阅读说明：本技术 一种多环线性聚合物及其制备方法 (Polycyclic linear polymer and preparation method thereof ) 是由 陈栋阳 李梦琴 林梅金 于 2021-02-24 设计创作，主要内容包括：本发明属于材料技术领域,具体涉及一种多环线性聚合物及其制备方法。本发明通过先合成环氧化柱[5]芳烃,然后将其与等摩尔量的双酚化合物聚合,得到一种新型多环线性聚合物。所得多环线性聚合物是一种热塑性高分子材料,分子量高,可溶于二氯甲烷、氯仿、N,N-二甲基甲酰胺等常见溶剂中,且能由溶液铺膜,所得膜具有良好的机械性能。(The invention belongs to the technical field of materials, and particularly relates to a polycyclic linear polymer and a preparation method thereof. The invention synthesizes epoxidation column [5] arene firstly, and then polymerizes the epoxidation column [5] arene with equimolar bisphenol compound to obtain a novel polycyclic linear polymer. The obtained polycyclic linear polymer is a thermoplastic high molecular material, has high molecular weight, can be dissolved in common solvents such as dichloromethane, chloroform, N-dimethylformamide and the like, can be spread into a film from a solution, and has good mechanical properties.)

1. A polycyclic linear polymer, wherein the polymer has the formula:

wherein n = 10 to 100,

，

。

2. the method for preparing the polycyclic linear polymer according to claim 1, comprising the following steps:

(1) at room temperature, adding dihydroxy column [5] arene, epichlorohydrin and potassium carbonate into N-methylpyrrolidone, reacting under the protection of nitrogen, extracting reactants by using dichloromethane and deionized water, collecting a dichloromethane phase, adding excessive anhydrous sodium sulfate, drying, performing rotary evaporation on filtered liquid to remove dichloromethane, and separating obtained solid by column chromatography to obtain epoxidized column [5] arene; structural formula is

；

(2) At room temperature, the epoxidation column [5] arene, the bisphenol compound and the sodium hydroxide are added into N-methyl pyrrolidone to react under the protection of nitrogen, then the reactant is poured into deionized water, and the polycyclic linear polymer is obtained after the solid is filtered, collected and dried in vacuum.

3. The method of claim 2, wherein the ratio of the mass of the dihydroxyl column [5] arene to the volume of the N-methylpyrrolidone in step (1) is 1: 5 to 100.

4. The method for preparing polycyclic linear polymer according to claim 2, wherein the molar ratio of the dihydroxyl column [5] arene, epichlorohydrin and potassium carbonate in the step (1) is 1: 10-40: 5 to 20.

5. The method for preparing the polycyclic linear polymer according to claim 2, wherein the amount of the N-methylpyrrolidone solvent added in the step (1) is 2 to 10 times the mass of epichlorohydrin.

6. The method for preparing the polycyclic linear polymer according to claim 2, wherein the reaction under nitrogen in the step (1) is carried out for 6 to 12 hours while the temperature is raised to 60 to 100 ℃.

7. The method of claim 2, wherein the molar ratio of the column [5] arene oxide, the bisphenol compound and the sodium hydroxide in the step (2) is 1: 1: 2-10; the ratio of the mass of the epoxidation column [5] arene to the volume of the N-methylpyrrolidone is 1: 2.5 to 10.

8. The method of claim 2, wherein the bisphenol compound in step (2) is bisphenol a or bisphenol AF.

9. The method for preparing the polycyclic linear polymer according to claim 2, wherein the reaction under nitrogen in the step (2) is carried out at 60 to 100 ℃ for 16 to 50 hours.

10. The method for preparing the polycyclic linear polymer according to claim 2, wherein the vacuum drying is specifically drying in a vacuum oven at 80-120 ℃ for 10-16 hours.

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a polycyclic linear polymer and a preparation method thereof.

Background

Column [5]]Aromatic hydrocarbon is an electron-rich macrocyclic molecule, has the advantages of simple synthesis, good structural symmetry, strong chemical modification, capability of complexing with various guest molecules and the like, is widely concerned in the field of supermolecular chemistry, and is used for preparing stimuli-responsive materials, adsorption and separation materials, phase transfer catalysts, organic and inorganic hybrid materials, biological materialsPlays a great role in medicine, artificial transmembrane channels and the like. For example, by placing a fully hydroxyl column [5]]The aromatic hydrocarbon is piled up to prepare a low-density solid state supermolecule organic framework porous material (P5-SOF), the material can adsorb carbon dioxide with high selectivity, and the adsorption of the carbon dioxide generated in the gas treatment after combustion and the natural gas desulfurization has great potential (adv. mater. 2014, 26, 7027-); subjecting the whole quinone column [5]]The aromatic hydrocarbon is used as a negative electrode of the organic lithium battery and shows excellent electrode performance: average operating voltage is about 2.6V, and initial capacity is as high as 418mAh g^-1And has stable cycle performance (J. Am. chem. Soc. 2014, 136(47): 16461-16464); column [5] modified with hydrophilic polymer such as polyethylene glycol (PEG), Polyglutamine (PGA), Polycaprolactone (PCL), etc]Aromatic hydrocarbon is easy to form nano particles such as vesicles and micelles, and can be used in the field of drug loading and delivery; column [5]]The arene can also be modified on the surface of inorganic porous materials such as mesoporous silicon nanoparticles, porous cerium oxide nanoparticles, graphene, metal organic framework Materials (MOFs) and the like, so as to prepare a multifunctional supramolecular transmission system for detection and imaging.

The invention synthesizes the epoxidation column [5] arene firstly, and then copolymerizes the epoxidation column [5] arene with the bisphenol compound to obtain a novel polycyclic linear polymer, which has important significance for the fields of high molecular materials and supramolecular materials.

Disclosure of Invention

The invention aims to provide a polycyclic linear polymer and a preparation method thereof. The obtained polycyclic linear polymer is a thermoplastic high molecular material, has high molecular weight, can be dissolved in common solvents such as dichloromethane, chloroform, N-dimethylformamide and the like, can be spread into a film from a solution, and has good mechanical properties.

A polycyclic linear polymer having the chemical formula:

wherein n = 10 to 100,

，

。

the preparation method of the polycyclic linear polymer comprises the following steps:

(1) adding dihydroxy column [5] arene, epichlorohydrin and potassium carbonate into N-methylpyrrolidone at room temperature, heating to 60-100 ℃ under the protection of nitrogen, reacting for 6-12 hours, extracting reactants by using dichloromethane and deionized water, collecting a dichloromethane phase, adding excessive anhydrous sodium sulfate, drying, performing rotary evaporation on the filtered liquid to remove dichloromethane, and separating the obtained solid by column chromatography to obtain epoxidation column [5] arene;

(2) adding the epoxidation column [5] arene, a bisphenol compound and sodium hydroxide into N-methyl pyrrolidone at room temperature, heating to 60-100 ℃ under the protection of nitrogen, reacting for 16-50 hours, then pouring reactants into deionized water, filtering, collecting solids, and drying in a vacuum oven at 80-120 ℃ for 10-16 hours to obtain the polycyclic linear polymer. The reaction process is as follows:

wherein n = 10 to 100,

，

。

the ratio of the mass of the dihydroxy column [5] arene to the volume of the N-methylpyrrolidone in the step (1) is 1: 5 to 100.

In the step (1), the molar ratio of dihydroxy column [5] arene, epichlorohydrin to potassium carbonate is 1: 10-40: 5 to 20.

The adding amount of the N-methylpyrrolidone solvent in the step (1) is 2-10 times of the mass of the epichlorohydrin.

The ratio of the mass of the epoxidized column [5] arene to the volume of the N-methylpyrrolidone in the step (2) is 1: 2.5 to 10.

The bisphenol compound in the step (2) is bisphenol A or bisphenol AF.

The molar ratio of the aromatic hydrocarbon in the epoxidation column [5], the bisphenol compound and the sodium hydroxide in the step (2) is 1: 1: 2 to 10.

Compared with the prior art, the invention has the following beneficial effects:

(1) the obtained polycyclic linear polymer has an electron-rich macrocyclic structure, can increase the entanglement and even the interpenetration complexation of molecules, and is favorable for improving the mechanical property of the product;

(2) the obtained polycyclic linear polymer is a thermoplastic high molecular material, has excellent solubility, film forming property and the like, is easy to dissolve in common solvents such as dichloromethane, acetone and the like, and is convenient to process and form;

(3) the obtained polycyclic linear polymer can complex guest small molecules and has potential application in the fields of molecular probes, separation, adsorption and the like.

Drawings

FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a bisphenol A type polycyclic linear polymer in example 1;

FIG. 2 is an infrared spectrum of a bisphenol A type polycyclic linear polymer in example 1;

FIG. 3 is a NMR spectrum of a bisphenol AF-type polycyclic linear polymer in example 2;

FIG. 4 is an infrared spectrum of a bisphenol AF-type polycyclic linear polymer in example 2;

FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of a mixture of 1, 4-dibromobutane of example 3 and a polycyclic linear polymer of bisphenol A type prepared in example 1;

FIG. 6 is a NMR hydrogen spectrum of a mixture of 1, 4-dibromobutane of example 3 and a bisphenol AF-type polycyclic linear polymer prepared in example 2.

Detailed Description

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.

EXAMPLE 1 preparation of bisphenol A polycyclic Linear Polymer

(1) At room temperature, adding 0.01mol (7.2283 g) of dihydroxy column [5] arene monomer, 0.15mol (13.8780 g) of epichlorohydrin, 0.1mol (13.821 g) of potassium carbonate and 100mL of N-methylpyrrolidone into a 250mL three-neck flask, heating to 90 ℃ under the protection of nitrogen, magnetically stirring for reaction for 12 hours, extracting a reactant with 300mL of dichloromethane and 300mL of deionized water, collecting a dichloromethane phase, adding excessive anhydrous sodium sulfate for drying, removing dichloromethane by rotary evaporation of filtered liquid, and separating the obtained solid by column chromatography to obtain epoxidation column [5] arene, wherein the yield is 70%;

(2) at room temperature, 2mmol (1.6687 g) of the compound, 2mmol (0.4566 g) of bisphenol A, 0.025mol (1.0 g) of sodium hydroxide and 5mL of N-methylpyrrolidone are added into a 25mL three-neck flask, the temperature is raised to 90 ℃ under the protection of nitrogen, magnetic stirring is carried out for reaction for 48 hours, then the reactant is poured into deionized water, vacuum filtration is carried out to collect solid, and the solid is placed in a vacuum oven to be dried for 12 hours at 120 ℃ to obtain the bisphenol A type polycyclic linear polymer. The obtained polycyclic linear polymer has a number average molecular weight of 23 kDa, a weight average molecular weight of 46 kDa and a polydispersity of 2.0 by gel permeation chromatography. The glass transition temperature of the obtained polycyclic linear polymer is 112 ℃ by the characterization of a differential scanning calorimeter.

EXAMPLE 2 preparation of bisphenol AF-type polycyclic Linear Polymer

(1) At room temperature, 5mmol (3.6142 g) of dihydroxy column [5] arene monomer, 0.15mol (13.8780 g) of epichlorohydrin, 0.05mol (6.9105 g) of potassium carbonate and 80mL of N-methylpyrrolidone are added into a 250mL three-neck flask, the temperature is raised to 90 ℃ under the protection of nitrogen, magnetic stirring is carried out for reaction for 12 hours, then the reactant is extracted by 300mL of dichloromethane and 300mL of deionized water, a dichloromethane phase is collected, excessive anhydrous sodium sulfate is added for drying, dichloromethane is removed by rotary evaporation of filtered liquid, the obtained solid is separated by column chromatography to obtain epoxidation column [5] arene, and the yield is 63%.

(2) At room temperature, 1mmol (0.8344 g) of the compound, 1mmol (0.3620 g) of hexafluorobisphenol A (bisphenol AF), 5mmol (0.2 g) of sodium hydroxide and 5mL of N-methylpyrrolidone are added into a 25mL three-neck flask, the temperature is raised to 90 ℃ under the protection of nitrogen, magnetic stirring is carried out for reaction for 48 hours, then the reactant is poured into deionized water, vacuum filtration is carried out to collect solid, and the solid is placed in a vacuum oven to be dried for 12 hours at 120 ℃ to obtain the bisphenol AF type polycyclic linear polymer. The obtained polycyclic linear polymer has the number average molecular weight of 33 kDa, the weight average molecular weight of 59 kDa and the polydispersity number of 1.8 by characterization of gel permeation chromatography. The glass transition temperature of the obtained polycyclic linear polymer is 127 ℃ by the characterization of a differential scanning calorimeter.

Example 3 Performance testing

And (3) testing a chemical structure: chemical structures were characterized by nuclear magnetic resonance hydrogen spectroscopy and infrared spectroscopy. The NMR spectrum of the bisphenol A type polycyclic linear polymer in example 1 is shown in FIG. 1: 6.64-6.87 ppm are chemical shifts of hydrogen of the benzene ring on the column [5] arene, 3.55-3.81 ppm are chemical shifts of hydrogen of the methyl group and the methylene group on the column [5] arene, 1.67 ppm is chemical shift of hydrogen of the methyl group on bisphenol A, and 6.87, 7.16 ppm are chemical shifts of hydrogen of the benzene ring on bisphenol A.

The IR spectrum of the bisphenol A polycyclic linear polymer of example 1 is shown in FIG. 2: 3443 cm^-1The left and the right are O-H stretching vibration peaks; 2930 cm^-1The left and the right are stretching vibration peaks of C-H on a benzene ring; 2831 cm^-1The left and right are C-H stretching vibration peaks of methyl and methylene; 1460 cm^-1The left and right are C-H bending vibration peaks of methylene; 1250 cm^-1The left and right are C-H bending vibration peaks of methyl; 1507 cm^-1The left and right are stretching vibration peaks of benzene ring C = C.

The NMR spectrum of the bisphenol AF-type polycyclic linear polymer in example 2 is shown in FIG. 3: 6.6-6.9 ppm are chemical shifts of hydrogen of the benzene ring on the column [5] arene, 3.49-3.81 ppm are chemical shifts of hydrogen of the methyl group and the methylene group on the column [5] arene, 1.60 ppm is chemical shift of hydrogen of the methyl group on the bisphenol AF, and 6.93, 7.33 ppm are chemical shifts of hydrogen of the benzene ring on the bisphenol AF.

The IR spectrum of the bisphenol AF-type polycyclic linear polymer in example 2 is shown in FIG. 4: 3453 cm^-1The left and the right are O-H stretching vibration peaks; 2938 cm^-1The left and the right are stretching vibration peaks of C-H on a benzene ring; 2831 cm^-1The left and right are C-H stretching vibration peaks of methyl and methylene; 1463 cm^-1The left and right are C-H bending vibration peaks of methylene; 1258 cm^-1The left and right are C-H bending vibration peaks of methyl; 1509 cm^-1The left and right are stretching vibration peaks of benzene ring C = C; 1167. 1211 cm^-1The C-F stretching vibration peak is shown on the left and the right.

Dissolution property: 0.1g of the bisphenol A type polycyclic linear polymer prepared in example 1 and the bisphenol AF type polycyclic linear polymer prepared in example 2 were taken and added to glass bottles containing 2mL of dichloromethane, acetone, chloroform, N-methylpyrrolidone, N-dimethylacetamide and N-methylpyrrolidone, respectively, the polymer and the solvent were sufficiently contacted by shaking, and after standing for several minutes, the solution in each glass bottle was clear and transparent, which indicated that the polymer had good solubility in each solvent.

Complexing function: after 2mg of guest molecule 1, 4-dibromobutane was mixed with 10mg of the bisphenol A type polycyclic linear polymer prepared in example 1 and the bisphenol AF type polycyclic linear polymer prepared in example 2, respectively, and dissolved in deuterated chloroform, the nuclear magnetic resonance hydrogen spectra thereof were measured, and the results are shown in FIGS. 5 and 6. And shifting a plurality of proton peaks of the polycyclic linear polymer to a low field, and simultaneously eliminating two proton peaks of the guest molecule, so that the polycyclic linear polymer and the guest molecule are subjected to complexation to form an inclusion complex.

Mechanical properties: 1g of the bisphenol A polycyclic linear polymer prepared in example 1 and the bisphenol AF polycyclic linear polymer prepared in example 2 were dissolved in 20mL of methylene chloride, respectively, cast onto a clean glass plate, dried in an oven at 80 ℃ for 20 hours, and after the glass plate was cooled to room temperature, immersed in deionized water until the film peeled off the glass plate. The tensile strength of the bisphenol A type polycyclic linear polymer film is 30.6MPa, and the elongation at break is 43 percent; the bisphenol AF type polycyclic linear polymer film had a tensile strength of 37.4MPa and an elongation at break of 52%.

The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.