阅读说明：本技术 一种手性自具微孔聚合物及其制备方法与应用 (Chiral self-possessed microporous polymer and preparation method and application thereof ) 是由 王新波 马小华 韩召斌 丁奎玲 于 2020-12-21 设计创作，主要内容包括：本发明涉及一种手性自具微孔聚合物及其制备方法与应用,具有如下式I所示的手性可溶性链状自聚微孔聚合物或所述聚合物的对映体或非对映异构体,本发明的可溶性自具微孔聚合物膜对二氧化碳/甲烷、二氧化碳/氮气、氧气/氮气、二氧化碳/甲烷、氦气/甲烷、氦气/氮气等气体选择性很高,高于文献中同类材料的选择性,可满足气体实际分离应用的要求。(The invention relates to a chiral self-microporous polymer and a preparation method and application thereof, wherein the chiral soluble chain self-microporous polymer or an enantiomer or a diastereoisomer of the polymer is shown in the following formula I.)

1. A chiral soluble chain-like self-polymeric microporous polymer having the formula I below or an enantiomer or diastereomer of the polymer:

wherein X is CR₅R₆、NR₇O or S; r₁、R₂、R₃、R₄、R₅、R₆、R₇Each independently is hydrogen, alkyl, cycloalkyl, alkoxy, aryl, fluoro, chloro, bromo, iodo, hydroxy, or mercapto; m is a positive integer, and n and z are 0 or positive integers.

2. The chiral soluble chain-like self-polymerization microporous polymer according to claim 1, wherein m, n and z are positive integers of 1 or more.

3. The chiral soluble chain-like self-polymeric microporous polymer of claim 1,characterized in that A is₁The structure of the monomer is one of the following polyphenol structures or the mixture of the following two structures and above:

4. the chiral soluble chain-like self-polymerizable microporous polymer according to claim 1, wherein A is₂The structure of the monomer is one of the following structures or the mixture of the following structures and more than two structures:

5. the chiral soluble chain-like self-polymerization microporous polymer according to claim 1, wherein the spiroindane unit in the structure shown in formula I is single chiral or enantiomer mixed polymerization, and the spiroindane unit structure is shown in formula II below:

6. the preparation process of chiral and spiral indan chain polymer with micropores includes the following steps:

mixing A1 monomer, A2 monomer and K₂CO₃Adding the mixture into a container with a volume ratio of 2-10: 1 in a mixed solvent of N-methylpyrrolidone and toluene, reacting for 3-8 hours at a constant temperature of 130-180 ℃, cooling a reaction system to room temperature, slowly pouring into a methanol solution, carrying out suction filtration to obtain a bright yellow polymer, sequentially washing with methanol and distilled water for 3-5 times, drying overnight at a temperature of 100-160 ℃ under a vacuum condition to obtain a yellow fluorescent product polymer, wherein the specific surface area range is 50m²G to 2000m²/g。

7. The preparation method according to claim 6, wherein the molar volume ratio of the A1 monomer to the mixed solvent is: 0.01 (20-35), unit, mol/mL.

8. An application of a chiral soluble chain-like self-polymerization microporous polymer shown as the following formula I in fluid separation or preparation of a luminescent film.

9. The use according to claim 8, wherein the luminescent film is prepared by:

dissolving a chiral soluble chain-like self-polymerization microporous polymer shown as the following formula I into chloroform to prepare a solution with the concentration of 1-5 wt%, filtering, pouring the filtrate into a mold, and slowly volatilizing the solvent at room temperature to obtain a yellow polymer membrane; the membrane is soaked in methanol for 24 hours and then taken out and dried to obtain the polymer membrane treated by the methanol.

Technical Field

The invention relates to a chiral self-contained microporous polymer and a preparation method and application thereof, belonging to the technical field of organic high molecular materials.

Background

The membrane separation technology has the functions of separation, concentration, purification and the like, has the unique advantages of high efficiency, low energy consumption, simple operation, easy large-scale production, environmental friendliness and the like, is widely applied in the fields of chemical industry, medicine, food, energy and the like, and generates huge economic and social benefits. However, the traditional membrane separation materials are difficult to be compatible with high permeability and high selectivity, and cannot meet the increasing industrial production requirements, so that the development of a membrane material with high permeability and high selectivity is one of the research hotspots in the chemical separation field at present. In 2004, Budd et al reported a class of rigid, twisted structure-containing chain-like self-microporous Polymers (PIMs), which cannot rotate freely due to the rigidity of the polymer backbone, so that the molecular chains cannot be effectively stacked, thereby forming an inherent continuous microporous structure inside the material, and the obtained membrane material has good gas flux and selectivity, and exhibits certain superiority in gas separation. Wherein PIM-1 is the best representative of PIMs due to the advantages of easily available raw materials, good film forming property and the like, and a large number of reports are made on the work of improving the gas separation performance based on post-modification and functionalization of PIM-1. However, the synthesis method of the PIM-1 monomer 5,5 ', 6, 6 ' -tetrahydroxy-3, 3, 3 ', 3 ' -tetramethyl-1, 1 ' -spirobiindan (TTSBI) limits, and the quaternary carbon center of the spirobiindan is difficult to improve, which is exactly the source part of PIM-1 pore formation. The development of a new spiral structure is an urgent problem to be solved in the current scientific research work for improving the pore structure of the separation membrane and improving the gas separation performance.

On the other hand, the PIMs membrane has been studied more in the field of gas membrane separation, but there is no research on liquid phase separation, especially chiral separation of liquid phase molecules, due to the lack of chiral PIMs membrane material. Kenneth J.Shea et al reported that chiral TTSBI was obtained by chiral resolution in 2015, and then condensed with 2, 3, 5, 6-tetrafluoroterephthalonitrile to prepare chiral PIM-1, which was used for chiral membrane separation of small molecules (Angew. chem. int. Ed.2015,54, 11214-. However, the chiral precursor molecular skeleton structure obtained by chiral resolution is still limited in PIM-1, only one chiral center in the TTSBI structure is in a face chirality mode, and a chiral reagent for resolution is expensive, low in resolution efficiency and difficult to produce in a large scale. Therefore, the development of novel PIMs (layered interpenetrating polymer membranes) with framework chirality has important academic significance, and new technologies are likely to be generated in the field of chiral membrane separation.

In addition, the chiral film material has great application potential in the circular polarization luminescent material (for example, in the aspect of developing a novel circular polarization luminescent material with strong solid state fluorescence).

Chinese patent documents CN201510974151.1 and International patent documents PCT int.appl. (2017), WO 2017107789A 120170629 and J.Am.chem.Soc.2018,140,10374-10381 butylquinuclidine, introduce a preparation method of chiral spiro indane skeleton compounds, and directly obtain high chiral pure condensed ring spiro indane skeleton small molecule compounds without adopting chiral starting materials or chiral resolution reagents under proper catalysts. The structure is mainly applied to asymmetric catalysis at present, and is not seen as a monomer for polymer synthesis.

Through search, no document reports on a polymer material with micropores based on a polycyclic spiroindane skeleton.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a chiral self-micropore polymer and a preparation method and application thereof.

The invention is realized by the following technical scheme:

a chiral soluble chain-like self-polymeric microporous polymer having the formula I below or an enantiomer or diastereomer of the polymer:

wherein X is CR₅R₆、NR₇O or S; r₁、R₂、R₃、R₄、R₅、R₆、R₇Each independently is hydrogen, alkyl, cycloalkyl, alkoxy, aryl, fluoro, chloro, bromo, iodo, hydroxy, or mercapto; m is a positive integer, and n and z are 0 or positive integers.

More preferably, m, n and z are positive integers of 1 or more.

According to a preferred embodiment of the invention, A₁The structure of the monomer is one of the following polyphenol structures or the mixture of the following two structures and above:

according to a preferred embodiment of the invention, A₂The structure of the monomer is one of the following structures or the mixture of the following structures and more than two structures:

according to the invention, the structure shown in the formula I is preferably a structure in which the spiroindane unit is single chiral or mixed enantiomer, and the structure of the spiroindane unit is shown as the following formula II:

the invention also provides a preparation method of the chiral self-micropore polymer.

The preparation method of the chiral spiro indane chain-shaped polymer with micropores comprises the following steps:

mixing A1 monomer, A2 monomer and K₂CO₃Adding the mixture into a container with a volume ratio of 2-10: 1 in a mixed solvent of N-methylpyrrolidone and toluene, reacting for 3-8 hours at a constant temperature of 130-180 ℃, cooling a reaction system to room temperature, slowly pouring into a methanol solution, carrying out suction filtration to obtain a bright yellow polymer, sequentially washing with methanol and distilled water for 3-5 times, drying overnight at a temperature of 100-160 ℃ under a vacuum condition to obtain a yellow fluorescent product polymer, wherein the specific surface area range is 50m²G to 2000m²/g。

According to the invention, the molar volume ratio of the A1 monomer to the mixed solvent is preferably as follows: 0.01 (20-35), unit, mol/mL.

The preparation method of the chiral spiro indane chain-shaped polymer with micropores is shown as the following formula III:

an application of a chiral soluble chain-like self-polymerization microporous polymer shown as the following formula I in fluid separation or preparation of a luminescent film.

According to a preferred embodiment of the present invention, the luminescent film is prepared as follows:

dissolving a chiral soluble chain-like self-polymerization microporous polymer shown as a formula I into chloroform to prepare a solution with the concentration of 1-5 wt%, filtering, pouring the filtrate into a mold, and slowly volatilizing the solvent at room temperature to obtain the yellow polymer membrane. The membrane is soaked in methanol for 24 hours and then taken out and dried to obtain the polymer membrane treated by the methanol.

The polymer film of the present invention may be chirally pure or racemic.

The invention has the technical characteristics and advantages that:

1. the self-microvoiding polymers of the invention may be optically pure.

2. The polymer with micropores is soluble in organic solvents such as chloroform, tetrahydrofuran and the like, and is convenient for preparing a membrane.

3. The selectivity of the soluble polymer membrane with micropores is high for gases such as carbon dioxide/methane, carbon dioxide/nitrogen, oxygen/nitrogen, carbon dioxide/methane, helium/nitrogen and the like, is higher than that of similar materials in documents, and can meet the requirements of actual separation and application of the gases.

4. The chiral self-microporous polymer has strong fluorescence characteristics, optical rotation characteristics and chiral polarized light characteristics.

5. The raw materials are easy to obtain, the operation is simple, and the condition is mild.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of the compound 2 spiroindane unit of example 1,

FIG. 2 is a nuclear magnetic carbon spectrum of the spiroindane unit of Compound 2 of example 1,

FIG. 3 is a circular dichroism plot of the Compound 2 spiroindane unit of example 1, the solid line being the absorption curve and the dotted line being the circular dichroism plot;

FIG. 4 is a nuclear magnetic hydrogen spectrum of the chiral soluble chain-like self-polymerization microporous polymer 3 of example 1,

FIG. 5 is a plot of the nitrogen physisorption isotherm of the chiral soluble chain-like self-polymerized microporous polymer 3 of example 1;

fig. 6 is a circular dichroism graph of the chiral soluble chain-like self-polymerized microporous polymer 3 of example 1, with the solid line being an absorption curve and the dotted line being a circular dichroism curve.

Fig. 7 is a chiral fluorescence spectrum of the chiral soluble chain-like self-microporous polymer 3 of example 1.

Detailed Description

The invention will be further explained with reference to the drawings and examples.

Example 1

(1) Preparation of Polymer monomers

Preparation of compound 1 see preparation of compound 3i in document j.am.chem.soc.2018,140,10374-10381, optical purity 96% ee.

The preparation procedure of compound 2 was as follows: adding 10mmol of compound 1 dry powder into a 1L glass flask, introducing nitrogen for protection, adding 200ml of dry dichloromethane, stirring to completely dissolve compound 1, placing the reaction bottle in an ice-water bath, cooling to 0 ℃, and dropwise adding BBr into the reaction bottle₃The reaction system was gradually warmed to room temperature and stirred at room temperature for 12 hours, and then 200ml of water was slowly added to the system to quench the reaction. The separation funnel separates the phases, the aqueous phase and the partially insoluble solid are extracted with a large amount of dichloromethane and the combined dichloromethane phases are dried over anhydrous sodium sulfate, concentrated and recrystallized from methanol to provide compound 2 as an off-white solid.

The compound 2, spiroindane unit, has low solubility in solvents such as dichloromethane and ethyl acetate, and has high solubility in polar solvents such as methanol and N, N-dimethylformamide. The nuclear magnetic spectrum and the circular dichroism chart of the spiroindane unit are shown in figure 1, figure 2 and figure 3.

(2) Preparation of chiral soluble chain-like self-polymerized microporous polymer 3:

adding compound 2(0.01mol), tetrafluoroterephthalonitrile TFTPN (0.01mol) and dried potassium carbonate particles (0.025mol) into a three-necked flask under the protection of nitrogen atmosphere, adding a mixed solvent of 18ml of N, N-dimethylacetamide (DMAc) and 9ml of toluene, stirring at a constant temperature of 160 ℃ for reacting for 6 hours, removing the heated system, cooling to room temperature, pouring the reaction liquid into methanol, filtering to obtain bright yellow powder precipitate, washing with methanol and distilled water for 5 times in sequence, and drying at a vacuum condition of 110 ℃ overnight to obtain yellow fluorescent product polymer 3 powder, wherein the conversion rate is 93%, and nuclear magnetic hydrogen spectrum, physical adsorption isotherm, ultraviolet absorption and circular dichroism spectrum and chiral fluorescence spectrum of the polymer 3 are respectively shown in figures 4, 5, 6 and 7.

(3) Preparation of chiral separation membrane:

dissolving a polymer 3 in chloroform to obtain a clear solution with the mass fraction of 3%, filtering the clear solution by using an organic phase filter membrane, pouring a polymer filtrate into a horizontal crystallized polytetrafluoroethylene culture dish, slowly volatilizing a solvent at room temperature to obtain a membrane material with the thickness of 50 +/-5 microns, soaking the membrane material in methanol for 24 hours, taking out the membrane material, drying the membrane material, and placing the membrane material in a vacuum drying oven for keeping the temperature of 100 ℃ overnight. The results of permeation tests of membrane materials without and with methanol soak for each gas are shown in table 1.

TABLE 1 permeation test results of chiral separation membrane materials for individual component gases

Example 2

(1) The preparation of the polymer monomers was carried out as in example 1.

(2) Preparation of chiral soluble chain-like self-polymerized microporous polymer:

adding compound 2(0.01mol), tetrafluoroterephthalonitrile TFTPN (0.01mol) and dried potassium carbonate particles (0.030mol) into a three-necked bottle under the protection of nitrogen atmosphere, adding a mixed solvent of 18ml of N, N-dimethylacetamide (DMAc) and 4ml of toluene, stirring at a constant temperature of 180 ℃ for reaction for 4 hours, removing heat until the temperature of the system is reduced to room temperature, pouring the reaction liquid into methanol, performing suction filtration to obtain bright yellow powder precipitate, sequentially washing with methanol and distilled water for 5 times, and drying at a vacuum condition of 130 ℃ overnight to obtain yellow fluorescent product polymer powder.

(3) Preparation of chiral separation membrane example 1 was performed.