阅读说明：本技术 一种蒽主链型自具微孔聚合物及其合成方法与应用 (Anthracene main chain type self-possessed microporous polymer and synthesis method and application thereof ) 是由 赵强 唐清泉 董志月 于 2019-11-08 设计创作，主要内容包括：本发明涉及一种蒽主链型自具微孔聚合物及其合成方法与应用,属于高分子领域。所述聚合物的分子量为4000-400000,分子量分布为1.15-3.50,比表面积为50-800m<Sup>2</Sup>/g。制备方法为：2,6-二氨基蒽与马来酰亚胺发生狄尔斯-阿尔德反应,或者2,6-二氨基蒽与马来酰亚胺衍生物发生狄尔斯-阿尔德反应,得到双苯胺单体；利用朝格尔碱反应使双苯胺单体发生缩聚反应,得到聚合物；再利用狄尔斯-阿尔德反应的逆反应脱去马来酰亚胺或马来酰亚胺衍生物,即得到蒽主链型自具微孔聚合物。本发明采用马来酰亚胺或者马来酰亚胺衍生物作为蒽官能团的保护基,所合成的聚合物具有微孔结构、可溶性和光敏特性,能够作为一种光敏化剂,应用于降解有机污染物和光动力制剂等领域。(The invention relates to an anthracene main chain type self-possessed microporous polymer and a synthesis method and application thereof, belonging to the field of macromolecules. The molecular weight of the polymer is 4000-400000, the molecular weight distribution is 1.15-3.50, and the specific surface area is 50-800m 2 (ii) in terms of/g. The preparation method comprises the following steps: carrying out Diels-Alder reaction on 2, 6-diaminoanthracene and maleimide, or carrying out Diels-Alder reaction on 2, 6-diaminoanthracene and a maleimide derivative to obtain a dianiline monomer; carrying out polycondensation reaction on a dianiline monomer by using a troger base reaction to obtain a polymer; reuse of Diels-AlderRemoving maleimide or maleimide derivative by reverse reaction of the Alder reaction to obtain the anthracene main chain type self-possessed microporous polymer. The invention adopts maleimide or maleimide derivatives as protecting groups of anthracene functional groups, and the synthesized polymer has microporous structure, solubility and photosensitive property, can be used as a photosensitizer, and can be applied to the fields of degrading organic pollutants, photodynamic preparations and the like.)

1. An anthracene main chain type self-contained microporous polymer is characterized in that the structural formula of the polymer is shown as a formula I; the rigid trapezoidal and bridge ring twisted structure of the polymer enables the polymer to be provided with micropores;

wherein the value range of n is 15-1500, and n is a positive integer.

2. The anthracene main chain type self-microporous polymer according to claim 1, wherein the polymer has a number average molecular weight of 4000-400000, a molecular weight distribution of 1.15-3.50, and a specific surface area of 50m²/g-800m²/g。

3. The method for producing the anthracene main chain type self-possessed microporous polymer according to claim 1 or 2, comprising the steps of:

(1) carrying out Diels-Alder reaction on 2, 6-diaminoanthracene and maleimide or carrying out Diels-Alder reaction on 2, 6-diaminoanthracene and maleimide derivative to obtain a dianiline monomer, so that an anthracene functional group is protected;

(2) carrying out polycondensation reaction on the dianiline monomer obtained in the step (1) by using a troger base reaction to obtain a polymer;

(3) and then removing maleimide or maleimide derivatives by using the reverse reaction of the Diels-Alder reaction to obtain the anthracene main chain type self-possessed microporous polymer.

4. The process according to claim 3, wherein the maleimide derivative of step (1) is N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide or N- (4-nitrophenyl) maleimide.

5. The preparation method according to claim 3, wherein the step (1) is specifically: blending and dissolving 2, 6-diaminoanthracene and maleimide with the same amount of substances in an organic solvent, or blending and dissolving 2, 6-diaminoanthracene and maleimide derivatives with the same amount of substances in an organic solvent, deoxidizing, placing at 60-80 ℃, stirring for reaction for at least 12 hours, and separating and purifying by using a chromatographic column to obtain the dianiline monomer.

6. The method according to claim 5, wherein the organic solvent is N, N-dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone.

7. The process according to claim 3, wherein the reaction temperature for removing the maleimide or maleimide derivative in the step (3) is 100 ℃ to 180 ℃ and the reaction time is 6 hours to 24 hours.

8. Use of the anthracene backbone-type self-supporting microporous polymer according to claim 1 or 2 as a photosensitizer.

9. Use of the anthracene backbone-type self-possessed microporous polymer according to claim 1 or 2 for degrading organic contaminants or as a photodynamic agent.

10. The application according to claim 8, characterized in that it is specifically: and uniformly dispersing the anthracene main chain type self-provided microporous polymer in water, and irradiating the solution by using visible light to enable the anthracene main chain type self-provided microporous polymer to catalyze oxygen dissolved in the water to react to generate singlet oxygen.

Technical Field

The invention belongs to the field of high molecular polymers, and particularly relates to an anthracene main chain type self-possessed microporous polymer and a synthesis method and application thereof.

Background

The polymer with micropores inhibits the free rotation of chain conformation in space by constructing a polymer chain with rigidity combined with a twisted structure, and the introduction of the twisted structure makes the polymer chain difficult to be regular on space stacking, so that a cavity or a larger free volume is generated. Compared with a three-dimensional framework porous material, the polymer with the micropores has high specific surface area and processability, so that the polymer has remarkable application in the fields of membrane separation, catalysis and the like and is concerned.

At present, nucleophilic substitution reaction (p.m. budd et al.chem.commun.2004,230) and troger's base reaction (m.carta et al.science 2013,339,303) are the main synthetic methods for polymers with micropores. The nucleophilic substitution reaction mainly utilizes the intermolecular polycondensation reaction of the catechol and the o-difluoro monomer, and realizes a polymer chain with rigidity and a twisted structure through the monomer with the twisted structure and the formed dioxin trapezoid structure. In the Schwerer's alkali reaction, diphenylamine is used as a raw material, trifluoroacetic acid is used as a catalyst, and a rigid bridge ring structure is constructed to obtain the self-prepared microporous polymer. Subsequently, norbornene-arene cyclization reactions (S.Liu et al.J.am.chem.Soc.2014,136,17434) and self-accelerating reactions (L.I.Olvera et al.macromolecules,2017,50,8480-8486) were also used for the synthesis of self-microporous polymers.

The anthracene group has a strong pi conjugation effect, so that the anthracene group has strong visible light absorption and fluorescence emission capability and a narrow optical band gap, and has potential application values in the fields of fluorescent probes, heavy metal detection and light emitting diodes. The synergistic combination of the anthracene functional group and the microporous structure endows the material with the properties different from those of the traditional microporous polymer, and has potential application value in the photoelectric field. However, the unique pi-conjugation effect and the large planar rigid structure of anthracene groups make it difficult to prepare anthracene backbone-type self-possessed microporous polymers directly using the developed synthetic methods.

Disclosure of Invention

The invention solves the problem that the anthracene main chain type self-prepared microporous polymer is difficult to prepare due to the unique pi conjugate effect and the larger plane rigid structure of the anthracene group in the prior art. The invention provides an anthracene main chain type self-micropore polymer and a synthesis method and application thereof.

According to the first aspect of the invention, an anthracene main chain type self-contained microporous polymer is provided, wherein the structural formula of the polymer is shown as a formula I; the rigid trapezoidal and bridge ring twisted structure of the polymer enables the polymer to be provided with micropores;

wherein the value range of n is 15-1500, and n is a positive integer.

Preferably, the polymer has a number average molecular weight of 4000-400000, a molecular weight distribution of 1.15-3.50 and a specific surface area of 50m²/g-800m²/g。

According to another aspect of the present invention, there is provided a method for preparing the anthracene main chain type polymer having micropores, comprising the steps of:

(1) carrying out Diels-Alder reaction on 2, 6-diaminoanthracene and maleimide or carrying out Diels-Alder reaction on 2, 6-diaminoanthracene and maleimide derivative to obtain a dianiline monomer, so that an anthracene functional group is protected;

(2) carrying out polycondensation reaction on the dianiline monomer obtained in the step (1) by using a troger base reaction to obtain a polymer;

(3) and then removing maleimide or maleimide derivatives by using the reverse reaction of the Diels-Alder reaction to obtain the anthracene main chain type self-possessed microporous polymer.

Preferably, the maleimide derivative of step (1) is N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide or N- (4-nitrophenyl) maleimide.

Preferably, the step (1) is specifically: blending and dissolving 2, 6-diaminoanthracene and maleimide with the same amount of substances in an organic solvent, or blending and dissolving 2, 6-diaminoanthracene and maleimide derivatives with the same amount of substances in an organic solvent, deoxidizing, placing at 60-80 ℃, stirring for reaction for at least 12 hours, and separating and purifying by using a chromatographic column to obtain the dianiline monomer.

Preferably, the organic solvent is N, N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone.

Preferably, the reaction temperature for removing the maleimide or maleimide derivative in the step (3) is 100-180 ℃, and the reaction time is 6-24 h.

According to another aspect of the present invention, there is provided the use of the anthracene main chain type polymer having micropores of its own as a photosensitizer.

Preferably, the application is specifically: and uniformly dispersing the anthracene main chain type self-provided microporous polymer in water, and irradiating the solution by using visible light to enable the anthracene main chain type self-provided microporous polymer to catalyze oxygen dissolved in the water to react to generate singlet oxygen.

According to another aspect of the present invention, there is provided the use of the anthracene backbone-type polymer having micropores of its own for degrading organic contaminants or as a photodynamic agent.

In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:

(1) the invention takes maleimide or maleimide derivative as a protective group, protects and deprotects an anthracene functional group through Diels-Alder reaction and reverse reaction thereof, and develops a synthetic method of an anthracene main chain type self-contained microporous polymer. The method overcomes the difficulty that diaminoanthracene can not be directly synthesized into the polymer with micropores by utilizing a Scherger's base reaction, and skillfully realizes the combination of anthracene functional groups and the structure with micropores. The synthesized polymer has a microporous structure, solubility and photosensitive characteristics, can be used as a photosensitizer, and is applied to the fields of photodynamic preparations and the like.

(2) The polymer prepared by the invention has the number average molecular weight of 4000-400000, the molecular weight distribution of 1.15-3.50 and the specific surface area of 50m²/g-800m²(ii) in terms of/g. The unique anthracene rigid plane and bridge ring twisted structure makes the macromolecular chains difficult to regularly stack in spatial arrangement and has micropores. The specific surface area of the polymer has a certain relation with the molecular weight, and the correlation between the molecular weight and the microporous structure and the specific surface area can be further understood by representing the specific surface area and the microporous structure of the polymers with different molecular weights, so that a corresponding theoretical basis is provided for the subsequent development of the material.

(3) The anthracene main chain type self-contained microporous polymer synthesized by the method is proved to have strong visible light absorption and fluorescence emission capabilities through characteristics such as solid ultraviolet spectrum and fluorescence spectrum, and can generate stronger photogenerated charge carriers. Through nitrogen adsorption/desorption equilibrium test, the material is proved to have higher specific surface area and microporous structure. The photoelectric properties of this material are due to the main chain anthracene functional group, and its microporous structure is mainly derived from the irregular packing of rigid twisted conformations. Compared with other self-prepared microporous polymers, the material has strong photoelectric property and can absorb and convert light energy into chemical energy; compared with conjugated polymer, the material has excellent machinability, can be made into various forms such as particles, fibers, membranes and the like, and meanwhile, the microporous structure is favorable for energy transfer between two phase interfaces, thereby greatly improving the catalytic efficiency of the material. In a word, the material is an excellent photosensitizer under the irradiation of visible light, can catalyze oxygen to be converted into singlet oxygen, and can be used in the fields of organic pollutant degradation, photodynamic preparations and the like.

Drawings

FIG. 1 is a scheme showing the synthesis scheme of an anthracene backbone-type self-microporous polymer of the present invention.

FIG. 2 is a GPC outflow graph of the anthracene backbone-type self-microporous polymer of example 1.

FIG. 3 is a drawing showing nitrogen adsorption/desorption of the anthracene main chain type self-supporting microporous polymer in example 7.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.