ウムを用い、オートクレーブを用いて酢酸溶液中で空気
酸化した生成物を濾別して固形分を熱酢酸および水で洗
浄後乾燥して純度９４．０％の粗４，４′ −ビフェ
ニルジカルボン酸を得た。Example 1 Using 4.4'-diethylbiphenyl as a raw material, using cobalt and manganese acetate and sodium bromide as catalysts, air oxidation was performed in an acetic acid solution using an autoclave.The product was filtered and the solid content was oxidized with hot acetic acid. After washing with water and drying, crude 4,4'-biphenyldicarboxylic acid with a purity of 94.0% was obtained.
得られた粗４，４′ −ビフェニルジカルボン酸中に
は４−アセチル−４−カルボキシビフェニル、４−ホル
ミル−４〜カルボキシビフエニル等の反応中間体、コバ
ルト、マンガン臭素等の触媒金属等が含まれ、着色物質
により粉末の状態で肌色に着色していた。The obtained crude 4,4'-biphenyl dicarboxylic acid contains reaction intermediates such as 4-acetyl-4-carboxybiphenyl and 4-formyl-4-carboxybiphenyl, and catalytic metals such as cobalt and manganese bromine. The powder was colored skin-colored by a coloring substance.
この粗４，４′ −ビフェニルジカルボン酸１００部
に５％水酸化カリウム水溶液を１４００部加え、８０℃
に°Ｃ加熱溶解せしめた。この時の液の色は茶かっ色で
あった。ついで、炭酸カリウム７０部を添加し、濃縮を
行なって全量を６５０部とした。1400 parts of 5% potassium hydroxide aqueous solution was added to 100 parts of this crude 4,4'-biphenyldicarboxylic acid, and the mixture was heated to 80°C.
The mixture was heated and dissolved at °C. The color of the liquid at this time was brownish. Then, 70 parts of potassium carbonate was added and concentrated to bring the total amount to 650 parts.
この濃縮液を５０℃まで除冷し、更に同じ濃度で１時間
攪拌を継続して充分結晶を析出させた後濾別した。This concentrated solution was gradually cooled to 50° C., and stirring was continued for 1 hour at the same concentration to sufficiently precipitate crystals, which were then filtered.
得られたジカリウム塩の結晶を、冷水９５部でリンス洗
浄し、ここでいったん乾燥して１０５部の結晶を得た。The obtained dipotassium salt crystals were rinsed with 95 parts of cold water and dried once to obtain 105 parts of crystals.
このときの結晶の色は淡黄色であった。この結晶に再び
熱水２，１００部を加え、攪拌下で完全に溶解せしめて
、活性炭１０部を添加し、８０℃の加熱下で３０分間攪
拌を継続後、濾別により活性炭を除去し、無色透明の濾
液を得た。The color of the crystals at this time was pale yellow. Add 2,100 parts of hot water to the crystals again, completely dissolve them under stirring, add 10 parts of activated carbon, continue stirring for 30 minutes under heating at 80°C, and remove the activated carbon by filtration. A colorless and transparent filtrate was obtained.
この液に攪拌下で５％塩酸を少量ずつｐＨが３になるま
で添加して、析出した結晶を濾別し、水洗後乾燥して純
白の４，４′ −ビフェニルジカルボン酸の結晶７５
部を得た。この結晶の純度は９９゜９％で収率は７９．
８％であった。5% hydrochloric acid was added little by little to this solution while stirring until the pH reached 3, and the precipitated crystals were filtered off, washed with water, and dried to give pure white crystals of 4,4'-biphenyldicarboxylic acid 75.
I got the department. The purity of this crystal is 99.9% and the yield is 79.9%.
It was 8%.
実施例２
実施例１と同じ粗４．４′ −ビフェニルジカルボン
酸１００部に２９％アンモニア水３００部を加え、更に
水５．ｏｏｏ部を加えて攪拌下で９０°Ｃに加熱して溶
液とした。この溶液を３０００部まで濃縮し、塩化カリ
ウム１００部を徐々に添加した後、攪拌を継続しながら
、２０℃まで徐冷して結晶を析出せしめ濾別した。Example 2 To 100 parts of the same crude 4.4'-biphenyldicarboxylic acid as in Example 1, 300 parts of 29% aqueous ammonia was added, and 5.0 parts of water was added. ooo part was added and heated to 90°C with stirring to form a solution. This solution was concentrated to 3,000 parts, and 100 parts of potassium chloride were gradually added thereto. While stirring was continued, the mixture was slowly cooled to 20° C. to precipitate crystals and filtered.
この結晶を冷水９５部でリンス洗浄後、９０℃の熱水５
．０００部を加え、攪拌しながらアンモニア水を少量ず
つ加えて、ｐＨを８．５以上に保ち、再溶解し、活性炭
１５部を添加し、更に攪拌を３０分間継続した後、濾過
により活性炭を除去した。このときの溶液の色は無色透
明であった。After rinsing the crystals with 95 parts of cold water, 5 parts of hot water at 90°C
．． 000 parts, add ammonia water little by little while stirring to keep the pH above 8.5, redissolve, add 15 parts of activated carbon, continue stirring for another 30 minutes, and remove the activated carbon by filtration. did. The color of the solution at this time was clear and colorless.
この液に５％塩酸を少量ずつｐＨが３になるまで添加し
て結晶を析出せしめ、濾別後、水洗、乾燥して純白の４
．４′ −ビフェニルジカルボン酸の結晶を８４．１
部得た。この結晶の純度は９９．９％で収率は８９．５
％であった。5% hydrochloric acid was added little by little to this solution until the pH reached 3 to precipitate crystals, which were separated by filtration, washed with water, and dried to give pure white 4.
．． 84.1 crystals of 4'-biphenyldicarboxylic acid
I got it. The purity of this crystal is 99.9% and the yield is 89.5
%Met.
［発明の効果］
以上述べたように、本発明は、粗４，４′ −ビフェ
ニルジ力ルポ多酸を４，４′ −ビフェニルジカルボ
ン酸塩の水溶液となし、次いで、該水溶液の濃縮および
／または４．４′ −ビフェニルジカルボン酸塩の溶
解度を下げる手段により４．４′ −ビフェニルジカ
ルボン酸塩を析出させ分離する工程を含んでなる４、４
′ −ビフェニルジカルボン酸の精製方法であるから
、高純度の４．４′ −ビフェニルジカルボン酸を高
収率で得ることができる。[Effects of the Invention] As described above, the present invention prepares crude 4,4'-biphenyl dicarboxylic acid into an aqueous solution of 4,4'-biphenyl dicarboxylate, and then concentrates and/or or 4,4 comprising a step of precipitating and separating 4.4'-biphenyl dicarboxylate by means of lowering the solubility of 4.4'-biphenyl dicarboxylate;
Since this is a method for purifying '-biphenyldicarboxylic acid, highly purified 4,4'-biphenyldicarboxylic acid can be obtained in high yield.
Claims (1)
）に示す４，４′−ビフェニルジカルボン酸塩の水溶液
となし、次いで、該水溶液の濃縮および／または４，４
′−ビフェニルジカルボン酸塩の溶解度を下げる手段に
より４，４′−ビフェニルジカルボン酸塩を析出させ分
離する工程を含むことを特徴とする４，４′−ビフェニ
ルジカルボン酸の精製法。 ▲数式、化学式、表等があります▼（ I ） （ただし、式中、ＸおよびＹはＬｉ、Ｎａ、Ｋ、Ｒｂま
たはＮＨ＿４を示し、ＸとＹは同一であっても、異なっ
てもよい）。[Claims] Crude 4,4'-biphenyldicarboxylic acid is prepared by the following formula (I
) of the 4,4'-biphenyldicarboxylic acid salt shown in Table 1.
1. A method for purifying 4,4'-biphenyldicarboxylic acid, comprising the step of precipitating and separating 4,4'-biphenyldicarboxylic acid salt by means of lowering the solubility of the 4,4'-biphenyldicarboxylic acid salt. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, in the formula, X and Y represent Li, Na, K, Rb, or NH_4, and X and Y may be the same or different.) .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18644288A JPH0737417B2 (en) | 1988-07-26 | 1988-07-26 | Method for purifying 4,4'-biphenyldicarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18644288A JPH0737417B2 (en) | 1988-07-26 | 1988-07-26 | Method for purifying 4,4'-biphenyldicarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0276837A true JPH0276837A (en) | 1990-03-16 |
| JPH0737417B2 JPH0737417B2 (en) | 1995-04-26 |
Family
ID=16188522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18644288A Expired - Lifetime JPH0737417B2 (en) | 1988-07-26 | 1988-07-26 | Method for purifying 4,4'-biphenyldicarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0737417B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002128729A (en) * | 2000-10-23 | 2002-05-09 | Nippon Steel Chem Co Ltd | Method for producing high-purity 4,4'- biphenyldicarboxylic acid |
| WO2012056544A1 (en) * | 2010-10-28 | 2012-05-03 | エア・ウォーター株式会社 | Production method for refined 6-bromo-2-naphthalenecarboxylic acid product |
-
1988
- 1988-07-26 JP JP18644288A patent/JPH0737417B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002128729A (en) * | 2000-10-23 | 2002-05-09 | Nippon Steel Chem Co Ltd | Method for producing high-purity 4,4'- biphenyldicarboxylic acid |
| WO2012056544A1 (en) * | 2010-10-28 | 2012-05-03 | エア・ウォーター株式会社 | Production method for refined 6-bromo-2-naphthalenecarboxylic acid product |
| CN103180284A (en) * | 2010-10-28 | 2013-06-26 | 爱沃特株式会社 | Production method for refined 6-bromo-2-naphthalenecarboxylic acid product |
| JP5613256B2 (en) * | 2010-10-28 | 2014-10-22 | エア・ウォーター株式会社 | Method for producing 6-bromo-2-naphthalenecarboxylic acid purified product |
| US8940931B2 (en) | 2010-10-28 | 2015-01-27 | Air Water Inc. | Production method for refined 6-bromo-2-naphthalenecarboxylic acid product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0737417B2 (en) | 1995-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5095390B2 (en) | Purification of carboxylic acids by complex formation using selective solvents. | |
| JPS5818332A (en) | Treatment of aromatic monocarboxylic acid reactant mixture | |
| JP2874223B2 (en) | Method for producing high-purity 2,6-naphthalene dicarboxylic acid | |
| JPH07118201A (en) | Purification of 2,6-naphthalene dicarboxylic acid | |
| JPH0276837A (en) | Method for purifying 4,4'-biphenyldicarboxylic acid | |
| JP2940155B2 (en) | Method for purifying 4,4'-biphenyldicarboxylic acid | |
| JPH07118200A (en) | Production of naphthalenedicarboxylic acid | |
| JPH01216955A (en) | Purification of 2-hydroxynaphthalene-6- carboxylic acid | |
| JP2664467B2 (en) | Purification method of biphenyldicarboxylic acid | |
| JP4626031B2 (en) | Method for producing high purity pyromellitic acid and high purity pyromellitic anhydride | |
| JPH0531535B2 (en) | ||
| JPH05194311A (en) | Purification of 4,4'-bisnaphthalic acid | |
| JPH04264050A (en) | Method for purifying 2,6-naphthalenedicarboxylic acid | |
| JP4183461B2 (en) | Process for producing 6-bromo-2-naphthalenecarboxylic acid | |
| JPH07206763A (en) | Production of purified 3,3',4,4',-biphenyltetracarboxylic acid or its acid dianhydride | |
| JPH0532586A (en) | Production of 2,6-naphthalenedicarboxylic acid | |
| JPH0733705A (en) | Purification of 2,6-naphtalenedicarboxylic acid | |
| JP3139175B2 (en) | Method for decolorizing recovered terephthalic acid | |
| US4317924A (en) | Process for producing purified terephthalic acid | |
| JP2917462B2 (en) | Method for purifying 4,4'-diphenyldicarboxylic acid | |
| JPH10273471A (en) | Production of furamic acid | |
| JPH06279355A (en) | Production of 2,6-naphthalene-dicarboxylic acid | |
| JPH02243652A (en) | Method for purifying naphthalenedicarboxylate | |
| JPH0769976A (en) | Method for purifying 4,4'-biphenyldicarboxylic acid | |
| JPH02160746A (en) | Production of 1-bromonaphthalene-2-carboxylic acid |