CN1312114C - Compound of aroma dihydroxy diamines and preparation method - Google Patents
Compound of aroma dihydroxy diamines and preparation method Download PDFInfo
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- CN1312114C CN1312114C CNB2004100930806A CN200410093080A CN1312114C CN 1312114 C CN1312114 C CN 1312114C CN B2004100930806 A CNB2004100930806 A CN B2004100930806A CN 200410093080 A CN200410093080 A CN 200410093080A CN 1312114 C CN1312114 C CN 1312114C
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Abstract
The present invention discloses a compound of aroma dihydroxy diamine shown in a right formula and a preparation method thereof. The compound uses aromatic dihydric phenol as raw material and can be prepared by two steps of reaction of nitration and reduction. Aromatic dihydroxy diamine is used as basic raw material and can react with aromatic binary acid to prepare polybenzoxazole (PBO for short). PBO is a heterocycle polymer with excellent mechanical properties and high heat resistance. As the PBO has the excellent fiber and thin film properties, the PBO is used for aerospace industry, textile industry, etc.
Description
Technical field:
The present invention relates to a class organic compound and a preparation method, particularly class compound of aroma dihydroxy diamines and preparation method thereof.
Background technology:
Polybenzoxazole (PBO) is a kind of aromatic heterocyclic polymer that has using value, and, high performance polymer high temperature resistant as a class is by commercialization.This aromatic heterocyclic polymer at high temperature has outstanding mechanical property and dielectric properties.PBO also has outstanding fiber and film performance except having outstanding thermostability, be widely used in space flight and aviation cause, textile industry and need strengthen the field of heat-stable material at other.Polybenzimidazole is to be formed by compound of aroma dihydroxy diamines and diprotic acid and derivative polycondensation thereof.Compound of aroma dihydroxy diamines by the design different structure can improve the over-all properties of corresponding PBO, thereby satisfies different practical application needs.
Summary of the invention:
The present invention is from Molecular Structure Design and point of practical use, a synthetic class compound of aroma dihydroxy diamines, and its structure is shown below:
Institute of the present invention synthetic compound of aroma dihydroxy diamines is to be basic raw material with fragrant dihydric phenol, prepares by nitrated, reduction two-step reaction, and its chemical equation can be expressed as follows:
The concrete preparation method of institute of the present invention synthetic compound of aroma dihydroxy diamines is as follows:
(1) nitration reaction: at ice bath, under the magnetic agitation condition, fragrant dihydric phenol and solvent are added in the reactor, wherein fragrant dihydric phenol mmol is 1: 5～5: 1 with the ratio of solvent mL, after treating that fragrant dihydric phenol dissolves fully, slowly add nitrating agent, the mol ratio of wherein fragrant dihydric phenol and nitrating agent is 1: 2～1: 5, under ice bath, reacted 0.5～4 hour, and then at room temperature continuing reaction 0～5 hour, after reaction finished, the product of generation was separated out product by separating out in the system or solution being poured in the deionized water, filter, use washing with alcohol, dry under vacuum condition, obtain the aroma dihydroxy dinitro compound;
(2) reduction reaction: in nitrogen protection, under the magnetic agitation condition, with aroma dihydroxy dinitro compound and ethanol and 1, the mixed solvent of 4-dioxane adds in the reactor, wherein the ratio of aroma dihydroxy dinitro compound mmol and ethanol mL is 1: 2～1: 8, ethanol and 1, the volume ratio of 4-dioxane is 1: 5～2: 1, the palladium charcoal that adds 10wt%, wherein the ratio of the palladium charcoal g of 10wt% and aroma dihydroxy dinitro compound mmol is 1: 30～1: 100, under refluxad drip the hydrazine hydrate that concentration is 70wt%～90wt%, after adding hydrazine hydrate, under refluxad reacted 10～30 hours, reaction finishes postcooling to room temperature again, filter, filtrate is poured in the deionized water under agitation condition, and wherein the volume ratio of deionized water and solvent is 10: 1～5: 1, and product is separated out in water, suction filtration, and wash with deionized water, dry under vacuum condition, obtain compound of aroma dihydroxy diamines; Wherein the chemical structural formula of compound of aroma dihydroxy diamines is as follows:
The used fragrant dihydric phenol structure of the present invention is shown below:
Wherein have: 2,2 '-dihydroxybiphenyl, 4,4 '-dihydroxybiphenyl, 2,2 '-dihydroxy diphenyl ether, 4,4 '-dihydroxy diphenyl ether, 4,4 '-dihydroxyl diphenyl sulfide, 2,4 '-dihydroxy diphenylsulphone, 4,4 '-dihydroxy diphenylsulphone, 2,2 '-dihydroxy benzophenone, 4,4 '-dihydroxy benzophenone, 2,2 '-dihydroxyl ditan, 2,4 '-dihydroxyl ditan, 4,4 '-dihydroxyl ditan, 4,4 '-dihydroxyl diphenylethane, 2, two (4-hydroxy phenyl) propane of 2-, 2, two (4-hydroxy phenyl) HFC-236fa of 2-, 1, two (4-hydroxy phenyl) benzene of 6-, 9, two (4-hydroxy phenyl) fluorenes of 9-, 4,4 '-dihydroxy-phenyl-cyclohexane.
Solvent used in the nitration reaction of the present invention comprises Glacial acetic acid, and diacetyl oxide or concentration are the sulfuric acid of 90wt%～98wt%.
Nitrating agent used in the nitration reaction of the present invention comprises: concentration is 50wt%～80wt% nitric acid or nitration mixture, wherein nitration mixture is to be that sulfuric acid and the concentration of 90wt%～98wt% is the nitric acid of 50wt%～80wt% by concentration, is to mix in 5: 1～1: 5 with volume ratio.
The resulting compound of aroma dihydroxy diamines of the present invention can prepare polybenzoxazole (being called for short PBO) with the aromatic dibasic acid reaction.PBO is that a class has the excellent mechanical property and the heterocycle polymer of resistance toheat.Because its outstanding fiber and film performance are widely used in aerospace industry, fields such as textile industry.
Description of drawings:
Fig. 1: 2, the infrared spectra IR (KBr) of 2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane (is solvent with the Glacial acetic acid)
Fig. 2: 2,2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane (is solvent with the Glacial acetic acid)
1HNMR (DMSO-d
6)
Fig. 3: 2, the infrared spectra IR (KBr) of 2-(4,4 '-dihydroxyl-3,3 '-two amido phenylbenzene) propane
Fig. 4: 2,2-(4,4 '-dihydroxyl-3,3 '-two amido phenylbenzene) propane
1H NMR (DMSO-d
6)
Fig. 5: 2, the infrared spectra IR (KBr) of 2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane (is solvent with the diacetyl oxide)
Fig. 6: 2,2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane (is solvent with the diacetyl oxide)
1HNMR (DMSO-d
6)
Fig. 7: 4,4 '-dihydroxyl-3, the infrared spectra IR (KBr) of 3 '-diphenylsulfone dinitro
Fig. 8: 4,4 '-dihydroxyl-3,3 '-diphenylsulfone dinitro
1H NMR (DMSO-d
6)
Fig. 9: 4,4 '-dihydroxyl-3, the infrared spectra IR (KBr) of 3 '-two amido sulfobenzides
Figure 10: 4,4 '-dihydroxyl-3,3 '-two amido sulfobenzides
1H NMR (DMSO-d
6)
Figure 11: the infrared spectra IR (KBr) of 9,9 '-two (4-hydroxyl-3-nitrophenyl) fluorenes
Figure 12: 9,9 '-two (4-hydroxyl-3-nitrophenyl) fluorenes
1H NMR (DMSO-d
6)
Figure 13: the infrared spectra IR (KBr) of 9,9 '-two (4-hydroxyl-3-aminophenyl) fluorenes
Figure 14: 9,9 '-two (4-hydroxyl-3-aminophenyl) fluorenes
1H NMR (DMSO-d
6)
Embodiment:
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
Synthesizing of (1) 2,2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane: in the three-necked bottle of 150mL, add 11.4 gram (0.05mol) 2, two (4-hydroxy phenyl) propane of 2-and 50mL Glacial acetic acid, dissolving fully under magnetic agitation.Concentrated nitric acid with 7.1mL 66wt% under ice bath cooling and magnetic agitation slowly splashes in the three-necked bottle with dropping funnel.After treating that concentrated nitric acid drips off, this mixed solution kept in ice bath 3 hours, and then at room temperature reacted 1 hour.After reaction finishes, reaction mixture is poured under magnetic agitation in the 1000mL deionized water, resulting precipitation is filtered with B, and gained precipitation head product is with methanol wash three times, 60 ℃ in vacuum dry 10 hours down.Get yellow powdery solid product 13.5 grams, productive rate is: 85%.Resulting product has been carried out structural characterization, comprised
1H nuclear-magnetism spectrum and infrared spectra prove that the synthetic product is 2,2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane.
Concrete characterization result is as follows:
Fig. 1 is 2, the infrared spectrum (KBr) of 2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane (is solvent with the Glacial acetic acid): wherein 3412.2, and 3327.0cm
-1Be-absorption peak of OH 3047.5cm
-1Be the Ar-H absorption peak, 2968.1cm
-1Be-CH
3Absorption peak, 1601.5,1512.7cm
-1Be-NO
2With on the phenyl ring-absorption peak of C=C-skeleton, 814.3,777.4,721.3cm
-1It is the Ar-H absorption peak; Fig. 2 is 2,2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane (is solvent with the Glacial acetic acid)
1H NMR is with DMSO-d
6Be solvent, wherein the ownership at each peak is indicated in collection of illustrative plates respectively.
(2) 2,2-(4,4 '-dihydroxyl-3,3 '-two amido phenylbenzene) propane is synthetic: be furnished with nitrogen inlet, add 6.36 gram (0.02mol) 2 in the three-necked bottle of the 150mL of magnetic agitation and reflux condensing tube, and 2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane, 40mL ethanol, 60mL1,4-dioxane, 0.2 the palladium charcoal of gram 10wt% stirs and is warming up to backflow.Under reflux temperature, the hydrazine hydrate of 8mL85wt% and 20mL alcoholic acid mixed solution are slowly splashed into by dropping funnel.After treating that hydrazine hydrate/alcohol mixeding liquid drips off, this is reflected in 95 ℃ of oil baths and kept 24 hours.Reaction system is cooled to room temperature, filters with B, and gained filtrate precipitating is in the 1000mL deionized water.The throw out that obtains filters and uses deionized water wash with B.60 ℃ in vacuum is following dry 10 hours then.Get faint yellow powdery solid product 4.64 grams, productive rate is: 90%.Resulting product has been carried out structural characterization, comprised
1H nuclear-magnetism spectrum and infrared spectra prove that the synthetic product is 2,2-(4,4 '-dihydroxyl-3,3 '-two amido phenylbenzene) propane.
Concrete characterization result is as follows:
Fig. 3 is 2, the infrared spectrum (KBr) of 2-(4,4 '-dihydroxyl-3,3 '-two amido phenylbenzene) propane: 3253.7cm wherein
-1Be-OH and-NH
2Absorption peak, 2968.2cm
-1Be-CH
3Absorption peak, 1629.7,1539.9cm
-1Be on the phenyl ring-absorption peak of C=C-skeleton 840.5cm
-1It is the Ar-H absorption peak; Fig. 4 is 2,2-(4,4 ' dihydroxyl-3,3 '-dinitro diphenyl) propane
1H NMR is with DMSO-d
6Be solvent, wherein the ownership at each peak is indicated in collection of illustrative plates respectively.
Embodiment 2:
Synthesizing of (1) 2,2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane: in the three-necked bottle of 150mL, add 22.8 gram (0.1mol) 2, two (4-hydroxy phenyl) propane of 2-and 70mL diacetyl oxide, dissolving fully under magnetic agitation.Concentrated nitric acid with 14.2mL66wt% under ice bath cooling and magnetic agitation slowly splashes in the three-necked bottle with dropping funnel.After treating that concentrated nitric acid drips off, this mixed solution kept in ice bath 3 hours.Then reaction mixture is filtered with B, gained precipitation head product usefulness methanol wash three times, 60 ℃ in vacuum is following dry 10 hours.Get yellow powdery solid product 26.3 grams, productive rate is: 83%.Resulting product has been carried out structural characterization, comprised
1H nuclear-magnetism spectrum and infrared spectra prove that the synthetic product is 2,2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane.
Concrete characterization result is as follows:
Fig. 5 is 2, the infrared spectrum (KBr) of 2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane (is solvent with the diacetyl oxide): wherein 3412.0, and 3327.1cm
-1Be-absorption peak of OH 3049.0cm
-1Be the Ar-H absorption peak, 2967.9cm
-1Be-CH
3Absorption peak, 1602.0,1513.9cm
-1Be-NO
2With on the phenyl ring-absorption peak of C=C-skeleton, 814.3,778.1,722.5cm
-1It is the Ar-H absorption peak; Fig. 6 is 2,2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane (is solvent with the diacetyl oxide)
1H NMR is with DMSO-d
6Be solvent, wherein the ownership at each peak is indicated in collection of illustrative plates respectively.
Synthesizing of (2) 2,2-(4,4 '-dihydroxyl-3,3 '-two amido phenylbenzene) propane: with embodiment 1 (2).
Embodiment 3:
(1) 4,4 '-dihydroxyl-3,3 '-dinitro diphenyl sulfone synthetic: in the three-necked bottle of 100mL, add 5 gram (0.02mol) 4,4 '-dihydroxy-diphenyl sulfone, the vitriol oil with 6mL96wt% under ice bath cooling and magnetic agitation slowly adds.Treat 4, after 4 '-dihydroxy-diphenyl sulfone dissolved fully, through the pre-cooled 6mL nitration mixture of ice bath, nitration mixture was made up of the vitriol oil 3mL of 96wt% and the concentrated nitric acid 3mL of 66wt%, slowly adds in the three-necked bottle.After treating that nitration mixture drips off, this mixed solution kept in ice bath 3 hours, at room temperature reacted then 2 hours.Then reaction mixture is poured in about 30 gram trash ices, the pale yellow colored solid body and function B that obtains filters, gained precipitation head product washing with alcohol.60 ℃ in vacuum is dry down then.Get faint yellow powdery solid product 6.46 grams, productive rate is: 95%.Resulting product has been carried out structural characterization, comprised
1H nuclear-magnetism spectrum and infrared spectra prove that the synthetic product is 4,4 '-dihydroxyl-3,3 '-diphenylsulfone dinitro.
Concrete characterization result is as follows:
Fig. 7 is 4,4 '-dihydroxyl-3, the infrared spectrum of 3 '-diphenylsulfone dinitro (KBr): 3277.9cm wherein
-1Be-absorption peak of OH 3113.3cm
-1Be the Ar-H absorption peak, 1621.0,1578.1cm
-1Be-NO
2With on the phenyl ring-absorption peak of C=C-skeleton, 1261.9,1158.5,1147.0cm
-1Be-SO
2-absorption peak, 911.8,841.1,825.0,765.5,744.7cm
-1It is the absorption peak of Ar-H; Fig. 8 is 4,4 '-dihydroxyl-3,3 '-diphenylsulfone dinitro
1H NMR is with DMSO-d
6Be solvent, wherein the ownership at each peak is indicated in collection of illustrative plates respectively.
(2) 4,4 '-dihydroxyl-3,3 '-two amido sulfobenzides synthetic: be furnished with nitrogen inlet, adding 6.8 gram (0.02mol) 2 in the three-necked bottle of the 150mL of magnetic agitation and reflux condensing tube, 2-(4,4 '-dihydroxyl-3,3 '-dinitro diphenyl) propane, 40mL ethanol, 60mL1, the 4-dioxane, the palladium charcoal of 0.2 gram 10wt% stirs and is warming up to backflow.Under reflux temperature, the hydrazine hydrate of 8mL85wt% and 20mL alcoholic acid mixed solution are slowly splashed into by dropping funnel.After treating that hydrazine hydrate/alcohol mixeding liquid drips off, this is reflected in 95 ℃ of oil baths and kept 24 hours.Reaction system is cooled to room temperature, filters with B, and gained filtrate precipitating is in the 500mL deionized water.Use extracted with diethyl ether, the gained organic phase is removed with Rotary Evaporators and is desolvated, and the gained solid places 60 ℃ in vacuum following dry 10 hours.Get rose pink solid product 4.36 grams, productive rate is: 78%.Resulting product has been carried out structural characterization, comprised
1H nuclear-magnetism spectrum and infrared spectra prove that the synthetic product is 4,4 '-dihydroxyl-3,3 '-two amido sulfobenzides.
Concrete characterization result is as follows:
Fig. 9 is 4,4 '-dihydroxyl-3, and the infrared spectrum of 3 '-two amido sulfobenzides (KBr): wherein 3458.2,3372.2,3354.5,3298.2cm
-1Be-OH and-NH
2Absorption peak, 3074.9cm
-1Be the absorption peak of Ar-H, 1598.5,1508.0cm
-1Be on the phenyl ring-absorption peak of C=C-skeleton, 1287.7,1145.0,1106.4,1079.3cm
-1Be-SO
2-Absorption peak, 938.1,855.9,811.1,695.1cm
-1It is the Ar-H absorption peak; Figure 10 is 4,4 '-dihydroxyl-3,3 '-two amido sulfobenzides
1H NMR is with DMSO-d
6Be solvent, wherein the ownership at each peak is indicated in collection of illustrative plates respectively.
Embodiment 4:
Synthesizing of (1) 9,9 '-two (4-hydroxyl-3-nitrophenyl) fluorenes: in the three-necked bottle of 100mL, add 5.52 gram (0.015mol) 9,9 '-two (4-hydroxy phenyl) fluorenes and 20mL diacetyl oxides, dissolving fully under magnetic agitation.Concentrated nitric acid with 2.18mL66wt% under ice bath cooling and magnetic agitation slowly splashes in the three-necked bottle with dropping funnel.After treating that concentrated nitric acid drips off, this mixed solution kept in ice bath 3 hours.Then reaction mixture is poured in the sodium bicarbonate aqueous solution of 30mL0.5wt%, after add water again, add solid sodium bicarbonate, regulator solution pH is to slightly acidic, and stirring is spent the night, and filters with B, the gained precipitated product is washed with water to neutrality, and 60 ℃ in vacuum is following dry 10 hours.Get yellow powdery solid product 5.38 grams, productive rate is: 81%.Resulting product has been carried out structural characterization, comprised
1H nuclear-magnetism spectrum and infrared spectra prove that the synthetic product is 9,9 '-two (4-hydroxyl-3-nitrophenyl) fluorenes.
Concrete characterization result is as follows:
Figure 11 is 9, the infrared spectrum (KBr) of 9 '-two (4-hydroxyl-3-nitrophenyl) fluorenes: 3254.0cm wherein
-1Be-absorption peak of OH 3040.1cm
-1Be the absorption peak of Ar-H, 1626.3,1536.0cm
-1Be on the phenyl ring-absorption peak of C=C-skeleton 1282.8cm
-1The absorption peak that is, 748.3cm
-1It is the absorption peak of Ar-H; Figure 12 is 9,9 '-two (4-hydroxyl-3-nitrophenyl) fluorenes
1H NMR is with DMSO-d
6Be solvent, wherein the ownership at each peak is indicated in collection of illustrative plates respectively.
(2) 9, synthesizing of 9 '-two (4-hydroxyl-3-aminophenyl) fluorenes: be furnished with nitrogen inlet, add 5.38 gram (0.012mol) 9 in the three-necked bottle of the 100mL of reflux condensing tube, 9 '-two (4-hydroxyl-3-nitrophenyl) fluorenes, 36mL ethanol, 36mL1,4-dioxane, 0.2 the palladium charcoal of gram 10wt% stirs and is warming up to backflow.Under reflux temperature, the hydrazine hydrate of 6mL85wt% and 12mL alcoholic acid mixed solution are slowly splashed into by dropping funnel.After treating that hydrazine hydrate/alcohol mixeding liquid drips off, this is reflected in 95 ℃ of oil baths and kept 24 hours.Reaction system is cooled to room temperature, adds 80mL1, and the white solid that 4-dioxane stirring and dissolving is separated out filters with B, and gained filtrate precipitating is in the 1000mL deionized water.The throw out that obtains filters and uses the deionized water repetitive scrubbing with B.60 ℃ in vacuum is following dry 10 hours then.Get canescence powdery solid product 3.9 grams, productive rate is: 83%.Resulting product has been carried out structural characterization, comprised 1H nuclear-magnetism spectrum and infrared spectra, proved that the synthetic product is 9,9 '-two (4-hydroxyl-3-aminophenyl) fluorenes.
Concrete characterization result is as follows:
Figure 13 is 9, the infrared spectrum (KBr) of 9 '-two (4-hydroxyl-3-aminophenyl) fluorenes: wherein 3441.1,3378.5, and 3306.7cm
-1Be-OH and-NH
2Absorption peak, 3067.2cm
-1Be the absorption peak of Ar-H, 1608.1,1510.5cm
-1Be on the phenyl ring-absorption peak of C=C-skeleton 1282.8cm
-1The absorption peak that is, 862.6,822.0,744.3cm
-1It is the absorption peak of Ar-H; Figure 14 is 9,9 '-two (4-hydroxyl-3-aminophenyl) fluorenes
1H NMR is with DMSO-d
6Be solvent, wherein the ownership at each peak is indicated in collection of illustrative plates respectively.
Claims (4)
1. the preparation method of compound of aroma dihydroxy diamines is characterized in that concrete preparation method is as follows:
(1) nitration reaction: at ice bath, under the magnetic agitation condition, fragrant dihydric phenol and solvent are added in the reactor, wherein fragrant dihydric phenol mmol is 1: 5～5: 1 with the ratio of solvent mL, after treating that fragrant dihydric phenol dissolves fully, slowly add nitrating agent, the mol ratio of wherein fragrant dihydric phenol and nitrating agent is 1: 2～1: 5, under ice bath, reacted 0.5～4 hour, and then at room temperature continuing reaction 0～5 hour, after reaction finished, the product of generation was separated out product by separating out in the system or solution being poured in the deionized water, filter, use washing with alcohol, dry under vacuum condition, obtain the aroma dihydroxy dinitro compound;
(2) reduction reaction: in nitrogen protection, under the magnetic agitation condition, with aroma dihydroxy dinitro compound and ethanol and 1, the mixed solvent of 4-dioxane adds in the reactor, wherein the ratio of aroma dihydroxy dinitro compound mmol and ethanol mL is 1: 2～1: 8, ethanol and 1, the volume ratio of 4-dioxane is 1: 5～2: 1, the palladium charcoal that adds 10wt%, wherein the ratio of the palladium charcoal g of 10wt% and aroma dihydroxy dinitro compound mmol is 1: 30～1: 100, under refluxad drip the hydrazine hydrate that concentration is 70wt%～90wt%, after adding hydrazine hydrate, under refluxad reacted 10～30 hours, reaction finishes postcooling to room temperature again, filter, filtrate is poured in the deionized water under agitation condition, and wherein the volume ratio of deionized water and solvent is 10: 1～5: 1, and product is separated out in water, suction filtration, and wash with deionized water, dry under vacuum condition, obtain compound of aroma dihydroxy diamines; Wherein the chemical structural formula of compound of aroma dihydroxy diamines is as follows:
-X-＝-；-O-；-S-；-SO
2-；-CO-；-CH
2-；-CH
2CH
2-；
2. the preparation method of compound of aroma dihydroxy diamines according to claim 1, it is characterized in that fragrant dihydric phenol is 2,2 '-dihydroxybiphenyl, 4,4 '-dihydroxybiphenyl, 2,2 '-dihydroxy diphenyl ether, 4,4 '-dihydroxy diphenyl ether, 4,4 '-dihydroxyl diphenyl sulfide, 2,4 '-dihydroxy diphenylsulphone, 4,4 '-dihydroxy diphenylsulphone, 2,2 '-dihydroxy benzophenone, 4,4 '-dihydroxy benzophenone, 2,2 '-dihydroxyl ditan, 2,4 '-dihydroxyl ditan, 4,4 '-dihydroxyl ditan, 4,4 '-dihydroxyl diphenylethane, 2, two (4-hydroxy phenyl) propane of 2-, 2; Two (4-hydroxy phenyl) HFC-236fa, 1 of 2-, two (4-hydroxy phenyl) benzene, 9 of 6-, two (4-hydroxy phenyl) fluorenes or 4 of 9-, 4 '-dihydroxy-phenyl-cyclohexane.
3. the preparation method of compound of aroma dihydroxy diamines according to claim 1 is characterized in that solvent used in the nitration reaction is a Glacial acetic acid, and diacetyl oxide or concentration are the sulfuric acid of 90wt%～98wt%.
4. the preparation method of compound of aroma dihydroxy diamines according to claim 1, it is characterized in that nitrating agent used in the nitration reaction is 50wt%～80wt% nitric acid or nitration mixture, wherein nitration mixture is to be to mix in 5: 1～1: 5 by the nitric acid of the sulfuric acid of 90wt%～98wt% and 50wt%～80wt% with volume ratio.
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| CN102584610B (en) * | 2011-12-28 | 2014-03-26 | 四川东材绝缘技术有限公司 | Bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride and preparation method and application thereof |
| CN102532498B (en) * | 2012-02-10 | 2013-06-12 | 四川大学 | Thioether-containing self-flame-retardant polyester and preparation method thereof |
| CN104478744B (en) * | 2014-11-18 | 2017-02-22 | 四川大学 | Preparation method of 4,4'-dihydroxy-3,3'-diamino diphenyl ketone |
| CN105348156A (en) * | 2015-08-27 | 2016-02-24 | 天津市众泰化工科技有限公司 | Preparation method for 3,3'-diamino-4,4'-dihydroxy diphenyl sulfone |
| CN105218415B (en) * | 2015-10-15 | 2016-09-14 | 天津市均凯化工科技有限公司 | The preparation method of 3,3 '-diaminourea-4,4 '-dihydroxydiphenylsulisomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5977413A (en) * | 1997-08-04 | 1999-11-02 | Nippon Kayaku Kabushiki Kaisha | Method for producing bis(3-amino-4-hydroxyphenyl) compounds |
| JP2004131386A (en) * | 2002-10-08 | 2004-04-30 | Nippon Kayaku Co Ltd | Method for producing diaminophenols |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5977413A (en) * | 1997-08-04 | 1999-11-02 | Nippon Kayaku Kabushiki Kaisha | Method for producing bis(3-amino-4-hydroxyphenyl) compounds |
| JP2004131386A (en) * | 2002-10-08 | 2004-04-30 | Nippon Kayaku Co Ltd | Method for producing diaminophenols |
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