JPS6113451B2 - - Google Patents
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- Publication number
- JPS6113451B2 JPS6113451B2 JP8605777A JP8605777A JPS6113451B2 JP S6113451 B2 JPS6113451 B2 JP S6113451B2 JP 8605777 A JP8605777 A JP 8605777A JP 8605777 A JP8605777 A JP 8605777A JP S6113451 B2 JPS6113451 B2 JP S6113451B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- biphenol
- parts
- aqueous solution
- formula
- 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.)
- Expired
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- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000005749 Copper compound Substances 0.000 claims 1
- 150000001880 copper compounds Chemical class 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 9
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 Cul Inorganic materials 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910016509 CuF 2 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、ｐ・p′−ビフエノールの製造に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of p.p'-biphenol.
本発明に係るｐ・p′−ビフエノールは、安定
剤、染料中間体およびポリエステル、ポリエポキ
サイド、ポリウレタンまはポリカーボネートなど
の樹脂製造原料として有用であり、特に最近、耐
熱性樹脂向けの原料として注目されている。従来
行なわれた、ｐ・p′−ビフエノールの製造法は、
初めはベンチジンをジアゾ分解し製造された〔ド
イツ化学会報告（Chemische Berichte）22、
335〕。その後、ｐ・p′−ビフエニルジスルホン酸
ナトリウムのアルカリ熔融により製造されている
〔米国特許第2368361号（1942）〕。しかし前者は、
有害なベンチジンを使用するため工業化は不可能
であり、後者は、スルホン化工程の排水処理の点
から工業化には問題がある。またハロゲン化ビフ
エニルを出発原料とする方法については、ｐ・
p′−ジクロルビフエニルを、CuO−SiO2存在下
に526〜600℃で加水分解する方法〔米国特許第
1925367号（1930）〕、ｐ・p′−ジプロムビフエニ
ルを湿性AgOの存在下に加水分解する方法〔結
晶と鉱物学雑誌（Zeitschrift fiir
Krystallographie and Mineralogie）55、77、註
２〕が知られているが、これらの方法は、両者共
に気相で反応を行うため工業化に当つて装置の材
質その他において問題がある。またAgO触媒を
用いる反応については、高価な触媒の使用のため
製造原価の上昇が考えられ、適当な方法といえな
い。さらに両者の方法は、高温で反応を行なうた
め異性化および副生物による純度および収率の低
下があり、工業化は問題である。 The p/p'-biphenol according to the present invention is useful as a stabilizer, a dye intermediate, and a raw material for producing resins such as polyester, polyepoxide, polyurethane, or polycarbonate, and has recently attracted attention as a raw material for heat-resistant resins. ing. The conventional method for producing p・p′-biphenol is as follows:
It was first produced by diazolysis of benzidine [Report of the German Chemical Society (Chemische Berichte) 22 ,
335]. Thereafter, it was produced by alkaline melting of sodium p.p'-biphenyldisulfonate [US Pat. No. 2,368,361 (1942)]. However, the former
Industrialization is impossible due to the use of harmful benzidine, and the latter has problems in industrialization from the point of view of wastewater treatment in the sulfonation process. Regarding the method using halogenated biphenyl as a starting material, p.
A method of hydrolyzing p'-dichlorobiphenyl at 526-600°C in the presence of CuO- SiO2 [U.S. Patent No.
No. 1925367 (1930)], Method for the hydrolysis of p.p'-diprombiphenyl in the presence of wet AgO [Crystal and Mineralogy Journal (Zeitschrift fiir
Krystallographie and Mineralogie) 55 , 77, note 2] are known, but since both of these methods carry out the reaction in the gas phase, there are problems with the material of the equipment and other issues when industrializing them. Furthermore, the reaction using an AgO catalyst is not considered to be an appropriate method because the production cost is likely to increase due to the use of an expensive catalyst. Furthermore, both methods involve a reduction in purity and yield due to isomerization and by-products since the reaction is carried out at high temperatures, making industrialization problematic.
本発明者ら、上記従来法の欠点を解決するた
め、廉価な触媒を用い、単純な設備で、高純度の
ｐ・p′−ビフエノールを得ることを目的に検討
し、廉価な銅化合物系触媒を用い、200〜300℃と
比較的低温で、しかも異性化せずに、高純度、高
収率で目的のｐ・p′−ビフエノールを製造できる
ことを見出し、本発明方法を完成した。 In order to solve the above-mentioned drawbacks of the conventional method, the present inventors conducted an investigation with the aim of obtaining high-purity p,p'-biphenol using an inexpensive catalyst and simple equipment. It was discovered that the desired p·p'-biphenol could be produced in high purity and yield at a relatively low temperature of 200 to 300°C without isomerization using the method, and the method of the present invention was completed.
すなわち、本発明は、ｐ・p′−ジハロゲン化ビ
フエニルをCuoRn（式中Ｒは、−OH基、酸素原
子、ハロゲン原子を示し、ｎおよびｍは、１また
は２の整数を示す。）で示される銅化合物系触媒
の存在下に、200〜300℃の温度で加圧下にアルカ
リ金属およびまたはアルカリ土類金属水酸化物の
水溶液または懸濁液と反応させることを特徴とす
るｐ・p′−ビフエノールの製造法である。 That is, the present invention provides p.p'-dihalogenated biphenyl as Cu o R n (wherein R represents an -OH group, an oxygen atom, or a halogen atom, and n and m represent an integer of 1 or 2). ) is reacted with an aqueous solution or suspension of an alkali metal and/or alkaline earth metal hydroxide under pressure at a temperature of 200 to 300°C. This is a method for producing p'-biphenol.
本発明の出発物質であるｐ・p′−ジハロゲン化
ビフエニルは、たとえばｐ・p′−ジクロルビフエ
ニル、ｐ・p′−ジプロムビフエニル、ｐ−ブロム
−p′−クロルビフエニルなどである。 The p·p'-dihalogenated biphenyl which is the starting material of the present invention is, for example, p·p'-dichlorobiphenyl, p·p'-diprombiphenyl, p-bromo-p'-chlorbiphenyl and the like.
これらのものは粉末または固体としてそのまま
使用される。本発明の加水分解触媒としては、
CuO、Cu2O、CuCl、CuCl2、CuBr、CuBr2、
Cul、CuF、CuF2・2H2O、Cu（OH）2などであ
り、それぞれ単独、または混合物、たとえば、
CuOとCu2Oとの混合物を使用することができ
る。使用量は、ｐ・p′−ジハロゲン化ビフエニル
に対して、0.1〜10.0モル％で、好ましくは2.0〜
7.0モル％である。 These materials are used directly as powders or solids. The hydrolysis catalyst of the present invention includes:
CuO, Cu2O , CuCl, CuCl2 , CuBr, CuBr2 ,
Cul, CuF, CuF 2 2H 2 O, Cu(OH) 2 , etc., each alone or in a mixture, for example,
Mixtures of CuO and Cu2O can be used. The amount used is 0.1 to 10.0 mol%, preferably 2.0 to 10.0 mol%, based on p・p′-dihalogenated biphenyl.
It is 7.0 mol%.
アルカリ金属またはアルカリ土類金属水酸化物
としては、NaOH、KOH、Ca（OH）2、Mg
（OH）2等が使用され、好ましくはNaOHおよび
KOHで、出発物質のハロゲン原子に対して、2.0
〜3.0当量使用する。NaOHおよびKOHなどは水
によく溶け水溶液として使用できるが、Ca
（OH）2、Mg（OH）2などは水に難溶性であり、懸
濁液として使用することができる。もちろん、こ
れらは単独または混合物として使用できる。 Alkali metal or alkaline earth metal hydroxides include NaOH, KOH, Ca(OH) 2 , Mg
(OH) 2 etc. are used, preferably NaOH and
In KOH, 2.0 for the halogen atom of the starting material
~3.0 equivalents are used. NaOH and KOH etc. dissolve well in water and can be used as an aqueous solution, but Ca
(OH) 2 , Mg(OH) 2 , etc. are sparingly soluble in water and can be used as a suspension. Of course, these can be used alone or as a mixture.
反応温度は、200〜300℃で一般には230〜280℃
が好ましい。 The reaction temperature is 200-300℃, generally 230-280℃
is preferred.
この温度を保つため密封容器内で加圧下に反応
させることとなる。たとえば、10％NaOH水溶液
を使用した場合約40気圧の圧力となる。 In order to maintain this temperature, the reaction is carried out under pressure in a sealed container. For example, if a 10% NaOH aqueous solution is used, the pressure will be approximately 40 atmospheres.
反応の実施に当つて、撹拌効率は、大きな反応
条件因子となるため、良好な撹拌状態にしておく
ことが必要である。またｐ・p′−ビフエノールの
着色を防止するため、オートクレープの空間は、
窒素雰囲気下で行うことが望ましい。 In carrying out the reaction, the stirring efficiency is a major factor in the reaction conditions, so it is necessary to maintain a good stirring state. In addition, in order to prevent p・p'-biphenol from coloring, the autoclave space is
It is desirable to carry out under a nitrogen atmosphere.
反応時間は、個々の反応条件に左右されるの
で、それらの条件に見合つた反応時間を選択する
のが好ましい。 Since the reaction time depends on individual reaction conditions, it is preferable to select a reaction time that is compatible with those conditions.
以下実施例をあげて本発明を説明する。文中部
とあるのは重量部を表わす。 The present invention will be explained below with reference to Examples. The term "part of the sentence" indicates the part by weight.
実施例 １
10.0部のｐ・p′−ジブロムビフエニル、64.1部
の10％NaOH水溶液および0.17部の亜酸化銅粉末
を、0.1のオートクレーブの中に仕込み、密閉
して空間の空気を窒素に置換したのち昇温し、
250℃３時間反応させた。次にオートクレーブを
室温まで冷却し、反応物を取り出す。反応物は
過をして触媒の亜酸化銅および未反応ｐ・p′−ジ
ブロムビフエニルの少量とを分離し、液のアル
カリ水層を、濃HClで酸性（PH≒1.0）にして析
出した白色結晶を別、水洗して乾燥することに
より目的のｐ・p′−ビフエノール5.5ｇ（収率
92.2％、融点276〜280℃）を得た。Example 1 10.0 parts of p・p'-dibromubiphenyl, 64.1 parts of 10% NaOH aqueous solution, and 0.17 parts of cuprous oxide powder were placed in a 0.1 part autoclave, the autoclave was sealed, and the air in the space was replaced with nitrogen. After replacing, the temperature is raised,
The reaction was carried out at 250°C for 3 hours. The autoclave is then cooled to room temperature and the reactants are removed. The reaction product is separated from the catalyst cuprous oxide and a small amount of unreacted p, p'-dibrombiphenyl, and the alkaline aqueous layer of the liquid is acidified (PH≒1.0) with concentrated HCl to precipitate. Separately, the white crystals were washed with water and dried to obtain 5.5 g of the desired p-p'-biphenol (yield:
92.2%, melting point 276-280°C).
実施例 ２
10.0部のｐ・p′−ジブロムビフエニル、64.1部
の10％NaOH水溶液および0.34部の塩化第２銅
を、0.1のオートクレーブに仕込み、実施例１
と同様に反応を行つた結果、目的のｐ・p′−ビフ
エノール5.4部（収率90.5％、融点275〜280℃）
を得た。Example 2 10.0 parts of p・p′-dibromubiphenyl, 64.1 parts of 10% NaOH aqueous solution and 0.34 parts of cupric chloride were charged into a 0.1 autoclave.
As a result of carrying out the reaction in the same manner as above, 5.4 parts of the target p・p'-biphenol (yield 90.5%, melting point 275-280℃) was obtained.
I got it.
実施例 ３
10.0部のｐ・p′−ジブロムビフエニル、64.1部
の10％KOH水溶液および0.19部の酸化銅を、0.1
のオートクレーブの中に仕込み、密閉して、空
間の空気を窒素に置換したのち昇温し、230℃で
８時間反応させた。反応液は実施例１と同様に処
理して、目的のｐ・p′−ビフエノール5.4部（収
率90.5％、融点276〜280℃）を得た。Example 3 10.0 parts of p.p'-dibromubiphenyl, 64.1 parts of a 10% KOH aqueous solution and 0.19 parts of copper oxide were added to 0.1
The autoclave was sealed, the air in the space was replaced with nitrogen, the temperature was raised, and the reaction was carried out at 230°C for 8 hours. The reaction solution was treated in the same manner as in Example 1 to obtain 5.4 parts of the target p·p'-biphenol (yield 90.5%, melting point 276-280°C).
実施例 ４
11.2部のｐ・p′−ジクロルビフエニル、50.0部
の20％NaOH水溶液および0.5部の亜酸化銅を、
0.1のオートクレーブの中に仕込み、密閉し
て、空間の空気を窒素に置換したのち、昇温し
275℃、３時間反応させた。反応液は実施例１と
同様に処理して、目的のｐ・p′−ビフエノール
8.6部（収率92.4％、融点276〜280℃）を得た。Example 4 11.2 parts of p.p'-dichlorobiphenyl, 50.0 parts of 20% NaOH aqueous solution and 0.5 parts of cuprous oxide,
0.1 in an autoclave, seal it, replace the air in the space with nitrogen, and then raise the temperature.
The reaction was carried out at 275°C for 3 hours. The reaction solution was treated in the same manner as in Example 1 to obtain the target p,p'-biphenol.
8.6 parts (yield 92.4%, melting point 276-280°C) were obtained.
Claims (1)
たは異種のものを示す。）で表わされるｐ・p′−
ジハロゲン化ビフエニルを 一般式 CuoRn （式中Ｒは、−OH基、酸素原子、ハロゲン原子を
示し、ｎおよびｍは１または２の整数を示す。）
で表わされる銅化合物系触媒の存在下に、アルカ
リ金属およびまたはアルカリ土類金属水酸化物の
水溶液あるいは懸濁液と加圧下に反応させること
を特徴とするｐ・p′−ビフエノールの製造法。[Claims] 1. General formula (In the formula, X 1 and X 2 represent halogen atoms, and are the same or different.)
Dihalogenated biphenyl has the general formula Cu o R n (wherein R represents an -OH group, an oxygen atom, or a halogen atom, and n and m represent an integer of 1 or 2.)
A method for producing p/p'-biphenol, which comprises reacting it with an aqueous solution or suspension of an alkali metal and/or alkaline earth metal hydroxide under pressure in the presence of a copper compound catalyst represented by the formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8605777A JPS5422347A (en) | 1977-07-20 | 1977-07-20 | Preparation of p,p'-diphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8605777A JPS5422347A (en) | 1977-07-20 | 1977-07-20 | Preparation of p,p'-diphenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5422347A JPS5422347A (en) | 1979-02-20 |
| JPS6113451B2 true JPS6113451B2 (en) | 1986-04-14 |
Family
ID=13876055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8605777A Granted JPS5422347A (en) | 1977-07-20 | 1977-07-20 | Preparation of p,p'-diphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5422347A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4475000A (en) * | 1983-01-21 | 1984-10-02 | Ethyl Corporation | Process for producing 4,4'-dihydroxybiphenyl |
| US4490564A (en) * | 1983-04-22 | 1984-12-25 | Ethyl Corporation | Mixed solvent recovery of 4,4'-dihydroxybiphenyl |
| JPS63178176A (en) * | 1987-01-19 | 1988-07-22 | Mitsubishi Pencil Co Ltd | Oil-based ink composition |
| FR2609711B1 (en) * | 1987-01-21 | 1989-06-16 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF HYDROXYBIPHENYLES |
| FR2610924B1 (en) * | 1987-02-12 | 1990-05-04 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF HYDROXYBIPHENYLES |
| US4873374A (en) * | 1987-04-14 | 1989-10-10 | Mitsui Toatsu Chemicals, Incorporated | Preparation process of 4,4'-biphenol, precursor of same and preparation process of precursor |
-
1977
- 1977-07-20 JP JP8605777A patent/JPS5422347A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5422347A (en) | 1979-02-20 |
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