JPS63188647A - Production of bis(3-tert-butyl-4-hydroxyphenyl)acetic acids - Google Patents
Production of bis(3-tert-butyl-4-hydroxyphenyl)acetic acidsInfo
- Publication number
- JPS63188647A JPS63188647A JP62021167A JP2116787A JPS63188647A JP S63188647 A JPS63188647 A JP S63188647A JP 62021167 A JP62021167 A JP 62021167A JP 2116787 A JP2116787 A JP 2116787A JP S63188647 A JPS63188647 A JP S63188647A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- tert
- butyl
- formula
- hydroxyphenyl
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- QUHBECTVXQMROA-UHFFFAOYSA-N 2,2-bis(3-tert-butyl-4-hydroxyphenyl)acetic acid Chemical class C1=C(O)C(C(C)(C)C)=CC(C(C(O)=O)C=2C=C(C(O)=CC=2)C(C)(C)C)=C1 QUHBECTVXQMROA-UHFFFAOYSA-N 0.000 title description 7
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 9
- 239000011707 mineral Substances 0.000 claims abstract description 9
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical class CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims abstract description 4
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims abstract description 3
- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical class OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000047 product Substances 0.000 abstract description 8
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 abstract description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 235000011054 acetic acid Nutrition 0.000 description 7
- YKROJXPZFTZLDK-UHFFFAOYSA-N 2,2-bis(3,5-ditert-butyl-4-hydroxyphenyl)acetic acid Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(C(O)=O)C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 YKROJXPZFTZLDK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- -1 ethyl Bis(3,5-ditertiary-butyl-4-hydroxyphenyl)acetic acid Chemical compound 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
本発明はビス（３−ターシャリーブチル−４−ヒドロキ
シフェニル）酢酸類を工業的に製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a method for industrially producing bis(3-tert-butyl-4-hydroxyphenyl)acetic acids.
［従来の技術１
ビス（３，５−ジターシャリ−ブチル−４−ヒドロキシ
フェニル）酢酸、あるいはビス（３−ターシャリーブチ
ル−４−ヒドロキシフェニル）酢酸は農業、医薬の原料
として有用な化合物であり、その製造法としてはジクロ
ル酢酸を出発原料とする方法が知られている。[Prior art 1 Bis(3,5-ditertiary-butyl-4-hydroxyphenyl)acetic acid or bis(3-tertiarybutyl-4-hydroxyphenyl)acetic acid is a compound useful as a raw material for agriculture and medicine, As a method for producing it, a method using dichloroacetic acid as a starting material is known.
［発明が解決しようとする問題点１
しかし、かかる方法では目的物の収率が低く、工業的規
模での実施に当っては、更に高収率で目的物が製造可能
な方法の開発が要望される、
［問題点を解決するための手段］
本発明者等は鋭意研究を重ねた結果、グリオキシル酸と
２．６−；／ターシャリーブチル７エ／−ル、あるいは
２−ターシャリ−ブチル７エ７−ルとをグリオキシル酸
に対し、０．０１〜０．２倍モルの鉱酸及び１０〜３０
倍モルの脂肪族カルボン酸の存在下で反応させる場合、
収率良＜ビス（３，５−ジターシャリ−ブチル−４−ヒ
ドロキシフェニル）酢酸、あるいはビス（３−ターシャ
リーブチル−４−ヒドロキシフェニル）酢酸が製造でき
ることを見出し、本発明を完成するに到った。[Problem to be solved by the invention 1 However, this method has a low yield of the target product, and when implemented on an industrial scale, there is a need to develop a method that can produce the target product with an even higher yield.] [Means for Solving the Problems] As a result of intensive research, the present inventors have found that glyoxylic acid and 2.6-; mineral acid in an amount of 0.01 to 0.2 times the mole of glyoxylic acid and 10 to 30 times
When reacting in the presence of twice the molar amount of aliphatic carboxylic acid,
It was discovered that bis(3,5-ditertiary-butyl-4-hydroxyphenyl)acetic acid or bis(3-tert-butyl-4-hydroxyphenyl)acetic acid can be produced in good yield, and the present invention was completed. Ta.
本発明を反応式で示せば、
あるいは
である。［但し、ｔ−Ｂｕはターシャリ−ブチル基］以
下、本発明の方法を具体的に説明する。If the present invention is represented by a reaction formula, it is or. [However, t-Bu is a tertiary-butyl group] The method of the present invention will be specifically explained below.
尚、２，６−ターシャリーブチルフェノール及び２−タ
ーシャリープチルフェノールを単にフェノールと略記す
る。In addition, 2,6-tert-butylphenol and 2-tert-butylphenol are simply abbreviated as phenol.
本発明の方法においては、
１、グリオキシル酸１モルに対してフェノールを２モル
以上反応させること。In the method of the present invention, 1. 1 mole of glyoxylic acid is reacted with 2 moles or more of phenol.
２、反応時にグリオキシル酸に対して０．０１〜０．２
倍モル、好ましくは０．１〜０．２倍モルの鉱酸及び１
（）〜３０倍モルの脂肪族カルボン酸を共存させること
が必要であり、かかる反応条件によって目的物が８５％
以上という極めて高収率で得られる。2. 0.01 to 0.2 to glyoxylic acid during reaction
twice the mole, preferably 0.1 to 0.2 times the mole of mineral acid and 1
It is necessary to coexist 30 times the molar amount of aliphatic carboxylic acid, and under these reaction conditions, 85% of the target product
It can be obtained in an extremely high yield.
フェノールはグリオキシル酸１モルに対して量論上、２
モル以上必要で、通常２〜２．５モルの範囲で使用すれ
ば充分である。２．５モル以上の使用は経済的に不利で
ある。The stoichiometric ratio of phenol to 1 mole of glyoxylic acid is 2
A mole or more is required, and it is usually sufficient to use it in a range of 2 to 2.5 moles. Use of 2.5 mol or more is economically disadvantageous.
又、反応時にはグリオキシル酸に対して０．０１〜０゜
２倍モルの鉱酸を共存させることが必要である。かがる
範囲外では副生物が生成して収率が低下する。鉱酸とし
ては硫酸、リン酸、塩酸等が例示されるが硫酸が好適に
使用される。Further, during the reaction, it is necessary to coexist a mineral acid in an amount of 0.01 to 0.2 times the mole of glyoxylic acid. Outside the range, by-products are produced and the yield is reduced. Examples of mineral acids include sulfuric acid, phosphoric acid, and hydrochloric acid, and sulfuric acid is preferably used.
更に反応時にグリオキシル酸に対して１０〜３０倍モル
好ましくは１０〜２０モルの脂肪族カルボン酸を共存さ
せる。Furthermore, during the reaction, an aliphatic carboxylic acid is allowed to coexist in an amount of 10 to 30 times the mole of glyoxylic acid, preferably 10 to 20 moles.
１０倍モル以下では、反応系が二層分離して反応が進行
せず、一方３０倍モル以上では反応速度の低下、容積効
率の低下のため、実用性に乏しい。If it is less than 10 times the molar amount, the reaction system will separate into two layers and the reaction will not proceed, while if it is more than 30 times the molar amount, the reaction rate will decrease and the volumetric efficiency will decrease, resulting in poor practicality.
脂肪族カルボン酸としては蟻酸、酢酸、プロピオン酸、
トリフロロ酢酸等が例示され、酢酸の使用が特に好まし
い。Aliphatic carboxylic acids include formic acid, acetic acid, propionic acid,
Examples include trifluoroacetic acid, and acetic acid is particularly preferred.
反応に当ってはグリオキシル酸、７エ／−ル、鉱酸、カ
ルボン酸を所定量混合し、加熱すれば良い。反応温度は
４０℃以上、好ましくは６０〜９０ ’Ｃ１反応時間は
７〜５０時間が必要である。かかる試薬の供給は連続、
分割、一括、いずれの方式で実施しても良い。グリオキ
シル酸は通常市販されている４０〜５０％濃度の水溶液
がそのまま使用出来るが、それの濃縮物及び結晶状物も
使用可能である。反応は通常水溶媒中で実施されるが、
水と相溶性の良好な有機溶媒を添加して実施することら
勿論可能である。For the reaction, predetermined amounts of glyoxylic acid, 7 ethanol, mineral acid, and carboxylic acid may be mixed and heated. The reaction temperature is 40°C or higher, preferably 60-90'C1 reaction time is 7-50 hours. The supply of such reagents is continuous;
It may be carried out either by division or all at once. Glyoxylic acid can be used as it is as a commercially available 40-50% aqueous solution, but its concentrates and crystals can also be used. The reaction is usually carried out in an aqueous medium,
Of course, this can be carried out by adding an organic solvent having good compatibility with water.
反応が終了すれば、析出したビス（３−ターシャリーブ
チル−４−ヒドロキシフェニル）酢酸類をｒ別する。When the reaction is completed, the precipitated bis(3-tert-butyl-4-hydroxyphenyl)acetic acid is separated.
必要に応じて活性炭処理、再結晶等の精製繰作を実施す
れば品質が一層向上する。If necessary, the quality will be further improved by performing purification operations such as activated carbon treatment and recrystallization.
［効 果１
本発明で得られるビス（３−ターシャリーブチル−４−
ヒドロキシフェニル）酢酸類は農薬、医薬等に有用であ
る。[Effect 1 Bis(3-tert-butyl-4-
Hydroxyphenyl)acetic acids are useful in agricultural chemicals, medicines, and the like.
［実施例］
次に実施例を挙げて本発明の方法を更に具体的に説明す
る。[Example] Next, the method of the present invention will be explained in more detail with reference to Examples.
実施例１
５０％グリオキシル酸水溶液７４部（０，５モル）に２
．６−ジターシャリ−ブチルフェノール２２６．６部（
１，１モル）を加え、更に酢酸３６０部（６モル）を加
えて均一溶液とし、８０°Ｃに加熱した。次に濃硫酸５
部（Ｏ，ＯＳモル）を添加して１０時間、８０’ｃで加
熱した。反応終了後、系を冷却し沈澱した目的物２６９
ｇを濾過し、１５０部の酢酸で洗浄した。Example 1 74 parts (0.5 mol) of 50% glyoxylic acid aqueous solution
．． 226.6 parts of 6-ditertiary-butylphenol (
Then, 360 parts (6 mol) of acetic acid was added to form a homogeneous solution, and the mixture was heated to 80°C. Next, concentrated sulfuric acid 5
(O, OS mol) was added and heated at 80'C for 10 hours. After the reaction was completed, the system was cooled and the desired product 269 precipitated.
g was filtered and washed with 150 parts of acetic acid.
該粗結晶をメタノール１．４００部に溶解し、次いで水
−１，０００部を加えて析出させ、精製した。The crude crystals were dissolved in 1.400 parts of methanol, and then 1,000 parts of water was added to precipitate and purify.
得られた結晶の融点は２１２℃であり、文献値と一致し
ビス （３，５−ジターシャリ−ブチル−４−ヒドロキ
シフェニル）酢酸であることを確認した。The melting point of the obtained crystals was 212°C, which agreed with the literature value, and was confirmed to be bis(3,5-ditertiary-butyl-4-hydroxyphenyl)acetic acid.
収率はグリオキシル酸に対して９２％であった。The yield was 92% based on glyoxylic acid.
実施例２
硫酸の使用量を１０部（０，１０モル）に変更した以外
は実施例１と同一の方法を行った。Example 2 The same method as Example 1 was carried out except that the amount of sulfuric acid used was changed to 10 parts (0.10 mol).
目的物の収率は９１％であった。The yield of the target product was 91%.
実施例３〜４
酢酸の使用量を４８０部（８モル）（実施例３）、及プ
６００部（１０モル）（実施例４）に変更した以外は、
実施例１と同一の方法を行った。Examples 3-4 Except that the amount of acetic acid used was changed to 480 parts (8 mol) (Example 3) and 600 parts (10 mol) (Example 4),
The same method as in Example 1 was carried out.
目的物の収率は、実施例３が９１％、実施例４が９０％
であった。The yield of the target product was 91% in Example 3 and 90% in Example 4.
Met.
対照例１
実施例１において酢酸の使用量を１５０部（２，５モル
）に変更した以外は同じ方法を行ったところ、反応系は
二層になり反応が進みに＜＜、収率も３６％であった。Comparative Example 1 When the same method as in Example 1 was carried out except that the amount of acetic acid used was changed to 150 parts (2.5 mol), the reaction system formed two layers and the reaction proceeded <<, and the yield was 36. %Met.
対照例２
実施例１において硫酸の使用量を５０部（０，５モル）
に変更した以外は実施例１と同一の方法を行ったところ
、得られる目的物は黄色に着色していた。融点も２０８
°Ｃと低く、収率も７３％に過ぎなかった。Comparative Example 2 The amount of sulfuric acid used in Example 1 was 50 parts (0.5 mol).
When the same method as in Example 1 was carried out except for the following changes, the obtained target product was colored yellow. The melting point is also 208
The yield was only 73%.
実施例５
２．６−ジターシャリ−ブチルフェノールに代えて２−
ターシャリ−ブチル７エ７−ルを用いた以外は実施例１
と同一の方法を行ったところ、ビス（３−ターシャリー
ブチル−４−ヒドロキシフェニル）酢酸が収率８５％で
得られた。Example 5 2- in place of 2.6-di-tert-butylphenol
Example 1 except that tert-butyl 7-er was used.
When the same method as above was carried out, bis(3-tert-butyl-4-hydroxyphenyl)acetic acid was obtained in a yield of 85%.
［発明の効果］
本発明においては、鉱酸及びカルボン酸を特定範囲の量
、共存させることにより、グリオキシル酸と２，６−ジ
ターシャリ−ブチルフェノール、あるいは２−ターシャ
リ−ブチル７エ／−ルから収率良くビス（３，５−ジタ
ーシャリ−ブチル−４−ヒドロキシフェニル）酢酸、あ
るいはビス（３−ジターシャリ−ブチル−４−ヒドロキ
シフェニル）酢酸が製造出来る。[Effects of the Invention] In the present invention, by allowing mineral acids and carboxylic acids to coexist in specific ranges of amounts, glyoxylic acid and 2,6-di-tert-butylphenol or 2-tert-butyl 7 ethyl Bis(3,5-ditertiary-butyl-4-hydroxyphenyl)acetic acid or bis(3-ditertiary-butyl-4-hydroxyphenyl)acetic acid can be produced with good efficiency.
Claims (1)
ール又は２−ターシャリーブチルフェノールとをグリオ
キシル酸に対し０．０１〜０．２倍モルの鉱酸及び１０
〜３０倍モルの脂肪族カルボン酸の存在下で反応させる
ことを特徴とするビス（３−ターシャリーブチル−４−
ヒドロキシフェニル）酢酸類の製造方法。Glyoxylic acid and 2,6-di-tert-butylphenol or 2-tert-butylphenol in a molar amount of 0.01 to 0.2 times the amount of mineral acid and 10
Bis(3-tert-butyl-4-
Method for producing (hydroxyphenyl)acetic acids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62021167A JPS63188647A (en) | 1987-01-30 | 1987-01-30 | Production of bis(3-tert-butyl-4-hydroxyphenyl)acetic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62021167A JPS63188647A (en) | 1987-01-30 | 1987-01-30 | Production of bis(3-tert-butyl-4-hydroxyphenyl)acetic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63188647A true JPS63188647A (en) | 1988-08-04 |
Family
ID=12047356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62021167A Pending JPS63188647A (en) | 1987-01-30 | 1987-01-30 | Production of bis(3-tert-butyl-4-hydroxyphenyl)acetic acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63188647A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0281020A (en) * | 1988-09-19 | 1990-03-22 | Canon Inc | Variable-power optical system with vibration-proof function |
| WO2006059903A1 (en) * | 2004-12-02 | 2006-06-08 | Dsm Ip Assets B.V. | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound |
| JP2009538942A (en) * | 2006-06-02 | 2009-11-12 | ディーエスエム アイピー アセッツ ビー．ブイ． | Method for preparing hydroxy aromatic resin, hydroxy aromatic resin, and modification thereof |
| JP2009538943A (en) * | 2006-06-02 | 2009-11-12 | ディーエスエム アイピー アセッツ ビー．ブイ． | Method for preparing hydroxy aromatic resin, hydroxy aromatic resin, and modification thereof |
-
1987
- 1987-01-30 JP JP62021167A patent/JPS63188647A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0281020A (en) * | 1988-09-19 | 1990-03-22 | Canon Inc | Variable-power optical system with vibration-proof function |
| WO2006059903A1 (en) * | 2004-12-02 | 2006-06-08 | Dsm Ip Assets B.V. | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound |
| US7678876B2 (en) | 2004-12-02 | 2010-03-16 | Dsm Ip Assets B.V. | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound |
| JP2009538942A (en) * | 2006-06-02 | 2009-11-12 | ディーエスエム アイピー アセッツ ビー．ブイ． | Method for preparing hydroxy aromatic resin, hydroxy aromatic resin, and modification thereof |
| JP2009538943A (en) * | 2006-06-02 | 2009-11-12 | ディーエスエム アイピー アセッツ ビー．ブイ． | Method for preparing hydroxy aromatic resin, hydroxy aromatic resin, and modification thereof |
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