阅读说明：本技术 一种手性分离多功能纤维素基材料及其制备方法 (Chiral separation multifunctional cellulose-based material and preparation method thereof ) 是由 王慧庆 钱浩 沈晓飞 张燕 张铭涛 王震宇 元佳丽 于 2019-10-31 设计创作，主要内容包括：本发明公开了一种手性分离多功能纤维素基材料及其制备方法,首先以化学试剂处理使得基材表面修饰上可点击反应的叠氮基团,然后利用点击化学反应将螺旋聚合物连接到材料表面,干燥后得到表面修饰了螺旋聚合物的基材。本发明通过简单的表面修饰,一步快速获得多种功能性,纤维素材料、手性分离、疏水性吸油等功能,可以用于手性药物、手性荧光分子等对映体的分离。(The invention discloses a multifunctional cellulose-based material for chiral separation and a preparation method thereof. The invention can rapidly obtain various functionalities, such as cellulose material, chiral separation, hydrophobic oil absorption and the like, by simple surface modification in one step, and can be used for separating enantiomers such as chiral drugs, chiral fluorescent molecules and the like.)

1. A preparation method of a chiral separation multifunctional cellulose-based material is characterized by comprising the following steps: firstly, modifying the surface of a base material with a click-reactable azide group through chemical reagent treatment, then connecting a hydrophobic spiral polymer containing alkynyl end groups to the surface of a material through a click chemical reaction, and drying to obtain the base material of which the surface is modified with the hydrophobic spiral polymer.

2. The method of claim 1, comprising the steps of:

step 1: cleaning and drying the base material, and then reacting with sodium azide to introduce azide to obtain a base material with surface azide modified;

step 2: preparing a hydrophobic spiral polymer containing alkynyl end groups;

and step 3: soaking the substrate with the azide modification obtained in the step 1 into the hydrophobic spiral polymer solution containing the alkyne terminal group obtained in the step 2, adding a catalyst CuI or CuCl, and carrying out alkynyl-azide click chemical reaction at 40-60 ℃ under the protection of nitrogen; after the reaction is finished, cleaning and drying to obtain a substrate of which the surface is modified with the hydrophobic spiral polymer;

and 4, step 4: repeating the treatment process of the step 3 for 1-5 times.

3. The method of claim 2, wherein:

in the step 1, the base material comprises various forms of cellulose and derivatives thereof such as cotton, paper, wood, filter paper, fabric, foam, microspheres and the like; the step of introducing the azide group through the reaction with the sodium azide is to modify the p-toluenesulfonyl group and then react with the sodium azide to obtain the azide group.

4. The method of claim 2, wherein:

in the step 2, the hydrophobic spiral polymer containing alkynyl end groups is D-menthol modified poly (phenylisonitrile).

5. The method of claim 2, wherein:

in the step 3, the concentration of the hydrophobic spiral polymer solution containing alkynyl end groups is 1-10 mg/mL; the addition mass of the catalyst CuI or CuCl is five per thousand to one hundredth of the mass of the hydrophobic spiral polymer containing the alkyne terminal group.

6. A chirally separated multifunctional cellulose-based material prepared by the preparation method of any one of claims 1 to 5.

Technical Field

The invention relates to a functional cellulose-based material, in particular to a multifunctional cellulose-based material for chiral separation and a method thereof.

Background

Cellulose is essentially a 1,4 β glycosidic bond connected with a glucose unit macromolecular chain, the 2,3,6 positions of the glucose unit of the cellulose contain 3 active hydroxyl groups, the spatial structure of the cellulose is a left-handed helix structure which has a rigid regular skeleton, the derivatives also retain the helix structure, and some cellulose derivatives are used as chiral stationary phases of a high performance liquid chromatography column for separation of chiral enantiomers, so far, among the developed polysaccharide derivative materials, the cellulose derivatives are the most effective chiral separation materials.

The present invention relates to a fiber-reinforced polymer, and more particularly, to a fiber-reinforced polymer, which has a helical structure, such as a right-handed α -helical structure, which is a very important chiral expression form, in a protein structure, such as DNA having a double helical structure, which is present in a nucleus, and which is a very important chiral expression form.

The surface of the cellulose product is rapidly endowed with multifunction, chiral separation, hydrophobicity, oil absorption and the like in one step by utilizing alkyne-azide click chemical reaction. The surface performance of the cellulose product is greatly improved by adding a trace amount of the cellulose. Has the advantages of high efficiency, convenience, rapidness and the like, and endows the cellulose product with chiral recognition and separation capability and hydrophobicity.

Disclosure of Invention

Based on the technical problems in the background art, the invention provides a multifunctional cellulose-based material for chiral separation and a preparation method thereof. According to the invention, the method of click chemical modification of the hydrophobic spiral polymer on the surface of the cellulose product can rapidly endow the cellulose product with chiral separation, hydrophobicity, oil absorption and other performances.

In the invention, the click chemistry reaction is an alkynyl-azide click reaction.

The preparation method of the chiral separation multifunctional cellulose-based material comprises the following steps:

step 1: cleaning and drying the base material, and then reacting with sodium azide to introduce azide to obtain a base material with surface azide modified;

step 2: preparing a hydrophobic spiral polymer containing alkynyl end groups;

and step 3: soaking the substrate with the azide modification obtained in the step 1 into the hydrophobic spiral polymer solution containing the alkyne terminal group obtained in the step 2, adding a catalyst CuI or CuCl, and carrying out alkynyl-azide click chemical reaction at 40-60 ℃ under the protection of nitrogen; after the reaction is finished, cleaning and drying to obtain a substrate of which the surface is modified with the hydrophobic spiral polymer;

and 4, step 4: repeating the treatment process of the step 3 for 1-5 times.

In step 1, the substrate comprises various forms of cellulose and derivatives thereof such as cotton, paper, wood, filter paper, fabric, foam, microspheres and the like.

In the step 1, the step of introducing the azide group through the reaction with the sodium azide is to modify the p-toluenesulfonyl group and then react with the sodium azide to obtain the azide group. The specific reaction process comprises the steps of putting a base material into an N, N-dimethylacetamide (225g) solvent (containing 3-6% of triethylamine) with the mass being 10-50 times that of the base material, adding p-toluenesulfonyl chloride with the mass being 1-2 times that of the base material, reacting for 12-36 hours at 8-50 ℃ in a closed container under the protection of nitrogen, precipitating, cleaning, carrying out suction filtration and separation to obtain a p-toluenesulfonylated cellulose material; putting the obtained p-toluenesulfonylated cellulose material into a closed container, adding 2-4 times of N, N-dimethylacetamide solvent and 1-2 times of NaN₃Reacting for 12-48h under the protection of nitrogen in an oil bath at 60-90 ℃, washing for 3 times by cold water, then washing for 1-3 times by ethanol, and drying to obtain the substrate with the surface modified by the azide.

In step 2, the hydrophobic spiral polymer containing alkynyl end groups comprises D-menthol modified poly (phenylisonitrile)¹。1Liu,N.；Ma,C.-H.；Sun,R.-W.；Huang,J.；Li,C.；Wu,Z.-Q.,Polymer Chemistry,2017,8,2152-2163.

In the step 3, the concentration of the hydrophobic spiral polymer solution containing alkynyl end groups is 1-10 mg/mL.

In the step 3, the addition mass of the catalyst CuI or CuCl is five per thousand to one hundredth of the mass of the hydrophobic spiral polymer containing the alkyne terminal group.

And in the step 3, the drying is natural airing and/or oven drying.

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

1. the invention adopts the click chemical reaction, so that the hydroxyl on the cellulose product is coupled with the functional polymer, the click chemical reaction efficiency is high, and the obvious effect can be achieved by modifying a trace amount of polymer.

2. The invention uses the artificially synthesized hydrophobic spiral polymer, and rapidly endows the cellulose product with multiple functions, such as chiral separation, hydrophobicity, oil absorption, water resistance, moisture resistance and hardness increase by a one-step method.

3. Various application functions of the spiral polymer can be reserved, and meanwhile, the cellulose product becomes a good support material and is favorable for recycling.

Drawings

FIG. 1 shows the grafting of D-menthol modified polybenzisonitrile (A) to cotton fiber in example 1 and the grafting of D-menthol modified polybenzisonitrile to ethylcellulose in example 4¹³CNMR nuclear magnetic spectrum, it can be seen from FIG. 1 that D-menthol-modified polybenzonitrile was successfully grafted to cellulose and ethyl cellulose.

Fig. 2A is an infrared spectrum of cellulose (a), cellulose azide (B) in example 1, cellulose graft polyphenylisonitrile (DP ═ 20) (c) in example 1, cellulose graft polyphenylitrile (DP ═ 50) (D) in example 2, and paper filter cellulose graft polyphenylitrile (DP ═ 100) (e) in example 3, and fig. 2B is an infrared spectrum of ethylcellulose (a), ethyl cellulose azide (B) and D-menthol-modified polyphenylitrile (c) in example 4. From FIG. 2 it can be seen that both D-menthol modified polybenzonitrile was successfully grafted onto cellulose and ethyl cellulose.

Fig. 3A is a uv-cdram of D-menthol-modified polybenzisonitrile (degree of polymerization 50) (D) and cellulose-grafted D-menthol-modified polybenzisonitrile (degree of polymerization 50) (b) of example 2, D-menthol-modified polybenzisonitrile (degree of polymerization 100) (c) and cellulose-grafted D-menthol-modified polybenzisonitrile (degree of polymerization 100) (a) of example 3, and it can be seen from fig. 3 that the CD values of the cellulose-grafted D-menthol-modified polybenzisonitrile are significantly increased, by 96.6% (degree of polymerization 50) and 93.7% (degree of polymerization 100), respectively, compared to the pure D-menthol-modified polybenzisonitrile. FIG. 3B shows UV-CID chromatograms of D-menthol-modified polyisocyanamide (degree of polymerization 20) (D) and cellulose-grafted D-menthol-modified polyisocyanamide (degree of polymerization 20) (B) in example 4, D-menthol-modified polyisocyanamide (degree of polymerization 50) (c) in example 5, and cellulose-grafted D-menthol-modified polyisocyanamide (degree of polymerization 50) (a), and it can be seen from FIG. 3B that the CD values of cellulose-grafted D-menthol-modified polyisocyanamide are significantly increased, by 144.3% (degree of polymerization 20) and 295.2% (degree of polymerization 50), respectively, compared to the pure D-menthol-modified polyisocyanamide

FIG. 4A is a graph showing the change of the chiral recognition fluorescence intensity of cellulose grafted D-menthol-modified polybenzisonitrile on L-type (a) and D-type phenylalanine methyl ester (b) modified by dansyl chloride in example 1 and a graph showing the change of the fluorescence under ultraviolet light, and it can be seen from FIG. 4 that cellulose grafted D-menthol-modified polybenzisonitrile has a very good selective recognition effect on dansyl chloride-modified D-type phenylalanine methyl ester. FIG. 4B is a graph showing the change of the fluorescence intensity of the cellulose-grafted D-menthol-modified polybenzisonitrile on L-type (a) and D-type alanine methyl ester (B) under the modification of dansyl chloride in example 5 and the change of the fluorescence under ultraviolet light, and it can be seen from FIG. 4 that the cellulose-grafted D-menthol-modified polybenzisonitrile has a good selective recognition effect on D-type phenylalanine methyl ester under the modification of dansyl chloride; the polybenzonitrile modified by ethyl cellulose grafted D-menthol has good selective recognition effect on D-type alanine methyl ester modified by dansyl chloride.

Detailed Description

In order to make the objects and advantages of the present invention more apparent, the following embodiments are further described.