JPH0637418B2 - Method for separating 4,4'-dihydroxydiphenyl ether - Google Patents
Method for separating 4,4'-dihydroxydiphenyl etherInfo
- Publication number
- JPH0637418B2 JPH0637418B2 JP29519485A JP29519485A JPH0637418B2 JP H0637418 B2 JPH0637418 B2 JP H0637418B2 JP 29519485 A JP29519485 A JP 29519485A JP 29519485 A JP29519485 A JP 29519485A JP H0637418 B2 JPH0637418 B2 JP H0637418B2
- Authority
- JP
- Japan
- Prior art keywords
- dhpe
- water
- reaction mixture
- separating
- temperature
- 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 - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 19
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 title claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000011541 reaction mixture Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- 238000006471 dimerization reaction Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 1
- UXDBPOWEWOXJCE-DIPNUNPCSA-N 1,2-dihexadecyl-sn-glycero-3-phosphoethanolamine Chemical class CCCCCCCCCCCCCCCCOC[C@H](COP(O)(=O)OCCN)OCCCCCCCCCCCCCCCC UXDBPOWEWOXJCE-DIPNUNPCSA-N 0.000 description 50
- 239000003054 catalyst Substances 0.000 description 21
- 239000013078 crystal Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 239000011973 solid acid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000013638 trimer Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- -1 After all Substances 0.000 description 1
- WZEYZMKZKQPXSX-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1.CC1=CC(C)=CC(C)=C1 WZEYZMKZKQPXSX-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
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 発明の技術分野 本発明は合成ポリマーあるいは有機薬品の原料としての
用途が期待される4,4′−ジヒドロキシジフェニルエー
テルの分離方法に関する。TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for separating 4,4′-dihydroxydiphenyl ether, which is expected to be used as a raw material for synthetic polymers or organic chemicals.
発明の技術的背景ならびにその問題点 4,4′−ジヒドロキシジフェニルエーテル（以下ＤＨＰ
Ｅと略記することがある）はポリマーあるいは有機薬品
の原料としての用途が期待されている。このＤＨＰＥ
は、原料としてのヒドロキノン（1,4-ジヒドロキシベン
ゼンの別名、以下ＨＱと略記することがある）を合成雲
母、活性白土、モンモリロナイト、イオン交換樹脂など
の固体酸触媒の存在下に縮合することによって製造でき
ることが知られている。この縮合反応に際しては、キシ
レン、トルエンなどの非水系溶媒が一般に用いられてい
る。なお参考までにＤＨＰＥの合成反応を式で示せば次
のとおりである。Technical background of the invention and its problems 4,4'-dihydroxydiphenyl ether (hereinafter referred to as DHP
(Sometimes abbreviated as E) is expected to be used as a raw material for polymers or organic chemicals. This DHPE
Is obtained by condensing hydroquinone (another name for 1,4-dihydroxybenzene, sometimes abbreviated as HQ below) as a raw material in the presence of a solid acid catalyst such as synthetic mica, activated clay, montmorillonite, and an ion exchange resin. It is known that it can be manufactured. In this condensation reaction, a non-aqueous solvent such as xylene or toluene is generally used. For reference, the synthetic reaction of DHPE can be shown by a formula as follows.
上記のような方法によりＤＨＰＥを合成すると、反応後
に得られる反応混合物には、ＤＨＰＥ、ＨＱ、固体酸触
媒および芳香族炭化水素などの非水系溶媒が含まれてい
る。この反応混合物から目的化合物であるＤＨＰＥを分
離するには、従来種々の方法が提案されており、たとえ
ば米国特許第4,306,094号明細書には次のようなＤＨＰ
Ｅの分離精製方法が開示されている。すなわち、反応混
合物を冷却した後濾過することによってイオン交換樹脂
触媒を除去する。除去されたイオン交換樹脂をジエチル
エーテルで洗浄し、得られた洗浄液を濾液に加え、この
濾液からジエチルエーテルを減圧蒸溜によって留去する
とＨＱ、ＤＨＰＥおよび副生成物からなる固形物が得ら
れ、この固形物を温水で洗浄することによってＨＱを除
去し、得られたＤＨＰＥを溶媒から晶析することによっ
て精製ＤＨＰＥを得ている。このＤＨＰＥの精製方法に
よれば、溶媒を減圧蒸溜法などによって留去しなければ
ならず分離精製に手間がかかり、また分離した結晶を温
水で洗浄する方法ではＨＱが完全には除去されず製品Ｄ
ＨＰＥの純度が高められないという大きな問題点があっ
た。 When DHPE is synthesized by the above method, the reaction mixture obtained after the reaction contains DHPE, HQ, a solid acid catalyst and a non-aqueous solvent such as aromatic hydrocarbon. Various methods have been conventionally proposed for separating the target compound DHPE from the reaction mixture. For example, U.S. Pat. No. 4,306,094 discloses the following DHP.
A method for separating and purifying E is disclosed. That is, the ion exchange resin catalyst is removed by cooling the reaction mixture and then filtering. The removed ion exchange resin was washed with diethyl ether, the obtained washing liquid was added to the filtrate, and the diethyl ether was distilled off from this filtrate by distillation under reduced pressure to obtain a solid substance consisting of HQ, DHPE and by-products. HQ is removed by washing the solid with warm water, and the obtained DHPE is crystallized from the solvent to obtain purified DHPE. According to this DHPE purification method, the solvent has to be distilled off by a vacuum distillation method or the like, which requires time and effort for separation and purification, and the method of washing the separated crystals with warm water does not completely remove HQ. D
There is a big problem that the purity of HPE cannot be improved.
また特開昭49-55,635号公報には、ＨＱ、ＤＨＰＥ、溶
媒および固体酸触媒からなる反応混合物を加圧加温状態
で濾過して触媒を除去した後、蒸溜操作によって未反応
のＨＱを除去し、さらに減圧加熱蒸溜によってＤＨＰＥ
を蒸溜分離するＤＨＰＥの分離精製方法が開示されてい
る。しかしながらこのＤＨＰＥの分離精製方法では高温
での蒸溜操作が必要となり、ＤＨＰＥは高温に加熱され
ると分解するためＤＨＰＥのロスが生じるという大きな
問題点があった。Further, in JP-A-49-55,635, a reaction mixture consisting of HQ, DHPE, a solvent and a solid acid catalyst is filtered under pressure and heating to remove the catalyst, and then unreacted HQ is removed by a distillation operation. DHPE by vacuum heating distillation
A method for separating and purifying DHPE by distilling and separating is disclosed. However, this method for separating and purifying DHPE requires a distillation operation at a high temperature, and DHPE decomposes when heated to a high temperature, resulting in a large problem of loss of DHPE.
本発明者らは、ＨＱ、ＤＨＰＥ、溶媒および触媒からな
る反応混合物から、ＤＨＰＥを蒸溜操作を用いることな
く分離精製するための方法について鋭意研究したとこ
ろ、ＨＱとＤＨＰＥとの水に対する溶解度の差を利用す
ればよいことを見出して本発明を完成するに到った。The present inventors have diligently studied a method for separating and purifying DHPE from a reaction mixture consisting of HQ, DHPE, a solvent and a catalyst without using a distillation operation. As a result, the difference in solubility between HQ and DHPE in water is found. The inventors have found that the present invention should be used and have completed the present invention.
発明の目的 本発明は上記のような従来技術に伴なう問題点を解決し
ようとするものであり、ＨＱ、ＤＨＰＥ、溶媒および触
媒からなる反応混合物から、高温での蒸溜操作などのＤ
ＨＰＥの分解をともなう操作を用いることなくＤＨＰＥ
を分離するための方法を提供することを目的としてい
る。OBJECT OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and a reaction mixture consisting of HQ, DHPE, a solvent and a catalyst is used to perform a distillation operation at a high temperature or the like.
DHPE without using the operation that involves the decomposition of HPE
The purpose is to provide a method for separating.
発明の概要 本発明に係るＤＨＰＥの分離方法は、ヒドロキノンを脱
水二量化して4,4′−ジヒドロキシジフェニルエーテル
を製造する方法において、反応を水非混和性溶媒を用い
て行なった後、得られる未反応ヒドロキノンを含有する
液状反応混合物に水を添加し、適宜温度に維持すること
により4,4′−ジヒドロキシジフェニルエーテルを析出
させることを特徴としている。SUMMARY OF THE INVENTION A method for separating DHPE according to the present invention is a method for producing 4,4′-dihydroxydiphenyl ether by dehydration dimerization of hydroquinone, which is obtained after the reaction is carried out using a water-immiscible solvent. It is characterized in that water is added to the liquid reaction mixture containing the reaction hydroquinone and the temperature is appropriately maintained to precipitate 4,4'-dihydroxydiphenyl ether.
本発明では、水に対するＤＨＰＥとＨＱとの溶解度の差
を利用して反応混合物からＤＨＰＥを蒸溜操作を用いる
ことなく分離しているため、ＤＨＰＥの分解が生ずる恐
れがなく、かつ分離操作を著しく簡素化することができ
る。In the present invention, since the DHPE is separated from the reaction mixture without using a distillation operation by utilizing the difference in solubility between DHPE and HQ in water, there is no risk of decomposition of DHPE, and the separation operation is extremely simple. Can be converted.
発明の具体的説明 以下本発明に係るＤＨＰＥの分離方法についてフローチ
ャートを参照しながら具体的に説明する。Detailed Description of the Invention Hereinafter, a method for separating DHPE according to the present invention will be specifically described with reference to a flowchart.
図は、ＤＨＰＥ、ＨＱ、溶媒および触媒を含む反応混合
物からＤＨＰＥを分離するための一例を示したフローチ
ャート図である。The figure is a flow chart diagram showing an example for separating DHPE from a reaction mixture containing DHPE, HQ, a solvent and a catalyst.
ヒドロキノン（ＨＱ）と、合成雲母、活性白土、モンモ
リロナイトなどの固体酸触媒と、溶媒としてのメシチレ
ン、キシレン、トルエン、クメンなどの非水系溶媒とを
混合し、この混合物を１１０〜２００℃程度に加熱しな
がら攪拌すると、ＨＱは縮合反応によりＤＨＰＥとな
り、ＤＨＰＥ、ＨＱ、溶媒および触媒を含む反応混合物
が得られる。Hydroquinone (HQ), a solid acid catalyst such as synthetic mica, activated clay and montmorillonite, and a non-aqueous solvent such as mesitylene, xylene, toluene and cumene as a solvent are mixed and the mixture is heated to about 110 to 200 ° C. While stirring, HQ becomes DHPE by a condensation reaction, and a reaction mixture containing DHPE, HQ, a solvent and a catalyst is obtained.
本発明において液状反応混合物に水を添加するに際して
は、通常触媒を予め分離除去しておくことが好ましい。
固体触媒を使用した場合には、反応混合物から生成物で
ある固体が析出しないような条件下で、濾過、沈降分
離、遠心分離などの通常の固液分離手段を採用して固体
触媒を除去することができる。この場合には、反応混合
物の組成によっても異なるが、１３０℃以上で行うのが
好ましい。もちろん水添加後に触媒を分離する方法を採
用することもできるが、この場合にも反応混合物から生
成物固体が析出しないような高温度で分離する必要があ
る。In the present invention, when water is added to the liquid reaction mixture, it is usually preferable to previously separate and remove the catalyst.
When a solid catalyst is used, the solid catalyst is removed by adopting ordinary solid-liquid separation means such as filtration, sedimentation separation, centrifugation, etc. under the condition that the solid product is not precipitated from the reaction mixture. be able to. In this case, it is preferably carried out at 130 ° C. or higher, though it depends on the composition of the reaction mixture. Of course, a method of separating the catalyst after adding water can be adopted, but in this case as well, it is necessary to separate at a high temperature so that the product solid does not precipitate from the reaction mixture.
本発明では反応混合物に対する水の添加量の割合として
は、未反応ＨＱに対し操作時の温度におけるＨＱの飽和
溶解度分に相当する量の水を添加することが好ましく、
従って水の量はＤＨＰＥから主としてなる固形物の分離
操作時の温度によっても多少異なるが、反応混合物の未
反応ＨＱの１００重量部当たり通常水は５０〜１０，０
００重量部好ましくは２００〜２，０００重量部の範囲
で加えられる。この水の添加量は先の触媒の除去前後の
両段階で分割して添加することができることは上述のと
おりである。In the present invention, as the ratio of the amount of water added to the reaction mixture, it is preferable to add an amount of water corresponding to the saturated solubility of HQ at the temperature during operation with respect to unreacted HQ,
Therefore, the amount of water is somewhat different depending on the temperature at the time of the operation of separating the solid matter mainly composed of DHPE, but usually 100 to 100 parts by weight of unreacted HQ of the reaction mixture is 50 to 10% water.
00 parts by weight, preferably 200 to 2,000 parts by weight. As described above, the amount of water added can be divided and added before and after the removal of the catalyst.
本発明では水の割合をこのように選ぶことによって、後
述するようにＨＱが随伴することなくＤＨＰＥを選択的
に析出させことができる。In the present invention, by selecting the proportion of water in this way, DHPE can be selectively deposited without being accompanied by HQ, as will be described later.
本発明ではこのようにして得られる触媒が除去された水
含有脱触媒混合物は、その温度を適宜温度に保つことに
よって油相、水相およびＤＨＰＥを主として含有する析
出した固相の固液相からなる固液相混合物とし、析出し
た固相を分離するとＤＨＰＥから主としてなる固形物が
得られる。本発明の固液相混合物を得る場合の温度は、
前記した水の添加量によっても多少異なるので一概には
言えないが、本発明では該温度を通常９５℃以下、好ま
しくは７０〜２０℃に、油相および水相からなる水含有
脱触媒混合物を冷却することにより、ＤＨＰＥを主とし
て含有する固形物を析出させ、これによってＤＨＰＥ粗
結晶が分離される。According to the present invention, the water-containing decatalyst mixture thus obtained from which the catalyst has been removed is obtained by maintaining the temperature at an appropriate temperature to obtain an oil phase, an aqueous phase and a solid-liquid phase of a precipitated solid phase mainly containing DHPE When a solid-liquid phase mixture is formed and the precipitated solid phase is separated, a solid mainly composed of DHPE is obtained. The temperature for obtaining the solid-liquid phase mixture of the present invention is
Although it can not be generally stated because it varies somewhat depending on the amount of water added, in the present invention, the temperature is usually 95 ° C. or lower, preferably 70 to 20 ° C., and a water-containing decatalyst mixture comprising an oil phase and an aqueous phase is used. By cooling, a solid substance mainly containing DHPE is precipitated, whereby crude DHPE crystals are separated.
得られた粗結晶は、常法によって精製することができる
が、たとえば本発明者らによって見出されたアルキルベ
ンゼンとアセトンとの混合溶媒などの晶析溶媒を用いて
晶析操作によって精製すると、高純度でしかも高回収率
でＤＨＰＥを回収できる。The obtained crude crystals can be purified by a conventional method, but when purified by a crystallization operation using a crystallization solvent such as a mixed solvent of alkylbenzene and acetone found by the present inventors, a high yield can be obtained. DHPE can be recovered with high purity and high recovery rate.
上述のように水含有脱触媒混合物を冷却することによ
り、反応混合物からＤＨＰＥから主としてなる固形物が
析出してくるが、一方母液の水相をさらに冷却すると、
やはり固形物が析出してくることがある。この固形物
は、ＤＨＰＥ、ＨＱ、ヒドロキノン三量体などの副生成
物を含んでいる。By cooling the water-containing decatalyst mixture as described above, solid matter mainly composed of DHPE is precipitated from the reaction mixture, while further cooling the aqueous phase of the mother liquor,
After all, solid matter may precipitate. This solid contains by-products such as DHPE, HQ, and hydroquinone trimer.
母液の水相から回収された固形物はそのまま反応に使用
してもよく、必要に応じてＤＨＰＥあるいはＨＱを回収
することもできる。または母液の油相はそのまま反応に
用いてもよく、粗ＤＨＰＥの晶析溶媒として用いてもよ
く、また蒸溜などの手段で溶媒を回収しても良い。The solid matter recovered from the aqueous phase of the mother liquor may be used in the reaction as it is, and DHPE or HQ may be recovered as necessary. Alternatively, the oil phase of the mother liquor may be used as it is for the reaction, may be used as a crystallization solvent for crude DHPE, and the solvent may be recovered by means such as distillation.
本発明において、ＨＱからＤＨＰＥを合成するに際し
て、触媒として固体酸触媒の代わりにプロトン酸などの
液体の酸触媒を用いることもできるが、この場合には、
反応終了後に反応混合物から固体酸触媒を濾過して除去
する代わりに、反応混合物にアルカリを必要に応じて水
溶液の形で加えて触媒を失活させればよく、この後本発
明に係るプロセスを行なってＤＨＰＥを分離することが
できる。In the present invention, when DHPE is synthesized from HQ, a liquid acid catalyst such as a protonic acid can be used as a catalyst instead of the solid acid catalyst. In this case,
After completion of the reaction, instead of removing the solid acid catalyst from the reaction mixture by filtration, the catalyst may be deactivated by adding an alkali to the reaction mixture in the form of an aqueous solution, if necessary. It is possible to separate the DHPEs.
発明の効果 本発明では、水に対するＤＨＰＥとＨＱとの溶解度の差
を利用して反応混合物からＤＨＰＥを蒸溜操作を用いる
ことなく分離しているため、分離操作を著しく簡素化す
ることができる。またＤＨＰＥの分離操作時にＤＨＰＥ
に過度の熱が加わることがないため、ＤＨＰＥが熱分解
してしまうことが防止できる。Effect of the Invention In the present invention, DHPE is separated from the reaction mixture without using a distillation operation by utilizing the difference in solubility between DHPE and HQ in water, and therefore the separation operation can be significantly simplified. Also, during the DHPE separation operation, DHPE
Since excessive heat is not applied to the DHPE, it is possible to prevent the DHPE from being thermally decomposed.
以下本発明を実施例によって説明するが、本発明はこれ
ら実施例に限定されるものではない。The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１ トピー工業者製合成雲母であるナトリウムテトラシリシ
ックマイカの１０wt％水性懸濁液１０００ｇを１０の
水に懸濁し、良く攪拌しながら５％−Ａ（ＮＯ３）３
水溶液２０００ｍを加え、さらに２５分間攪拌を続け
アルミニウム型にイオン交換した。アルミニウム型にイ
オン交換された合成雲母を遠心分離により回収し、水で
よく洗浄し、更に乾燥（４０℃、５０mmHg、１０時間）
した。Example 1 1000 g of a 10 wt% aqueous suspension of sodium tetrasilicic mica, which is a synthetic mica manufactured by Topy Industries, was suspended in 10 water, and 5% -A (NO 3 ) 3 with good stirring.
An aqueous solution of 2000 m was added, and stirring was continued for further 25 minutes to perform ion exchange with an aluminum mold. The synthetic mica ion-exchanged into the aluminum mold was collected by centrifugation, washed well with water, and dried (40 ° C, 50 mmHg, 10 hours).
did.
このようにして調製された固体酸触媒であるアルミニウ
ム交換型合成雲母（イオン交換率４５％）８０ｇ、ヒド
ロキノン（ＨＱ）４００ｇ、メシチレン２５００ｍを
５の４つ口フラスコ中に仕込み、ディーンスターク水
補集トラップを取付け反応中に生成した水をメシチレン
との共沸により系外へ除去しながらメチシレン還流下２
時間加熱攪拌しヒドロキノンの二量化反応を行なった。A solid acid catalyst thus prepared, 80 g of aluminum-exchanged synthetic mica (ion exchange rate: 45%), 400 g of hydroquinone (HQ), and 2500 m of mesitylene were charged into a 4-necked flask of 5, and Dean-Stark water was collected. Attach a trap and remove the water generated during the reaction to the outside of the system by azeotropic distillation with mesitylene.
The mixture was heated and stirred for a time to carry out a dimerization reaction of hydroquinone.
反応終了後、反応混合物を１５０℃で濾過し、固体酸触
媒と反応液を分離した。この分離した反応液２４２０ｇ
中には未反応のＨＱ１７２ｇ、目的とする4,4′−ジヒ
ドロキシジフェニルエーテル１７２ｇ、ＨＱの三量体お
よびその他の多量体が２７ｇならびに反応溶媒としての
メシチレン（1,3,5-トリメチルベンゼン）が含まれてい
た。After completion of the reaction, the reaction mixture was filtered at 150 ° C. to separate the solid acid catalyst and the reaction solution. 2420 g of this separated reaction solution
Contains 172 g of unreacted HQ, 172 g of the target 4,4'-dihydroxydiphenyl ether, 27 g of HQ trimer and other multimers, and mesitylene (1,3,5-trimethylbenzene) as a reaction solvent. It was
このようにして触媒が分離された反応混合液２４２０ｇ
に水を７４８ｇ加え、攪拌を行ないながら徐々に温度を
下げ５０℃まで冷却し、５０℃に保温したバスケット型
遠心分離機を使用し析出した結晶を油および水層から分
離した。2420 g of the reaction mixture in which the catalyst has been separated in this way
748 g of water was added to the mixture, the temperature was gradually lowered to 50 ° C. with stirring, and the precipitated crystals were separated from the oil and water layers using a basket type centrifuge kept at 50 ° C.
分離した結晶を乾燥したところ、ＨＱを全く含まないＤ
ＨＰＥ８５．０％、ＨＱ三量体及びその他の多量体１
５．０％からなる１５３ｇの粗4,4′−ジヒドロキシジ
フェニルエーテルが得られた。When the separated crystals were dried, D containing no HQ
HPE 85.0%, HQ trimer and other multimers 1
153 g of crude 4,4'-dihydroxydiphenyl ether consisting of 5.0% were obtained.
一方、先の析出結晶が分離された残りの油層および水層
を攪拌しながら室温まで冷却した結晶を析出させバスケ
ット型遠心分離機を使用して析出した結晶を分離した。On the other hand, while stirring the remaining oil layer and aqueous layer from which the precipitated crystals were separated, the crystals were cooled to room temperature and precipitated, and the precipitated crystals were separated using a basket type centrifuge.
得られた結晶は、ＤＨＰＥを２４．６％、ＨＱを６１．
１％、ＨＱ三量体および多量体を２．３％含み、さらに
水１２ ．０％を含む１７１ｇの湿りケーキであった。The obtained crystals had DHPE of 24.6% and HQ of 61.
1%, 2.3% HQ trimer and multimer, and water 12. It was 171 g of wet cake containing 0%.
実施例２ 実施例１と同様にして得た未反応のＨＱ１６９ｇ、目的
とする4,4′−ジヒドロキシジフェニルエーテル（ＤＨ
ＰＥ）１７３ｇ、三量体およびその他の多量体２６ｇを
含む反応液２４９０ｇ中に水１１２７ｇを仕込み、攪拌
を行いながら徐々に温度を下げ４０℃まで冷却したとこ
ろで、４０℃に保温されたバスケット型遠心分離機を使
用して析出した結晶を油および水層から分離した。Example 2 Unreacted HQ169g obtained in the same manner as in Example 1 and the desired 4,4'-dihydroxydiphenyl ether (DH
PE) was added to 1490 g of water in 2490 g of a reaction solution containing 173 g of PEG, 26 g of trimer and other multimers, and the temperature was gradually lowered with stirring and cooled to 40 ° C. The precipitated crystals were separated from the oil and aqueous layers using a separator.
分離した結晶を乾燥したところＨＱを全く含まないＤＨ
ＰＥ８４．７％、ＨＱ三量体及びその他の多量体１５．
３％からなる１５５ｇの粗4,4′−ジヒドロキシジフェ
ニルエーテルが得られた。When the separated crystals were dried, DH containing no HQ
PE 84.7%, HQ trimer and other multimers 15.
155 g of crude 4,4'-dihydroxydiphenyl ether consisting of 3% were obtained.
また上記のようにして分離して得た油相および水層を攪
拌しながら室温まで冷却し、バスケット型遠心分離機を
使用して析出した結晶を分離した。The oil phase and aqueous layer obtained by separation as described above were cooled to room temperature with stirring, and the precipitated crystals were separated using a basket type centrifuge.
得られた結晶は、ＤＨＰＥを２３．１％、ＨＱを６０．
７％、ＨＱ三量体および多量体を１．２％含みさらに水
１５．０％を含み１７３ｇの湿りケーキであった。The obtained crystals had DHPE of 23.1% and HQ of 60.
173 g of wet cake containing 7%, 1.2% HQ trimer and multimer and 15.0% water.
実施例３〜１４ 実施例１で得られた粗ＤＨＰＥの乾燥結晶１０ｇを、表
１に示した極性有機溶媒と、炭化水素溶媒またはハロゲ
ン置換炭化水素溶媒とからなる混合溶媒５０ｇを用いて
再結晶した。結果を表１に示す。Examples 3 to 14 Recrystallized 10 g of dried crystals of crude DHPE obtained in Example 1 using 50 g of a mixed solvent consisting of the polar organic solvent shown in Table 1 and a hydrocarbon solvent or a halogen-substituted hydrocarbon solvent. did. The results are shown in Table 1.
図は本発明に係る4,4′−ジヒドロキシジフェニルエー
テルの分離方法のフローチャートである。 図中点線内は必要に応じて行なわれる分離工程である。The figure is a flow chart of a method for separating 4,4'-dihydroxydiphenyl ether according to the present invention. In the figure, the inside of the dotted line is a separation process performed as necessary.
Claims (3)
ヒドロキシジフェニルエーテルを製造する方法におい
て、反応を水非混和性溶媒を用いて行なった後、得られ
る未反応ヒドロキノンを含有する液状反応混合物に水を
添加し、適宜温度に維持することにより4,4′−ジヒド
ロキシジフェニルエーテルを析出させることを特徴とす
る4,4′−ジヒドロキシジフェニルエーテルの分離方
法。1. A method for producing 4,4'-dihydroxydiphenyl ether by dehydration dimerization of hydroquinone, wherein the reaction is carried out using a water immiscible solvent, and the obtained liquid reaction mixture contains unreacted hydroquinone. A method for separating 4,4'-dihydroxydiphenyl ether, which comprises precipitating 4,4'-dihydroxydiphenyl ether by adding water to and maintaining the temperature at an appropriate temperature.
フェニルエーテルを析出させる際の温度を９５℃以下に
する特許請求の範囲第１項に記載の方法。2. The method according to claim 1, wherein water is added to the liquid reaction mixture so that the temperature for precipitating 4,4'-diphenyl ether is 95 ° C. or lower.
水の量として少なくとも液状反応混合物中にある未反応
ヒドロキノンの全量を７０℃以上の温度で溶解するに足
る量の水を用いる特許請求の範囲第１項に記載の方法。3. When the liquid reaction mixture is contacted with water,
The method according to claim 1, wherein the amount of water used is at least an amount of water sufficient to dissolve the total amount of unreacted hydroquinone present in the liquid reaction mixture at a temperature of 70 ° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29519485A JPH0637418B2 (en) | 1985-12-27 | 1985-12-27 | Method for separating 4,4'-dihydroxydiphenyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29519485A JPH0637418B2 (en) | 1985-12-27 | 1985-12-27 | Method for separating 4,4'-dihydroxydiphenyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62155234A JPS62155234A (en) | 1987-07-10 |
| JPH0637418B2 true JPH0637418B2 (en) | 1994-05-18 |
Family
ID=17817413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29519485A Expired - Fee Related JPH0637418B2 (en) | 1985-12-27 | 1985-12-27 | Method for separating 4,4'-dihydroxydiphenyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0637418B2 (en) |
-
1985
- 1985-12-27 JP JP29519485A patent/JPH0637418B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62155234A (en) | 1987-07-10 |
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