CN105801471A - Bisphenol containing pyridine side groups and synthesis method of bisphenol - Google Patents
Bisphenol containing pyridine side groups and synthesis method of bisphenol Download PDFInfo
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- CN105801471A CN105801471A CN201610205640.5A CN201610205640A CN105801471A CN 105801471 A CN105801471 A CN 105801471A CN 201610205640 A CN201610205640 A CN 201610205640A CN 105801471 A CN105801471 A CN 105801471A
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- bisphenol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/50—Ketonic radicals
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Abstract
The invention discloses bisphenol containing pyridine side groups and a synthesis method of the bisphenol and relates to a compound and a synthesis method thereof. In an organic solvent, a reaction is performed in the presence of an alkaline catalyst, and bisphenol compounds and isonicotinoyl chloride or nicotinoyl chloride produce phenolic ester compounds; then, the phenolic ester compounds are subjected to a reaction in an organic solvent in the presence of an acid catalyst, and the phenolic ester compounds are rearranged to form the bisphenol containing the pyridine side groups. Bisphenol monomers containing the pyridine side groups can be constructed, the monomers can be used for synthesis of high-performance aryl polymers, and the polymers serving as an organic membrane material have important application prospect in the fields of new energy and environment, can also be taken as matrixes of high-performance composites and used in other aspects requiring high-performance polymer materials, and have wide application prospect.
Description
Technical field
The present invention relates to a kind of compound and synthetic method thereof, particularly relate to a kind of containing pyridine side base bis-phenol and synthetic method thereof.
Background technology
Anion exchange membrane has extraordinary application prospect in fields such as alkaline membrane fuel cell, flow batteries.The approach of tradition preparation anion exchange membrane material is that (such as polystyrene, polyarylether etc.) containing aromatic ring polymer are carried out chloromethylation, introduces chloro-methyl group in the polymer backbone and obtains chloromethylated polymer.Utilize the feature of chloro-methyl group high reaction activity, introduce positively charged anion exchange groups in the polymer with the nitrogenous little molecular reaction such as amine, pyridines, imidazoles and obtain anion exchange membrane.This approach is called chloromethylation route, and it has highly versatile, it is adaptable to multiple containing aromatic ring polymer.But, there are some wretched insufficiencies in chloromethylation route, for instance, chloromethylation process uses the chloromethyl methyl ether with carcinogenic toxicity；It is susceptible to the side reactions such as crosslinking；The position of chloromethyl and quantity poor controllability, film properties is easy-regulating not.Carry out solution polycondensation can prepare containing pyridine lateral group polyarylether with containing pyridine side base biphenol monomer and double; two halogen monomer, and then functionalization constructs anion exchange membrane.By regulating and controlling the ratio containing pyridine side base biphenol monomer, can accurately regulate the quantity of function base in polymer, the position of anion exchange groups and the accurate control of quantity can be realized, easily realize membrane material structure regulating and film properties optimization, be the new way of eco-friendly structure anion exchange membrane material.But, how efficiently to obtain these by raw material simple and easy to get and contain pyridine side base biphenol monomer and have become as focus and the huge challenge that needs are studied.
Summary of the invention
It is an object of the invention to provide a kind of containing pyridine side base bis-phenol and synthetic method thereof, the present invention utilizes common inexpensive commercial bis-phenol, nicotinoyl chlorine, different nicotinoyl chlorine to be raw material, realize the successful synthesis containing pyridine side base bisphenol compound, the synthesis of novel anionic exchange membrane material and high-performance polymer is had great importance.
It is an object of the invention to be achieved through the following technical solutions:
1. one kind containing pyridine side base bis-phenol, it is characterised in that it has following structure formula:
。
2. the synthetic method containing pyridine side base bis-phenol, it is characterised in that described method is obtained by following step:
；
At 100 DEG C and in organic solvent, under base catalyst exists, the response time is 1-12 hour, and bisphenol compound generates phenolic ester compound with different nicotinoyl chlorine or nicotinoyl chlorine；Wherein bisphenol compound is 1:2-4 with the mol ratio of different nicotinoyl chlorine or nicotinoyl chlorine；Then phenolic ester compound is in organic solvent, under the existence of acidic catalyst, reacts 1-24 hour at 20-150 DEG C, and phenolic ester compound is rearranged into containing pyridine side base bis-phenol；Above-mentioned organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, Nitrobenzol, chlorobenzene, Carbon bisulfide, N-Methyl pyrrolidone；Wherein, Ar and R is defined as above.
The described synthetic method containing pyridine side base bis-phenol, base catalyst includes one or more the mixture in Lithium hydrate, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, Strontium hydrate., barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, brium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate or calcium bicarbonate or organic amine such as triethylamine, pyridine etc..
The described synthetic method containing pyridine side base bis-phenol, acidic catalyst includes hydrochloric acid, sulphuric acid, phosphoric acid, trifluoromethanesulfonic acid, anhydrous zinc chloride, anhydrous ferric chloride, anhydrous Aluminum chloride, Zinc Bromide Anhydrous, anhydrous ferric bromide, ALUMINIUM BROMIDE ANHYDROUS, anhydrous stannic chloride, chlorine Ion-selective electrod.
The described synthetic method containing pyridine side base bis-phenol, product adopts and adds water washing, organic solvent extraction in reaction system, and anhydrous sodium sulfate dries, and concentrates recrystallization or column chromatography separation method purification.
Advantages of the present invention and effect be:
The present invention can build containing pyridine side base biphenol monomer, such monomer can be used for the synthesis of high-performance aryl polymer, this base polymer can as organic film material, new forms of energy, environmental area have important application prospect, also other can need the aspect of high-performance polymer material as matrix of high-performance composite materials etc., have very broad prospect of application.
Accompanying drawing explanation
Fig. 1 is infrared spectrum (KBr pressed disc method) figure of the pyridine side base bisphenol A-type compound of embodiment 1.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Following example contribute to understanding the present invention, but are not limited to present disclosure.
Embodiment 1
Under nitrogen protection, by bisphenol-A (0.1mol), different nicotinoyl chlorine (0.22mol), K2CO3(0.22mol), DMF40mL join equipped with mechanical agitator, thermometer, condensing tube, nitrogen inlet there-necked flask in, stirring, heat temperature raising react, at 100 DEG C, react 10 hours.Solution is poured in a large amount of water, bisphenol A-type phenolic ester Precipitation, filtering drying, recrystallization in DMF after terminating by reaction.The rearrangement of bisphenol A-type phenolic ester: bisphenol A-type phenolic ester (0.1mol), anhydrous Aluminum chloride (0.3mol), Nitrobenzol 100mL join equipped with mechanical agitator, thermometer, condensing tube, nitrogen inlet there-necked flask in, stirring, heat temperature raising reacts, and at 140 DEG C, reacts 8 hours.After reaction terminates, adding 100mL water in reaction system, vapor distillation removes Nitrobenzol, then n-butyl alcohol (50mL) aqueous layer extracted 3 times, and anhydrous sodium sulfate dries, concentration, precipitates out containing pyridine side base bisphenol A-type compound after solution cooling.
Embodiment 2
Under nitrogen protection, by bisphenol S (0.1mol), different nicotinoyl chlorine (0.22mol), K2CO3(0.22mol), DMF40mL join equipped with mechanical agitator, thermometer, condensing tube, nitrogen inlet there-necked flask in, stirring, heat temperature raising react, at 100 DEG C, react 10 hours.Solution is poured in a large amount of water, bisphenol S type phenolic ester Precipitation, filtering drying, recrystallization in DMF after terminating by reaction.The rearrangement of bisphenol S type phenolic ester: bisphenol S type phenolic ester (0.1mol), anhydrous Aluminum chloride (0.3mol), Nitrobenzol 100mL join equipped with mechanical agitator, thermometer, condensing tube, nitrogen inlet there-necked flask in, stirring, heat temperature raising reacts, and at 140 DEG C, reacts 8 hours.After reaction terminates, adding 100mL water in reaction system, vapor distillation removes Nitrobenzol, then n-butyl alcohol (50mL) aqueous layer extracted 3 times, and anhydrous sodium sulfate dries, concentration, precipitates out containing pyridine side base bisphenol S type compound after solution cooling.
Embodiment 3
。
Under nitrogen protection, by 4,4 '-'-biphenyl diphenol (0.1mol), different nicotinoyl chlorine (0.22mol), K2CO3(0.22mol), DMF40mL join equipped with mechanical agitator, thermometer, condensing tube, nitrogen inlet there-necked flask in, stirring, heat temperature raising react, at 100 DEG C, react 10 hours.Solution is poured in a large amount of water, 4,4 '-'-biphenyl diphenol type phenolic ester Precipitation, filtering drying, recrystallization in DMF after terminating by reaction.4, the rearrangement of 4 '-'-biphenyl diphenol type phenolic ester: 4,4 '-'-biphenyl diphenol type phenolic ester (0.1mol), anhydrous Aluminum chloride (0.3mol), Nitrobenzol 100mL join equipped with mechanical agitator, thermometer, condensing tube, nitrogen inlet there-necked flask in, stirring, heat temperature raising react, at 140 DEG C, react 8 hours.After reaction terminates, adding 100mL water in reaction system, vapor distillation removes Nitrobenzol, then n-butyl alcohol (50mL) aqueous layer extracted 3 times, and anhydrous sodium sulfate dries, concentration, precipitates out containing pyridine side base 4,4 '-'-biphenyl diphenol compound after solution cooling.
Above the specific embodiment of the present invention is described; but these can not be considered as limiting the scope of protection of the present invention; protection scope of the present invention is limited by appended claims, and any change on the claims in the present invention basis is all protection scope of the present invention.
Claims (5)
1. one kind containing pyridine side base bis-phenol, it is characterised in that it has following structure formula:
。
2. the synthetic method containing pyridine side base bis-phenol, it is characterised in that described method is obtained by following step:
；At 100 DEG C and in organic solvent, under base catalyst exists, the response time is 1-12 hour, and bisphenol compound generates phenolic ester compound with different nicotinoyl chlorine or nicotinoyl chlorine；Wherein bisphenol compound is 1:2-4 with the mol ratio of different nicotinoyl chlorine or nicotinoyl chlorine；Then phenolic ester compound is in organic solvent, under the existence of acidic catalyst, reacts 1-24 hour at 20-150 DEG C, and phenolic ester compound is rearranged into containing pyridine side base bis-phenol；Above-mentioned organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, Nitrobenzol, chlorobenzene, Carbon bisulfide, N-Methyl pyrrolidone；Wherein, Ar and R is defined as above.
3. according to claim 2 containing the synthetic method of pyridine side base bis-phenol, it is characterized in that, base catalyst includes one or more the mixture in Lithium hydrate, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, Strontium hydrate., barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, brium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate or calcium bicarbonate or organic amine such as triethylamine, pyridine etc..
4. the synthetic method containing pyridine side base bis-phenol according to claim 2, it is characterized in that, acidic catalyst includes hydrochloric acid, sulphuric acid, phosphoric acid, trifluoromethanesulfonic acid, anhydrous zinc chloride, anhydrous ferric chloride, anhydrous Aluminum chloride, Zinc Bromide Anhydrous, anhydrous ferric bromide, ALUMINIUM BROMIDE ANHYDROUS, anhydrous stannic chloride, chlorine Ion-selective electrod.
5. the synthetic method containing pyridine side base bis-phenol according to claim 2, it is characterised in that product adopts and adds water washing, organic solvent extraction in reaction system, and anhydrous sodium sulfate dries, concentration recrystallization or column chromatography separation method purification.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024800A (en) * | 2021-04-15 | 2021-06-25 | 沈阳化工大学 | Polyarylether containing pyridine group and preparation method thereof |
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| EP2424018A1 (en) * | 2010-08-27 | 2012-02-29 | JSR Corporation | Polyarylene block copolymer having sulfonic acid group and use thereof |
| CN104311828A (en) * | 2014-10-28 | 2015-01-28 | 沈阳化工大学 | Polyarylether containing adamantine structure and preparation method |
| CN104327304A (en) * | 2014-10-27 | 2015-02-04 | 沈阳化工大学 | Fire retardant for polyolefin high polymers and epoxy resin and preparation method of fire retardant |
-
2016
- 2016-04-06 CN CN201610205640.5A patent/CN105801471A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2424018A1 (en) * | 2010-08-27 | 2012-02-29 | JSR Corporation | Polyarylene block copolymer having sulfonic acid group and use thereof |
| CN104327304A (en) * | 2014-10-27 | 2015-02-04 | 沈阳化工大学 | Fire retardant for polyolefin high polymers and epoxy resin and preparation method of fire retardant |
| CN104311828A (en) * | 2014-10-28 | 2015-01-28 | 沈阳化工大学 | Polyarylether containing adamantine structure and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 刘孝波等: ""3, 3′-二苯甲酰基双酚-S及苯甲酰侧基聚芳醚腈的合成"", 《合成化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024800A (en) * | 2021-04-15 | 2021-06-25 | 沈阳化工大学 | Polyarylether containing pyridine group and preparation method thereof |
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