CN104892929A - Method for simply and efficiently synthesizing poly(hydroquinone) - Google Patents

Method for simply and efficiently synthesizing poly(hydroquinone) Download PDF

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CN104892929A
CN104892929A CN201510291765.XA CN201510291765A CN104892929A CN 104892929 A CN104892929 A CN 104892929A CN 201510291765 A CN201510291765 A CN 201510291765A CN 104892929 A CN104892929 A CN 104892929A
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resorcinol
poly
solution
effective synthesis
synthesis according
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CN104892929B (en
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黄美荣
李新贵
郭世坚
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Tongji University
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Tongji University
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Abstract

The invention relates to a method for simply and efficiently synthesizing poly(hydroquinone). The method comprises the following steps of dissolving hydroquinone into an acid water medium and mixing uniformly to prepare a monomer solution; dissolving an oxidizing agent into deionized water to prepare an oxidizing agent solution; adding the oxidizing agent solution into the monomer solution; after the mixed reaction liquid reacts completely in the water bath environment at a certain temperature, separating the product to obtain poly(hydroquinone). Compared with the prior art, a chemical oxidative polymerization method is adopted in the invention, so that poly(hydroquinone) can be synthesized at the water bath temperature not more than 100 DEG C. The method is economical and effective, is simple in operation, and has the potential of synthesizing in batches and large scales. The obtained product has well application prospects, and is expected to be applied to the fields of antioxidants, noble metal ionic adsorption treatment in waste water, biosensors and the like.

Description

The method of the poly-Resorcinol of a kind of simple and effective synthesis
Technical field
The present invention relates to a kind of synthetic method of polymers, especially relate to the method for the poly-Resorcinol of a kind of simple and effective synthesis.
Background technology
Poly-Resorcinol (PHQ) is a kind of polymkeric substance with redox active.Poly-Resorcinol only contains quinone and quinhydrones on main chain, and be the polymkeric substance with aromatic conjugated system, this polymkeric substance not only has the feature that redox potential is low, electron transfer speed is fast, and can carry out the redox of two electronics, there is higher electric density, there is good redox reversible (Zhang Aijuan, Zhang Wenjing, Zhang Yongjun, Deng. the progress of the poly-Resorcinol of redox active, polymer is circulated a notice of, and 2011, (5): 17-26.).Exactly because PHQ has so excellent characteristic, it can be applied to the field such as antioxidant, biosensor.In recent years, PHQ is especially subject to the favor of numerous investigator.
The preparation method of poly-Resorcinol generally has base catalyzed polymerization method, Louis acid catalysis polymerization, electrochemically oxidative polymerization method, enzymatic oxidation polymerization, organo-metallic nickel catalysis dehalogenation condensation methods, H 2o 2-FeSO 4catalyst polymerization, Catalyzed by Chitosan polymerization.
Base catalyzed polymerization method is that highly basic or weak base are initiator with the aqueous solution or organic solvent for reaction medium.Resorcinol (HQ) or benzoquinone (BQ) are monomer.Under the condition of room temperature, synthesis obtains PHQ, and the method is simple and easy to operate.Relative to HQ monomer, when taking BQ as monomer, the productive rate of resulting polymers is much higher, can reach 113.3% (Cataldo, F.On the Structure of Macromolecules Obtained by Oxidative Polymerization of Polyhydroxyhenols and Quinones.Polym.Int., 1998,46:263-268.).Be have hydroxyquinol to generate in monomer base catalyzed polymerization process with BQ, also benzenetriol unit is there is in polymerisate, the 50%-100% that benzenetriol unit accounts for total unit number in polymerisate chain does not wait (Sadykh-Zade, S.I., Ragimov, A.V., Suleimanova, S.S.The Polymerization of Quinones in an Alkaline Medium and the Structure of the Resulting Polymers.Polymer Science USSR, 1972,14:1395-1403.).The speed of response of synthesizing PHQ in highly basic medium is faster, and as in the strong base solution media such as KOH, polyreaction can complete in 24h, and at weak alkaline medium as NH 3h 2in O (30%), then need the reaction times (Furlani of 6d, A., Russo, M.V., Cataldo, F.Oxidative Polymerization of P-Benzoquinone and hydroquinone.Conductivity of Doped and UndopedPolymol/Lerization Products.Synthetic.Met., 1989,29:507-510.).Prepare PHQ by base catalyzed polymerization, method is simple and easy to operate, but the PHQ polymerization degree that this method prepares generally only has 5 ~ 8, and molecular weight is too low.
Louis acid catalysis polymerization is as ZnCl with Lewis acid 2, AlCl 3, BF 3oEt 2for catalyzer, BQ is monomer in solid-state or solvent under heating condition polymerization generates PHQ.This kind of method synthesis PHQ, at 100 DEG C, BQ is monomer, BF 3oEt 2for catalyzer, be under the condition of reaction medium with Nitromethane 99Min., the polymerization yield rate of reaction 5h PHQ can reach the highest by 90.7% (Berlin, A.A., Ragimov, A.V., Sadykh-Zade, S.I., Gadzhieva, T.A., Takhmazov, B.M.Effect of The Type of Lewis Acid on the Structure, Properties and Yield of Polycondensation products of P-Benzoquinone.Polymer Science USSR, 1975,17:126-134.).The disadvantage of the Louis acid catalysis synthesis PHQ stable combination that has been chlorion and polymer formation and cause chlorion not easily to be removed, product is not easily purified (Berlin A.A., Ragimov A.V., Sadykh-Zade S.I.Polycondensation of p-Benzoquinone in the presence of Lewis acids.Polymer Science USSR, 1973, 15 (4): 887-891.), and its polymer molecular weight is lower, (Berlin between 410 ~ 770, A.A., Ragimov, A.V., Sadykh-Zade, S.I., Gadzhieva, T.A., Takhmazov, B.M.Effect of The Type of Lewis Acid on the Structure, Properties and Yield of Polycondensation products ofp-Benzoquinone.Polymer Science USSR, 1975, 17:126-134.).
Electrochemically oxidative polymerization legal system is for PHQ, generally using glass-carbon electrode, expanded graphite etc. as electrode, in the electrolyte solution containing HQ, electropolymerization prepares PHQ (Chen Zhidong, Chen little Hui, Yuan Jia, Wang Wenchang, Kong Yong. poly-Resorcinol modifies preparation and the character thereof of expanded graphite electrode. analytical chemistry, 2010,38 (4): 555-558.).The method of electrochemically oxidative polymerization PHQ is generally used for the electrode of preparation PHQ modification, is not suitable for mass-producing and prepares PHQ.
Enzymatic oxidation polymerization synthesis PHQ is for monomer with HQ derivative, primary product is obtained through peroxide horseradish enzyme-catalyzed polymerization, primary product obtains PHQ (Wang.P., Martin, B.D. through hydrolysis again, Rethwisch, D.G., Parida, J.S.Multienzymic Synthesis of Poly (Hydroquinone) for Use as A Redox Polymer.J.Am.Chem.Soc., 1995,117 (51): 12885-12886.).Utilize enzymatic oxidation polymerization can obtain having the molecular structure comparatively determined, molecular weight is also relatively high, has good redox active, this preparation method's environmental protection, but preparation step is played loaded down with trivial details, and preparation cost is higher.In addition, organo-metallic nickel catalysis dehalogenation condensation methods also has similar relative merits, it is to 1 with zero valent nickel complex, 4-bis-bromo-2, 5-diacetyl benzene carries out dehalogenate polycondensation and obtains single poly-2 of structure of determining, 5-diacetyl benzene, product can obtain PHQ (Yarnamoto after lithium aluminum hydride and HCl treatment, T., Kimura, T., Shiraishi, K.Preparation of π-Conjugated Polymers Composed of Hydroquinone, P-Benzoquinone, and P-Diacetoxyphenylene Units.Optical and Redox Properties of the Polymers.Macromolecules, 1999, 32 (26): 8886-8896.).
In recent years also have the synthesis about poly-Resorcinol to report, but all carry out at polymer shell glycan or under belonging to the templates such as supermolecule polymer, the poly-Resorcinol formed is a kind of hydrogel.This method length consuming time, productive rate are low.(He,J.,Zhang,A.J.,Zhang,Y.J.,Guang,Y.Novel Redox Hydrogel by in Situ Gelation of Chitosan as A Result of Template Oxidative Polymerization of Hydroquinone.Macromolecules,2011,44(7):2245-2252.)。
Up to the present, although the method preparing PHQ comparatively horn of plenty.But all methods preparing PHQ still can not take into account easy and simple to handle, productive rate is higher, the feature such as with low cost.Therefore, find a kind of simple, can the synthetic method of the poly-Resorcinol of cheap mass-producing preparation will develop significant to it.
Summary of the invention
Object of the present invention is exactly provide a kind of simple and effective to synthesize the method for poly-Resorcinol to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
The method of the poly-Resorcinol of a kind of simple and effective synthesis, comprise the following steps: Resorcinol is dissolved in sour water medium mixing and makes monomer solution, oxygenant is dissolved in deionized water and makes oxidizing agent solution, oxidizing agent solution is joined in monomer solution, after mixed reaction solution reacts completely in the water bath of certain temperature, by product separation out, poly-Resorcinol is namely obtained.
Described sour water medium comprises sulphuric acid soln, hydrochloric acid soln or acetum.
Described oxygenant is selected from ammonium persulphate, Potassium Persulphate or ammonium persulphate and Potassium Persulphate arbitrary proportion mixture, is preferably ammonium persulphate.
Described oxygenant and the mol ratio of Resorcinol are 0.5:1 ~ 4:1, are preferably 0.5:1 ~ 2:1.
The oxidizing agent solution mode joined in monomer solution is that disposable impouring or dropping add, and rate of addition is 1/3 seconds.
Temperature of reaction be room temperature to 90 DEG C, be preferably 40 ~ 80 DEG C, the reaction times is 6h ~ 72h, be preferably 24h.
Product separation mode is: by reaction soln centrifugal treating, after thing sedimentation to be polymerized, is sucked by supernatant liquid and uses deionized water wash polymkeric substance, recentrifuge after dispersion; Repeat above operation, until supernatant liquid is clarified and used 0.01mol/L BaCl 2solution detects without SO 4 2-till ion.
Compared with prior art, the present invention utilizes the method for chemical oxidising polymerisation, obtains poly-Resorcinol being no more than can to synthesize under the water bath condition of 100 DEG C.The method economical and effective, simple to operate, there are the potentiality of mass-producing batch synthesis.Products therefrom has good application prospect, is expected to be applied to the field such as precious metal ion adsorption treatment, biosensor in antioxidant, sewage.
Accompanying drawing explanation
Fig. 1 is the poly-Resorcinol ultraviolet-visible absorption spectroscopy of synthesis in embodiment 6;
Fig. 2 is the poly-Resorcinol Fourier ATR-FTIR absorption spectrum of synthesis in embodiment 4,5,6;
Fig. 3 is the poly-Resorcinol X ray diffracting spectrum of synthesis in embodiment 6;
Fig. 4 is poly-Resorcinol and KMnO in embodiment 15 4the UV of solution reaction follows the tracks of collection of illustrative plates.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Accurately take 1.5g Resorcinol and be dissolved in 35mL 0.1mol/L H 2sO 4in solution reaction medium, by oxygenant and the dihydroxy-benzene mol ratio (hereinafter referred to as oxygen digital ratio) of 2:1, accurately take 6.218g ammonium persulphate and be dissolved in 15mL 0.1mol/L H 2sO 4in solution.Above-mentioned two kinds of solution water-baths are heated to 50 DEG C.Under magnetic stirring, oxidizing agent solution is joined in monomer solution in the disposable mode poured into.Dropwise, continue reaction until 24h.Reaction terminates, and reaction soln is poured into centrifuge tube and carries out centrifugal, to be sucked by supernatant liquid and uses deionized water wash, again wash after dispersion after thing sedimentation to be polymerized with dropper; Repeat above operation, until the clarification of centrifuge tube supernatant liquid is washed till use 0.01mol/LBaCl 2without SO in solution inspection clear liquid 4 2-till ion.Transferred to by product in watch-glass, in air atmosphere, in loft drier, temperature is dry under 60 DEG C of conditions, until constant weight, obtain black powder polymerisate, ultimate yield is 46.3%.
Embodiment 2 ~ 3
Repeat embodiment 1, change the acidic medium solution of dissolved monomer and oxygenant, make acidic medium solution be respectively 0.1mol/L hydrochloric acid soln and 0.1mol/L acetum.The productive rate of final product is 38.3%, 45.0%.
Embodiment 4 ~ 7
Repeat embodiment 1, change oxygenant feed postition within every 3 seconds, to add with 1, change oxygen digital ratio, oxygen digital ratio is respectively 2:1,1.5:1,1:1,0.5:1.The productive rate of final product is 43.7%, 37.4%, 34.0%, 14.7%.
Embodiment 8 ~ 11
Repeat embodiment 1, change oxygenant feed postition within every 3 seconds, to add with 1, changing oxygen digital ratio is 1.5:1, and change bath temperature, bath temperature is respectively 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C.The productive rate of final product is 34.7%, 40.5%, 44.0%, 42.0%.
Embodiment 12
Getting reaction medium in 2mg embodiment 6 is the H of 0.1mol/L 2sO 4, drip oxygenant ammonium persulfate solution in reaction medium with the every 3 seconds speed of 1.Oxygen digital ratio is 1:1, and the product synthesized under reaction water bath temperature 50 DEG C of conditions is dissolved in 10mLN-methylpyrrole alkane (NMP), and the nmp solution being dissolved with poly-Resorcinol utilizes ultraviolet-visible pectrophotometer to carry out ultraviolet test subsequently.Uv-spectrogram, as Fig. 1, shows in collection of illustrative plates after product is dissolved in NMP and has occurred three place's ultraviolet absorption peaks at long wavelength region 396nm, 416nm, 540nm place, the planar conjugate structure that there is a certain size is described in polymkeric substance, comprises a certain size condensed cyclic structure.Particularly for the hangover absorption peak higher than 500nm, polymkeric substance is pointed out to have a wider wire conjugated structure.This shows that Resorcinol monomer there occurs polyreaction, and generates the wire with large conjugated structure and gather Resorcinol.
Embodiment 13
In embodiment, reaction medium is the H of 0.1mol/L in 4,5,6 2sO 4, with every 3 seconds 1 dropping oxygenant ammonium persulfate solutions, oxygen digital ratio was 2:1,1.5:1,1:1, and the poly-Resorcinol synthesized under reaction water bath temperature 50 DEG C of conditions carries out the test of Fourier's ATR-FTIR, and infrared spectra is as Fig. 2.3246cm -1locate wide absorption peak and represent in polymkeric substance to there is hydroxyl, after polymerization is described, remain the hydroxyl of Phenol Monomer; 1752cm -1absorption peak represents the existence of carbonyl-C=O, and after the appearance of this new functional group prompting polymerization, hydroxyl is transformed into the possibility of quinonyl, but from the quinoid structure of hexa-atomic phenyl ring at 1583cm -1absorption peak well below the benzene formula structure of hexa-atomic phenyl ring at 1507cm -1the absorption peak at place, can know by inference, and quinoid structure, far fewer than benzene formula structure, namely only has a small amount of hydroxyl to be transformed into quinonyl after polymerization.Meanwhile, 1200cm -1-the C-O-of place represented by strong absorption peak also can show that the hydroxyl existed in polymkeric substance is more than quinonyl further.On the other hand, in conjunction with a certain size the two dimensional structure of UV suggested by the hangover absorption peak higher than 500nm, can infer there is dibenzo dioxy six ring structure.Therefore synthesized poly-Resorcinol is inferred containing following structure:
Visible, Phenol Monomer can be polymerized by present method, and polymerization mainly through the removing of hydrogen atom on the carbon of monomer hydroxyl ortho position, coupling becomes linear structure.
Embodiment 14
In embodiment 6, reaction medium is the H of 0.1mol/L 2sO 4, within every 3 seconds, add oxygenant ammonium persulfate solution with 1, oxygen digital ratio is respectively 1:1, and the poly-Resorcinol synthesized under reaction water bath temperature 50 DEG C of conditions utilizes X-ray diffractometer to carry out X-ray diffraction test, and diffracting spectrum is as Fig. 3.Within the scope of Bragg angle 5 ~ 70 °, the X ray diffracting spectrum of polymkeric substance and monomer is contrasted known, there is not the sharp diffraction peak of any feature of monomer in poly-Resorcinol, a wide in range diffraction peak is shown only Bragg angle 24 °, show that Phenol Monomer can be polymerized by present method, and after polymerization gained to gather Resorcinol be amorphous unformed.
Embodiment 15
Get the KMnO of the 25mg/L of 3mL 4solution joins in the thick cuvette of 1cm, utilizes ultraviolet-visible pectrophotometer to scan 0 moment UV, and getting in 0.06mg embodiment reaction medium in 6 is the H of 0.1mol/L 2sO 4, within every 3 seconds, add oxygenant ammonium persulfate solution with 1, oxygen digital ratio is 1:1, and the poly-Resorcinol synthesized under reaction water bath temperature 50 DEG C of conditions joins above-mentioned KMnO 4in solution, rock, make it be evenly distributed on KMnO 4in solution, carry out UV scanning at regular intervals, till UV collection of illustrative plates no longer changes.Along with the increase in reaction times, represent KMnO 4the ultraviolet absorptivity being positioned at 525nm constantly reduce, this represents KMnO in solution 4concentration reduce, poly-Resorcinol reduces KMnO 4, namely poly-Resorcinol shows reductibility due to the existence of phenolic hydroxyl group.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.

Claims (9)

1. a method for the poly-Resorcinol of simple and effective synthesis, is characterized in that, comprise the following steps:
Resorcinol is dissolved in sour water medium mixing and makes monomer solution, oxygenant is dissolved in deionized water and makes oxidizing agent solution, oxidizing agent solution is joined in monomer solution, after mixed reaction solution reacts completely in the water bath of certain temperature, by product separation out, poly-Resorcinol is namely obtained.
2. the method for the poly-Resorcinol of a kind of simple and effective synthesis according to claim 1, it is characterized in that, described sour water medium comprises sulphuric acid soln, hydrochloric acid soln or acetum.
3. the method for the poly-Resorcinol of a kind of simple and effective synthesis according to claim 1, it is characterized in that, described oxygenant is selected from ammonium persulphate, Potassium Persulphate or ammonium persulphate and Potassium Persulphate arbitrary proportion mixture.
4. the method for the poly-Resorcinol of a kind of simple and effective synthesis according to claim 1, it is characterized in that, described oxygenant and the mol ratio of Resorcinol are 0.5:1 ~ 4:1.
5. the method for the poly-Resorcinol of a kind of simple and effective synthesis according to claim 4, it is characterized in that, described oxygenant and the mol ratio of Resorcinol are 0.5:1 ~ 2:1.
6. the method for the poly-Resorcinol of a kind of simple and effective synthesis according to claim 1, it is characterized in that, the oxidizing agent solution mode joined in monomer solution is that disposable impouring or dropping add, and rate of addition is 1/3 seconds.
7. the method for the poly-Resorcinol of a kind of simple and effective synthesis according to claim 1, is characterized in that, temperature of reaction be room temperature to 90 DEG C, the reaction times is 6h ~ 72h.
8. the method for the poly-Resorcinol of a kind of simple and effective synthesis according to claim 7, it is characterized in that, temperature of reaction is 40 ~ 80 DEG C, and the reaction times is 24h.
9. the method for the poly-Resorcinol of a kind of simple and effective synthesis according to claim 1, it is characterized in that, product separation mode is: by reaction soln centrifugal treating, after thing sedimentation to be polymerized, supernatant liquid is sucked and uses deionized water wash polymkeric substance, recentrifuge after dispersion; Repeat above operation, until supernatant liquid is clarified and used 0.01mol/LBaCl 2solution detects without SO 4 2-till ion.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111073550A (en) * 2019-12-23 2020-04-28 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of graphene oxide-ammonia-hydroquinone conductive binder

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070072940A1 (en) * 2005-09-28 2007-03-29 Sal Abraham Use of quinol derivatives thereof for cosmetic, dietary supplement or pharmaceutical compositions and compositions thereby obtained.
CN104280436A (en) * 2014-10-14 2015-01-14 广州盈思传感科技有限公司 Preparation method of glassy carbon electrode for detecting pyrocatechol and/or paradioxybenzene in water

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
US20070072940A1 (en) * 2005-09-28 2007-03-29 Sal Abraham Use of quinol derivatives thereof for cosmetic, dietary supplement or pharmaceutical compositions and compositions thereby obtained.
CN104280436A (en) * 2014-10-14 2015-01-14 广州盈思传感科技有限公司 Preparation method of glassy carbon electrode for detecting pyrocatechol and/or paradioxybenzene in water

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张爱娟等: "氧化还原活性的聚对苯二酚的研究进展", 《高分子通报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111073550A (en) * 2019-12-23 2020-04-28 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of graphene oxide-ammonia-hydroquinone conductive binder

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