JPH045254A - Production of 4,4'-dihydroxydiphenyl ethers - Google Patents
Production of 4,4'-dihydroxydiphenyl ethersInfo
- Publication number
- JPH045254A JPH045254A JP2107756A JP10775690A JPH045254A JP H045254 A JPH045254 A JP H045254A JP 2107756 A JP2107756 A JP 2107756A JP 10775690 A JP10775690 A JP 10775690A JP H045254 A JPH045254 A JP H045254A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- hydroquinone
- compound
- heteropolyacid
- 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
- -1 4,4'-dihydroxydiphenyl ethers Chemical class 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000013078 crystal Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006471 dimerization reaction Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 239000011541 reaction mixture Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 150000002170 ethers Chemical class 0.000 description 9
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VJIDDJAKLVOBSE-UHFFFAOYSA-N 2-ethylbenzene-1,4-diol Chemical compound CCC1=CC(O)=CC=C1O VJIDDJAKLVOBSE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- GPASWZHHWPVSRG-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C)C=C1O GPASWZHHWPVSRG-UHFFFAOYSA-N 0.000 description 1
- HIGSPBFIOSHWQG-UHFFFAOYSA-N 2-Isopropyl-1,4-benzenediol Chemical compound CC(C)C1=CC(O)=CC=C1O HIGSPBFIOSHWQG-UHFFFAOYSA-N 0.000 description 1
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- 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）
本発明は、耐熱性ポリマー原料として有用な４．４′−
ジヒドロキシジフェニルエーテル類を製造する方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides 4.4'-
The present invention relates to a method for producing dihydroxydiphenyl ethers.
（従来の技術）
従来、ヒドロキノン類の脱水二量化によって、４．４′
−ジヒドロキシジフェニルエーテル類を得る方法におい
て、触媒として、■スルホン酸または硫酸を用いた例（
独国特許第３５３２８８１号公報、特公昭６０−４３０
５２号公報）、■スルホン酸基含有スチレンービニルベ
ンセン共重合体等からなるイオン交換樹脂を用いた例（
米国特許第４，３０６，０９４号公報）などが知られて
いる。(Prior art) Conventionally, by dehydration dimerization of hydroquinones, 4.4'
- Example of using sulfonic acid or sulfuric acid as a catalyst in the method for obtaining dihydroxydiphenyl ethers (
German Patent No. 3532881, Special Publication No. 60-430
(No. 52), (1) Examples using ion exchange resins made of styrene-vinylbenzene copolymers containing sulfonic acid groups (
U.S. Pat. No. 4,306,094) and the like are known.
（発明が解決しようとする課題）
ところが、従来より提案されているいずれの製進法を用
いた場合でも、ヒドロキノン類の三量体や四量体が多く
生成するため、目的の４，４′ジヒドロキシジフエニル
エーテル類の選択率か低いという欠点がある。(Problem to be Solved by the Invention) However, when using any of the conventionally proposed production methods, many trimers and tetramers of hydroquinones are produced, so that the desired 4,4' The drawback is that the selectivity of dihydroxydiphenyl ethers is low.
４．４′−ジヒドロキシジフェニルエーテル類の選択性
を向上させる方法として、ヒドロキノンの転化率が低い
段階で反応を停止することも可能であるが、この場合に
は、１バツチあたりの収量が著しく低下するという問題
がある。4. As a method of improving the selectivity of 4'-dihydroxydiphenyl ethers, it is possible to stop the reaction at a stage when the conversion rate of hydroquinone is low, but in this case, the yield per batch decreases significantly. There is a problem.
さらに、上記のいずれの製造法においても、４．４′−
ジヒドロキシジフェニルエーテル類の高純度品を得るた
めには、別途再結晶や溶媒抽出等の操作によって、粗生
成物中の三量体や四量体を除去する必要がある。しかし
、別途このような精製工程をいれると製造工程全体が長
くなり、生産性そのものが低下するし、しかも目的とす
る４゜４′−ジヒドロキシジフェニルエーテル類の単離
収率が低下する等の問題が生じる。Furthermore, in any of the above production methods, 4.4'-
In order to obtain highly purified dihydroxydiphenyl ethers, it is necessary to separately remove trimers and tetramers from the crude product by operations such as recrystallization and solvent extraction. However, if such a separate purification step is included, the entire manufacturing process becomes longer and the productivity itself decreases, and furthermore, there are problems such as a decrease in the isolation yield of the target 4゜4'-dihydroxydiphenyl ethers. arise.
（課題を解決するための手段）
本発明者らは上記事情に鑑みて、検討した結果、触媒と
して、ヘテロポリ酸またはその酸性金属塩を用いると、
４． ４’ −ジヒドロキシジフェニルエーテル類の選
択性が高く、反応後の後処理が簡便であることを見い出
し、本発明を完成するに至った。(Means for Solving the Problems) In view of the above circumstances, the present inventors investigated and found that when a heteropolyacid or an acidic metal salt thereof is used as a catalyst,
4. The present inventors discovered that 4'-dihydroxydiphenyl ethers have high selectivity and that post-reaction treatment is simple, leading to the completion of the present invention.
すなわち、本発明は、ヒドロキノン類を、触媒の存在下
、溶媒中で脱水二量化する４、４′ −ジヒドロキシジ
フェニルエーテル類の製造法において、触媒として、ヘ
テロポリ酸またはその酸性金属塩を用いることを特徴と
する４、４′ −ジヒドロキシジフェニルエーテル類の
製造法を提供するものである。That is, the present invention is characterized in that a method for producing 4,4'-dihydroxydiphenyl ethers in which hydroquinones are dehydrated and dimerized in a solvent in the presence of a catalyst uses a heteropolyacid or an acidic metal salt thereof as a catalyst. The present invention provides a method for producing 4,4'-dihydroxydiphenyl ethers.
以下、本発明の４，４′ −ジヒドロキシジフェニルエ
ーテル類の製造法について詳しく説明する。Hereinafter, the method for producing 4,4'-dihydroxydiphenyl ethers of the present invention will be explained in detail.
本発明に用いられる原料のヒドロキノン類としては、例
えばヒドロキノン、メチルヒドロキノン、２．５−ジメ
チルヒドロキノン、トリメチルヒドロキノン、エチルヒ
ドロキノン、イソプロピルヒドロキノン、ｎ−ブチルヒ
ドロキノンなどを挙げることができる。Examples of hydroquinones used as raw materials in the present invention include hydroquinone, methylhydroquinone, 2,5-dimethylhydroquinone, trimethylhydroquinone, ethylhydroquinone, isopropylhydroquinone, and n-butylhydroquinone.
また、本発明において触媒として使用されるヘテロポリ
酸およびその酸性金属塩としては、例えばヘテロポリタ
ングステン酸およびその酸性金属塩、ヘテＤポリモリブ
デン酸およびその酸性金属塩等が挙げられ、なかでもリ
ンまたはケイ素を中心原子とするものが好ましい。酸性
金属塩として好適に使用される金属としては、ナトリウ
ム、カリウム等のアルカリ金属、マグネシウム等のアル
カリ土類金属、銅、亜鉛、カドミウム、アルミニウム等
が挙げられる。In addition, examples of the heteropolyacid and acidic metal salt thereof used as a catalyst in the present invention include heteropolytungstic acid and its acidic metal salt, heteropolymolybdic acid and its acidic metal salt, etc. Among them, phosphorus or silicon Preferably, the central atom is . Examples of metals suitably used as acidic metal salts include alkali metals such as sodium and potassium, alkaline earth metals such as magnesium, copper, zinc, cadmium, and aluminum.
これらの化合物の中で、４，４′ −ジヒドロキシジフ
ェニルエーテル類の選択率だけでな（、転化率および収
率も高い点でケイタングステン酸およびリンタングステ
ン酸が特に好ましい。Among these compounds, silicotungstic acid and phosphotungstic acid are particularly preferred because they not only have a high selectivity for 4,4'-dihydroxydiphenyl ethers (but also a high conversion rate and yield).
触媒の使用量は、原料のヒドロキノン類１００重量部に
対して、通常１〜５０重量部であり、好適には５〜２０
重量部である。The amount of the catalyst used is usually 1 to 50 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the raw material hydroquinone.
Parts by weight.
触媒は、そのまま反応系に加えても良く、また活性炭や
アルミナ−シリカ等に担持した状態で加えても良い。The catalyst may be added to the reaction system as it is, or may be added in a state supported on activated carbon, alumina-silica, or the like.
本発明で使用される溶媒は、特に制限されないが、原料
のヒドロキノン類と生成物の４．４′ジヒドロ牛シジフ
エニルエーテル類の溶解度差が大きなものが適しており
、ベンゼン、トルエン、キシレン、キュメン、メシチレ
ン等の芳香族炭化水素が好ましく、なかでもキュメンが
特に好適である。The solvent used in the present invention is not particularly limited, but it is suitable that there is a large difference in solubility between the raw material hydroquinones and the product 4,4' dihydroboxydyphenyl ethers, such as benzene, toluene, xylene, etc. Aromatic hydrocarbons such as cumene and mesitylene are preferred, with cumene being particularly preferred.
本発明における反応温度は、用いられる溶媒によっても
異なるが、反応の進行を促進するためには、用いられる
溶媒と反応により生成する水との共沸温度、具体的には
８０〜２００ ’Ｃの範囲内が好ましい。The reaction temperature in the present invention varies depending on the solvent used, but in order to promote the progress of the reaction, it is necessary to set the azeotropic temperature between the solvent used and the water produced by the reaction, specifically 80 to 200'C. Preferably within this range.
反応終了後、口過して触媒を除き、四肢の反応混合物を
室温まで冷却する。析出した結晶を口過して採取し、適
当な温度の温水で洗浄して未反応のヒドロキノン類を除
去後乾燥するという簡単な操作によって、純度９９モル
％以上の純粋な４゜４′−ジヒドロキシジフェニルエー
テル類を得ることができる。After the reaction is complete, remove the catalyst by sieving and cool the extremity reaction mixture to room temperature. Pure 4゜4'-dihydroxy with a purity of 99 mol% or more can be obtained by a simple operation of collecting the precipitated crystals by mouth, washing with warm water at an appropriate temperature to remove unreacted hydroquinones, and drying. Diphenyl ethers can be obtained.
また、触媒として用いたヘテロポリ酸またはその酸性金
属塩および未反応のヒドロキノン類は上記のように容易
に回収が可能であり、連続して使用することができる。Furthermore, the heteropolyacid or its acidic metal salt used as a catalyst and unreacted hydroquinones can be easily recovered as described above and can be used continuously.
（実施例）
以下に本発明の４，４′ −ジヒドロキシジフェニルエ
ーテル類の製造法について、実施例および比較例を用い
て具体的に説明するが、以下の実施例は、本発明の方法
を限定するものではない。(Example) The method for producing 4,4'-dihydroxydiphenyl ethers of the present invention will be specifically explained below using Examples and Comparative Examples. However, the following Examples will limit the method of the present invention. It's not a thing.
なお、収率（モル％）は消費されたヒドロキノン類に対
する収率であり、転化率（モル％）はヒドロキノン類の
消費率である。また、選択率は（収率／転化率）ｘｌｏ
ｏである。Note that the yield (mol%) is the yield based on the consumed hydroquinones, and the conversion rate (mol%) is the consumption rate of the hydroquinones. In addition, the selectivity is (yield/conversion rate) xlo
It is o.
実施例１〜７
水分離装置を付けた３ ００ ｍ ｌの４つロフラスコ
にヒドロキノン３３ｇ（０，３モル）、キュメン１２０
ｇおよび第１表に示すヘテロポリ酸５ｇを入れた。上記
混合物を１６０°Ｃに３時間加熱して反応させた。反応
後、１２０°Ｃで口過して触媒のへテロポリ酸を口利し
、四肢を室温まで冷却した。析出した結晶を口過して採
取し、５０°Ｃの温水で洗浄して未反応のヒドロキノン
を除去し、残った結晶を乾燥して４，４−−ジヒドロキ
シジフェニルエーテルを得た。４，４ −ジヒドロキン
ジフェニルエーテルの収率と転化率と選択率を第１表に
示す。Examples 1 to 7 In a 300 ml four-bottle flask equipped with a water separator, 33 g (0.3 mol) of hydroquinone and 120 g of cumene were added.
g and 5 g of the heteropolyacid shown in Table 1 were added. The above mixture was heated to 160°C for 3 hours to react. After the reaction, the heteropolyacid catalyst was passed through the mouth at 120°C, and the limbs were cooled to room temperature. The precipitated crystals were collected by sieving and washed with warm water at 50°C to remove unreacted hydroquinone, and the remaining crystals were dried to obtain 4,4-dihydroxydiphenyl ether. Table 1 shows the yield, conversion rate, and selectivity of 4,4-dihydroquine diphenyl ether.
比較例１
水分離装置を付けた３００ｍ１の４つロフラスコにヒド
ロキノン３３ｇ（０，３モル）と触媒としてｐ−トルエ
ンスルホン酸０．７５ｇとを入れた。上記混合物に窒素
を吹き込みながら２１０ ’Ｃで３０分間反応させたが
、実施例１と同様の方法では４，４′−ジヒドロキシジ
フェニルエーテルを単離できないため、反応液をガスク
ロマトグラフで分析した。４，４−−ジヒドロキシジフ
ェニルエーテルの収率と転化率と選択率を第１表に示す
。Comparative Example 1 33 g (0.3 mol) of hydroquinone and 0.75 g of p-toluenesulfonic acid as a catalyst were placed in a 300 ml four-bottle flask equipped with a water separator. The mixture was reacted at 210'C for 30 minutes while blowing nitrogen, but since 4,4'-dihydroxydiphenyl ether could not be isolated by the same method as in Example 1, the reaction solution was analyzed by gas chromatography. Table 1 shows the yield, conversion rate, and selectivity of 4,4-dihydroxydiphenyl ether.
比較例２
触媒トして、スルホン酸基含有スチレン−ビニルベンセ
ン共重合体からなるイオン交換樹脂（ローム・アンド・
ハース社製 Ａｍｂｅｒ１３’ｓｔ Ｒ−１５）を用い
て、ヒドロキノン３３ｇをキュメン中で５時間１６０°
Ｃに加熱した。反応後、室温まで冷却して、触媒を口利
した後、四肢を室温まで冷却した。Comparative Example 2 Ion exchange resin (ROHM &
Using Amber 13'st R-15 (manufactured by Haas), 33 g of hydroquinone was heated at 160° in cumene for 5 hours.
It was heated to C. After the reaction, the mixture was cooled to room temperature and the catalyst was removed, and then the limbs were cooled to room temperature.
析出した結晶は多量のヒドロキノンを含み、実施例１と
同様の方法では４，４−−ジヒドロキシジフェニルエー
テルを単離できないため、四肢をガスクロマトグラフで
分析した。４，４−−ジヒドロキシジフェニルエーテル
の収率と転化率と選択率を第１表に示す。The precipitated crystals contained a large amount of hydroquinone, and 4,4-dihydroxydiphenyl ether could not be isolated by the same method as in Example 1, so the limbs were analyzed by gas chromatography. Table 1 shows the yield, conversion rate, and selectivity of 4,4-dihydroxydiphenyl ether.
実施例８〜１１
原料のヒドロキノン類として、第２表に示す化合物を用
いたほかは、実施例１と同様に実験を行った。４，４−
−ジヒドロキシジフェニルエーテルの収率と転化率と選
択率を第２表に示す。Examples 8 to 11 Experiments were conducted in the same manner as in Example 1, except that the compounds shown in Table 2 were used as the raw material hydroquinones. 4,4-
-Dihydroxydiphenyl ether yield, conversion rate and selectivity are shown in Table 2.
第１表
（発明の効果）
本発明の方法は、４． ４’−ジヒドロキシジフェニル
エーテル類の選択性カダ高く、反応後の後処理が簡便で
あるという利点を有する。Table 1 (Effects of the Invention) The method of the present invention has 4. It has the advantage of high selectivity for 4'-dihydroxydiphenyl ethers and easy post-treatment after the reaction.
Claims (1)
量化する４，４′−ジヒドロキシジフェニルエーテル類
の製造法において、触媒として、ヘテロポリ酸またはそ
の酸性金属塩を用いることを特徴とする４，４′−ジヒ
ドロキシジフェニルエーテル類の製造法。 ２、ヘテロポリ酸またはその酸性金属塩が、リンまたは
ケイ素を中心原子とするヘテロポリタングステン酸、そ
の酸性金属塩、リンまたはケイ素を中心原子とするヘテ
ロポリモリブデン酸およびその酸性金属塩からなる群か
ら選ばれる１種以上の化合物である請求項１記載の製造
法。 ３、触媒としてケイタングステン酸および／またはリン
タングステン酸を用いる請求項１記載の製造法。[Claims] 1. A method for producing 4,4'-dihydroxydiphenyl ethers in which hydroquinones are dehydrated and dimerized in a solvent in the presence of a catalyst, using a heteropolyacid or an acidic metal salt thereof as a catalyst. A method for producing 4,4'-dihydroxydiphenyl ethers, characterized by: 2. The heteropolyacid or its acidic metal salt is selected from the group consisting of heteropolytungstic acid having a central atom of phosphorus or silicon, its acidic metal salt, heteropolymolybdic acid having a central atom of phosphorus or silicon, and its acidic metal salt. The method according to claim 1, which is one or more kinds of compounds. 3. The production method according to claim 1, wherein silicotungstic acid and/or phosphotungstic acid is used as the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2107756A JPH045254A (en) | 1990-04-24 | 1990-04-24 | Production of 4,4'-dihydroxydiphenyl ethers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2107756A JPH045254A (en) | 1990-04-24 | 1990-04-24 | Production of 4,4'-dihydroxydiphenyl ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH045254A true JPH045254A (en) | 1992-01-09 |
Family
ID=14467187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2107756A Pending JPH045254A (en) | 1990-04-24 | 1990-04-24 | Production of 4,4'-dihydroxydiphenyl ethers |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH045254A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391532A (en) * | 1993-05-06 | 1995-02-21 | Exxon Research And Engineering Company | Zirconium hydroxide supported metal and heteropolyacid catalysts |
| US5420092A (en) * | 1993-05-06 | 1995-05-30 | Exxon Research And Engineering Company | Silica supported metal and heteropolyacid catalysts |
| JP2007297315A (en) * | 2006-04-28 | 2007-11-15 | Kawasaki Kasei Chem Ltd | 4,4'-oxybi-1-naphthol compound, method for producing the same and photosensitizer containing the same |
-
1990
- 1990-04-24 JP JP2107756A patent/JPH045254A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391532A (en) * | 1993-05-06 | 1995-02-21 | Exxon Research And Engineering Company | Zirconium hydroxide supported metal and heteropolyacid catalysts |
| US5420092A (en) * | 1993-05-06 | 1995-05-30 | Exxon Research And Engineering Company | Silica supported metal and heteropolyacid catalysts |
| US5489733A (en) * | 1993-05-06 | 1996-02-06 | Exxon Research And Engineering Company | Zirconium hydroxide supported metal and heteropolyacid catalysts |
| JP2007297315A (en) * | 2006-04-28 | 2007-11-15 | Kawasaki Kasei Chem Ltd | 4,4'-oxybi-1-naphthol compound, method for producing the same and photosensitizer containing the same |
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