阅读说明：本技术 一种新型螺旋聚苯乙炔/硅基杂化多孔材料的制备方法 (Preparation method of novel spiral polyphenylacetylene/silicon-based hybrid porous material ) 是由 张春红 周正金 周艳丽 朱睿琪 刘旭东 刘立佳 董红星 于 2020-03-19 设计创作，主要内容包括：本发明提供了一种新型螺旋聚苯乙炔/硅基杂化多孔材料的制备方法,首先合成带有脯氨酸寡肽衍生物的苯乙炔单体,然后在铑系催化剂的作用下实现其与共聚单体的聚合,合成侧链带有脯氨酸寡肽衍生物的螺旋聚苯乙炔共聚物,利用该共聚物与二氧化硅微球种子液,通过种子生长法制备螺旋聚苯乙炔/硅基杂化多孔材料。本发明的螺旋聚苯乙炔/硅基杂化多孔材料的制备方法操作简单,反应温和,且螺旋聚苯乙炔有机组分和硅基无机组分比例可控,为有机/无机杂化材料的合成提供了新思路。本发明的螺旋聚苯乙炔/硅基杂化多孔材料可用于高效液相色谱手性固定相,具有较好的手性识别与拆分能力,在手性化合物的分离领域具有良好的应用价值及前景。(The invention provides a preparation method of a novel spiral polyphenylacetylene/silicon-based hybrid porous material, which comprises the steps of firstly synthesizing a phenylacetylene monomer with a proline oligopeptide derivative, then realizing the polymerization of the phenylacetylene monomer with the copolymerization monomer under the action of a rhodium catalyst, synthesizing a spiral polyphenylacetylene copolymer with a side chain with the proline oligopeptide derivative, and preparing the spiral polyphenylacetylene/silicon-based hybrid porous material by using the copolymer and a silicon dioxide microsphere seed solution through a seed growth method. The preparation method of the helical polyphenylacetylene/silicon-based hybrid porous material has the advantages of simple operation, mild reaction and controllable proportion of the helical polyphenylacetylene organic component and the silicon-based inorganic component, and provides a new idea for synthesis of organic/inorganic hybrid materials. The spiral polyphenylacetylene/silicon-based hybrid porous material can be used for a chiral stationary phase of a high performance liquid chromatography, has good chiral recognition and resolution capability, and has good application value and prospect in the field of separation of chiral compounds.)

1. A preparation method of a novel spiral polyphenylacetylene/silicon-based hybrid porous material is characterized by comprising the following steps:

(1) 4-acetylenyl benzoic acid and L-proline methyl ester hydrochloride are subjected to amidation reaction to synthesize phenylacetylene monomer with proline oligopeptide derivative;

(2) adopting 2, 5-norbornadiene rhodium tetraphenyl borate as a catalyst to realize the polymerization of phenylacetylene monomer with proline oligopeptide derivative and N- (4-ethynylphenylcarbonyl) -aminopropyltriethoxysilane, and synthesizing a helical polyphenylacetylene copolymer with side chain with proline oligopeptide derivative;

(3) the method comprises the steps of preparing silicon dioxide microsphere seed liquid by a Stober method, and preparing the helical polyphenylacetylene/silicon-based hybrid porous material by a seed growth method by utilizing the helical polyphenylacetylene copolymer and the silicon dioxide microsphere seed liquid.

2. The preparation method of the novel helical polyphenylacetylene/silicon-based hybrid porous material as claimed in claim 1, is characterized in that the step (1) specifically comprises the steps of weighing 4-acetylenyl benzoic acid, L-proline methyl ester hydrochloride, dimethylaminopyridine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride according to a molar ratio of 1: 1.5-10: 1.1-5, dissolving the weighed 4-acetylenyl benzoic acid, L-proline methyl ester hydrochloride, dimethylaminopyridine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride in dichloromethane for amidation reaction, wherein the molar concentration of the 4-acetylenyl benzoic acid is 0.02-1.0 mol/L, the reaction temperature is 20-30 ℃, the reaction time is 10-24 hours, after the reaction is finished, purifying the obtained through column chromatography, a phenylacetylene monomer with proline methyl ester is obtained, dissolving the phenylacetylene monomer with proline methyl ester in methanol at a concentration of 0.5-1.2 mol/L, adding 2-34 mol of sodium hydroxide according to a molar ratio of the phenylacetylene monomer with proline methyl ester to sodium hydroxide, performing the amidation reaction at a temperature of 2-1-2-6, performing the phenylacetylene hydrochloride and the amidation reaction for a period of the phenylacetylene hydrochloride, removing the proline methyl ester, wherein the phenylacetylene hydrochloride, the phenylacetylene hydrochloride is carried out the phenylacetylene hydrochloride, the phenylacetylene hydrochloride after the amidation reaction is completed, the reaction time of the phenylacetylene hydrochloride is 1-10, the phenylacetylene hydrochloride is obtained through a purification method, the processes of the phenylacetylene hydrochloride, the phenylacetylene hydrochloride by dropwise adding the phenylacetylene hydrochloride by a dipeptide amino-3-1-10-1-10-3-5-10-3-1-10-3-10-2-1-3-.

3. The preparation method of the novel helical polyphenylacetylene/silicon-based hybrid porous material as claimed in claim 1, wherein the step (2) is specifically as follows: under the protection of inert gas at normal temperature and normal pressure, according to phenylacetylene monomer with proline oligopeptide derivative, PA-APTES and Rh (nbd) BPh₄The molar ratio of 50: 0.5-1.55: 1-10, and the phenylacetylene monomer with the proline oligopeptide organisms, PA-APTES and Rh (nbd) BPh are mixed₄Dissolving the proline oligopeptide derivative in a polymerization reaction solvent for reaction, wherein the molar concentration of the phenylacetylene monomer with the proline oligopeptide derivative is 0.03-1.0 mol/L, the reaction temperature is 20-30 ℃, the reaction time is 18-30 h, and after the reaction is finished, carrying out reprecipitation extractionAnd purifying to obtain the helical polyphenylacetylene copolymer with the side chain having the proline oligopeptide derivative.

4. The preparation method of the novel spiral polyphenylacetylene/silicon-based hybrid porous material as claimed in claim 1, wherein the preparation of the silica microsphere seed solution by the Stober method in the step (3) is specifically that 0.1-0.6 mol/L n-ethyl orthosilicate aqueous solution is dropwise added into a mixed solvent of distilled water, alcohol and ammonia water in a volume ratio of 12:1:1, the volume ratio of the n-ethyl orthosilicate aqueous solution to the mixed solvent is 4:14, the reaction temperature is 25-35 ℃, the reaction time is 6-12 h, and the mass fraction of the ammonia water is 25%.

5. The preparation method of the novel spiral polyphenylacetylene/silicon-based hybrid porous material according to claim 1, which is characterized in that the preparation method of the spiral polyphenylacetylene/silicon-based hybrid porous material by the seed growth method in the step (3) comprises the steps of preparing a mixed solution according to the volume ratio of silicon dioxide microsphere seed liquid, distilled water and ammonia water of 1:10:1, preparing an aqueous solution of hexadecyltrimethylammonium bromide with the mass fraction of 40% as a pore-forming agent solution, adding the pore-forming agent solution into the mixed solution according to the mass ratio of 1: 40-60 of ethyl orthosilicate to hexadecyltrimethylammonium bromide in the mixed solution, fully stirring, dropwise adding an aqueous solution of ethyl orthosilicate with the concentration of 0.1-0.6 mol/L according to the molar ratio of 1: 120-150 of ethyl orthosilicate to be added, reacting at 25-30 ℃ for 6-12 h, mixing the reacted solution, distilled water, ethanol and ammonia water according to the volume ratio of 4:12:6:1, reacting at 7-1: 15: 6:1 of ethyl orthosilicate and spiral polyphenylacetylene copolymer, and drying the porous polyphenylacetylene/silicon-based hybrid porous material after the reaction is finished in a centrifugal reaction, and drying at a temperature of 16-8 h.

6. The method for preparing the novel helical polyphenylacetylene/silicon-based hybrid porous material as claimed in claim 3, wherein the inert gas is one of nitrogen or argon.

7. The method for preparing the novel helical polyphenylacetylene/silicon-based hybrid porous material as claimed in claim 3, wherein the polymerization solvent is one of tetrahydrofuran, N-dimethylformamide and chloroform.

8. The method for preparing the novel helical polyphenylacetylene/silicon-based hybrid porous material as claimed in claim 4, wherein the alcohol is one of ethanol or n-propanol.

Technical Field

The invention relates to the field of material preparation, mainly relates to a preparation method of an organic/inorganic hybrid porous material, and particularly relates to a preparation method of a spiral polyphenylacetylene/silicon-based hybrid porous material.

Background

Through the function composition, performance complementation and optimization of two or more materials, the composite material with excellent performance can be prepared. The organic phase and inorganic phase of the organic/inorganic hybrid material can be combined together by means of strong chemical bonds (ionic or covalent bonds) to form an interpenetrating organic/inorganic network, and the shape and the performance of the material can be adjusted in a considerable range, so that the performance of the material is diversified.

The mesoporous silica has the advantages of stable skeleton structure, uniform and adjustable mesoporous channels, rich hydroxyl on the surface and the like. As an inorganic porous material, the mesoporous silica has a plurality of potential application values. However, in view of practical application of mesoporous silica, it is difficult to realize by only relying on a pure mesoporous silica skeleton. In order to develop mesoporous silica functional materials with different special properties, scientists introduce different types of organic functional groups on the surfaces of the pores of the mesoporous silica. The organic functional groups improve the surface property of the mesoporous silica on one hand, and endow the mesoporous silica with different characteristics such as molecular recognition, catalysis, ion adsorption and the like on the other hand.

The functionalized polyacetylene has the advantages of luminescence, fluorescence patterning, liquid crystallinity, cell compatibility, gas separation and the like, and the research thereof becomes the mainstream of polyacetylene compounds. The polyphenylacetylene is one of polyacetylenes with unique structures, a benzene ring structure is inserted between a main chain and a side chain, and the benzene ring has a strong pi conjugation effect, so that the polyphenylacetylene has excellent stability in air due to the conjugation effect. The functionalized polyphenylacetylene derivative has good optical, electric and magnetic properties due to the unique single-double bond alternating structure, and has wide application prospects in the fields of photoluminescence materials, catalysis, information storage, chiral identification and the like.

Disclosure of Invention

The invention aims to solve the problem of low chiral polymer load in a chiral stationary phase and provide a preparation method of a spiral polyphenylacetylene/silicon-based hybrid porous material.

The object of the present invention is achieved by the following steps

A preparation method of a novel spiral polyphenylacetylene/silicon-based hybrid porous material comprises the following steps:

(1) 4-acetylenyl benzoic acid and L-proline methyl ester hydrochloride are subjected to amidation reaction to synthesize phenylacetylene monomer with proline oligopeptide derivative;

(2) adopting 2, 5-norbornadiene rhodium tetraphenyl borate as a catalyst to realize the polymerization of phenylacetylene monomer with proline oligopeptide derivative and N- (4-ethynylphenylcarbonyl) -aminopropyltriethoxysilane, and synthesizing a helical polyphenylacetylene copolymer with side chain with proline oligopeptide derivative;

(3) the method comprises the steps of preparing silicon dioxide microsphere seed liquid by a Stober method, and preparing the helical polyphenylacetylene/silicon-based hybrid porous material by a seed growth method by utilizing the helical polyphenylacetylene copolymer and the silicon dioxide microsphere seed liquid.

The method comprises the following steps of (1) specifically, weighing 4-ethynylbenzoic acid, L-proline methyl ester hydrochloride, dimethylaminopyridine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride according to a molar ratio of 1: 1.5-10: 1.1-5, dissolving the weighed materials in dichloromethane for amidation reaction, wherein the molar concentration of the 4-ethynylbenzoic acid is 0.02-1.0 mol/L, the reaction temperature is 20-30 ℃, the reaction time is 10-24 hours, purifying the materials by using a column chromatography after the reaction is finished to obtain a phenylacetylene monomer with proline methyl ester, dissolving the phenylacetylene monomer with proline methyl ester in methanol at the concentration of 0.5-1.2 mol/L, dropwise adding a 2.0-3.0 mol/L aqueous solution of sodium hydroxide according to a molar ratio of the phenylacetylene monomer with proline methyl ester to sodium hydroxide in the molar ratio of 1: 2-6, carrying out elimination reaction at the reaction temperature of 20-30 ℃, reacting for 10 hours, purifying the phenylacetylene hydrochloride with proline methyl ester and the reaction time of the phenylacetylene hydrochloride after the reaction is finished, carrying the reaction of the phenylacetylene hydrochloride, the phenylacetylene hydrochloride with proline methyl ester, the reaction is completed by using a dipeptide amino pyridine hydrochloride, the method for synthesizing the phenylacetylene hydrochloride with proline, the phenylacetylene hydrochloride and the phenylacetylene hydrochloride, wherein the phenylacetylene hydrochloride with proline methyl ester, the phenylacetylene hydrochloride with the phenylacetylene hydrochloride are obtained by using a dipeptide ethyl-5-1-5 molar ratio of the phenylacetylene hydrochloride, the phenylacetylene hydrochloride after the phenylacetylene hydrochloride is obtained by using a dipeptide amino pyridine hydrochloride by dissolving the phenylacetylene hydrochloride by using a dipeptide amino pyridine hydrochloride and the phenylacetylene hydrochloride by using a dipeptide amino pyridine hydrochloride by using a;

the step (2) is specifically as follows: under the protection of inert gas at normal temperature and normal pressure, according to phenylacetylene monomer with proline oligopeptide derivative, PA-APTES and Rh (nbd) BPh₄The molar ratio of 50: 0.5-1.55: 1-10, and the phenylacetylene monomer with the proline oligopeptide organisms, PA-APTES and Rh (nbd) BPh are mixed₄Dissolving the raw materials in a polymerization reaction solvent for reaction, wherein the molar concentration of phenylacetylene monomers with proline oligopeptide derivatives is 0.03-1.0 mol/L, the reaction temperature is 20-30 ℃, the reaction time is 18-30 h, and after the reaction is finished, purifying by a precipitation method to obtain a helical polyphenylacetylene copolymer with side chains with proline oligopeptide derivatives;

the preparation method of the silicon dioxide microsphere seed liquid by the Stober method in the step (3) is specifically that 0.1-0.6 mol/L of tetraethoxysilane aqueous solution is dripped into a mixed solvent with the volume ratio of distilled water, alcohol and ammonia water being 12:1:1, the volume ratio of the tetraethoxysilane aqueous solution to the mixed solvent being 4:14, the reaction temperature is 25-35 ℃, the reaction time is 6-12 h, and the mass fraction of the ammonia water is 25%;

the method for preparing the helical polyphenylacetylene/silicon-based hybrid porous material by using the seed growth method in the step (3) comprises the steps of preparing a mixed solution according to the volume ratio of silicon dioxide microsphere seed solution, distilled water and ammonia water being 1:10:1, preparing an aqueous solution of hexadecyl trimethyl ammonium bromide with the mass fraction of 40% as a pore-foaming agent solution, adding the pore-foaming agent solution into the mixed solution according to the mass ratio of ethyl orthosilicate to hexadecyl trimethyl ammonium bromide being 1: 40-60, fully stirring, dropwise adding an aqueous solution of ethyl orthosilicate with the concentration of 0.1-0.6 mol/L according to the molar ratio of the ethyl orthosilicate to be added being 1: 120-150, reacting at the temperature of 25-30 ℃ for 6-12 hours, mixing the reacted solution, the distilled water, the ethanol and the ammonia water according to the volume ratio of 4:12:6:1, adding a helical polyphenylacetylene copolymer according to the mass ratio of the ethyl orthosilicate to the helical polyphenylacetylene copolymer being 7-15: 1, reacting at the temperature of 10-35 ℃, reacting for 8 hours, washing, reacting, centrifuging for 24-24 hours, and drying to obtain a helical polyphenylacetylene/silicon-based hybrid porous material after the reaction is finished;

the inert gas is one of nitrogen or argon;

the polymerization solvent is one of tetrahydrofuran, N-dimethylformamide and chloroform;

the alcohol is one of ethanol or n-propanol.

The invention has the beneficial effects that:

the preparation method of the helical polyphenylacetylene/silicon-based hybrid porous material can realize chemical bonding between an organic phase and an inorganic phase and control of the proportion between the organic phase and the inorganic phase, and obtain the hybrid material with higher helical polyphenylacetylene content. The spiral polyphenylacetylene/silicon-based hybrid porous material can be used for a chiral stationary phase of a high performance liquid chromatography, has better chiral recognition and resolution capabilities and good solvent tolerance, can introduce a polar solvent into a mobile phase to further improve the chiral resolution capability of the mobile phase, overcomes the problem that the traditional coating type chiral stationary phase cannot be used in the mobile phase containing the polar solvent, can solve the problem of low chiral polymer load capacity in the chiral stationary phase, and has good application value and prospect in the field of separation of chiral compounds.

Detailed Description

The present invention will be described in detail with reference to specific embodiments.