CN110841613B - Chiral separation multifunctional cellulose-based material and preparation method thereof - Google Patents

Chiral separation multifunctional cellulose-based material and preparation method thereof Download PDF

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CN110841613B
CN110841613B CN201911051296.9A CN201911051296A CN110841613B CN 110841613 B CN110841613 B CN 110841613B CN 201911051296 A CN201911051296 A CN 201911051296A CN 110841613 B CN110841613 B CN 110841613B
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cellulose
azide
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menthol
spiral polymer
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王慧庆
钱浩
沈晓飞
张燕
张铭涛
王震宇
元佳丽
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Hefei University of Technology
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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Abstract

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.

Description

Chiral separation multifunctional cellulose-based material and preparation method thereof
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
Various natural cellulose-based products, such as filter paper, wallpaper, wrapping paper, wood, cotton, cellulose-based aerogels, hydrogels, films, and the like, exist in our lives and scientific research. Cellulose is essentially a 1,4 beta glycosidic bond connected glucose unit macromolecular chain, the 2,3,6 sites of the glucose unit contain 3 active hydroxyl groups, the spatial structure of the cellulose is a left-handed helical structure, the cellulose has a rigid regular skeleton, the derivatives thereof also retain a helical structure, and some cellulose derivatives are used as a chiral stationary phase of a high performance liquid chromatography column for separation of chiral enantiomers, so that the cellulose derivatives have a wide application prospect. Based on this background, there are many methods to improve the hydrophobicity of cellulose products such as wood and paper, for example, patent 201510635704.0 utilizes tris (3, 5-dimethylphenylcarbamoylated) cellulose or tris (4-methylphenylcarbamoylated) cellulose as chiral stationary phase to separate dihydromyricetin enantiomer. Patent 201811610928.6 discloses the use of optically pure mandelic acid or optically pure mandelic acid derivative acyl halide and microcrystalline cellulose to prepare chiral separation materials for the separation and analysis of various chiral substances.
Helical structures are secondary structures that are ubiquitous in nature, such as right-handed alpha-helices found in protein structures, and double-helical DNA found in the nucleus, which is a very important form of chiral representation. Examples of the synthetic helical polymer include stereoregular polypropylene, polyacetylene, polymethyl methacrylate, polyisonitrile, helical vinyl polymer (PTrMA), polyisocyanate, and polycarbodiimide in a crystalline state. The polyisonitrile is the earliest discovered, the main chain of the polyisonitrile contains pi conjugated C-N bond, the existence of carbon-nitrogen bond makes the main chain of the polymer easy to twist to obtain helical structure, and the polymerization method is simple and convenient, and the helical structure can be well maintained in both solution and solid state. In addition, the optically active polyisonitriles generally have chiral main chains, chiral side groups or chiral helical conformations, have very unique rigid structures, and the properties make the optically active polyisonitriles have wide application prospects in the aspects of chiral resolution, chiral recognition and asymmetric catalysis. For example, the synthetic hydrophobic spiral polymer-polybenzene isonitrile, polypentafluorophenol isonitrile, polyhexafluoroisopropanol isonitrile, etc., the monomer unit contains super-dense hydrophobic groups such as D-menthol and fluorine elements, endowing property, the spiral structure of the polyisonitrile endows chiral separation effect, the chiral separation has important application in the field of medicament purification, the cellulose graft polyisonitrile with cellulose as a substrate combines the hydrophobic property and the chiral separation property, can endow the wood with the functions of wear resistance, water resistance, hydrophobic property, chiral separation, oil absorption, etc., can be used for separating enantiomers such as chiral medicaments, chiral fluorescent molecules, etc., and the material can be recovered.
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 N, N-dimethylacetamide (225g) solvent (containing 3-6% of triethylamine) with the mass of 10-50 times, adding p-toluenesulfonyl chloride with the mass of 1-2 times of the base material, reacting for 12-36h at 8-50 ℃ in a closed container under the protection of nitrogen, and precipitatingCleaning, filtering and separating to obtain 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.
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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.
Example 1:
in this example, the method for chiral separation of the multifunctional cellulose-based material is as follows:
(1) triethylamine (11.88ml, 85.44mmol) and p-toluenesulfonyl chloride (8.14g, 42.72mmol) are added to a solution of anhydrous lithium chloride (25.0g) and N, N-dimethylacetamide (225g) in cotton fibers (5.0g), and the mixture is reacted at 25 ℃ for 24 hours, precipitated, washed, and separated by suction filtration to obtain p-toluenesulfonylated cellulose.
(2) Weighing 4.0g of p-toluenesulfonylated cellulose, placing the p-toluenesulfonylated cellulose into a polymerization bottle, adding 10mL of N, N-dimethylacetamide and NaN3(4.68g and 72.08mmol), reacting for 24h under an oil bath at 80 ℃, cleaning in ethanol for 1-3 times, and drying in vacuum to obtain the azido cellulose.
(3) D-menthol modified benzilonitrile monomer a (0.171g,0.6mmol), alkyne-terminated palladium (II) catalyst b (0.017mg,0.03mmol) were dissolved in anhydrous THF (2.5 mL). The reaction was stirred for 6h at 55 ℃ in an oil bath. Cooling, centrifuging and washing to obtain the D-menthol modified poly (phenylisonitrile) helical polymer as a yellow solid, wherein the polymerization degree is 20, and the molecular weight is 7.74kDa and the molecular weight distribution is 1.77.
(4) Azoic cellulose (0.304g, GPC: Mn: 29.08kDa), D-menthol-modified polybenzonitrile (1.574g, GPC: Mn: 7742), cuprous chloride (0.1mg, 1.01. mu. mol), and 5ml of an anhydrous THF solution containing 0.2uL of 1.8-diazabicycloundec-7-ene were mixed, and the mixture was stirred at 55 ℃ in an oil bath for 12 hours. And cooling, centrifuging and washing to obtain the cellulose grafted polybenzisonitrile polymer, wherein the water contact angle is 150 degrees, and the material has obvious selective absorption of 99 percent on the dansyl chloride modified D-phenylalanine methyl ester fluorescent probe.
Example 2:
in this example, the method for chiral separation of the multifunctional cellulose-based material is as follows:
(1) soaking pinewood (5.0g) in N, N-dimethylacetamide (250g) solution, adding triethylamine (10mL) and p-toluenesulfonyl chloride (6g), reacting at 35 ℃ for 12h, precipitating, cleaning, and performing suction filtration separation to obtain p-toluenesulfonylated modified wood.
(2) Weighing 5.0g of the p-toluenesulfonylation modified wood, placing the p-toluenesulfonylation modified wood into a sealed glass bottle, adding 50mL of N, N-dimethylacetamide and NaN3(5.0g), reacting for 36h in an oil bath at 70 ℃, washing with water for 3 times, washing with ethanol for 2 times, and naturally drying to obtain the azide modified wood.
(3) D-menthol modified benzilonitrile monomer a (0.425g,1.5mmol), alkyne-terminated palladium (II) catalyst b (0.017mg,0.03mmol) were dissolved in anhydrous THF (2.5 mL). The reaction was stirred for 6h at 55 ℃ in an oil bath. And cooling, centrifuging and washing to obtain the D-menthol modified poly (phenylisonitrile) helical polymer with yellow solid and the polymerization degree of 50.
(4) Azide-modified wood (0.5g), D-menthol-modified polybenzonitrile (1.574g, Mn ═ 14234), cuprous chloride (0.1mg, 1.01. mu. mol), and 5ml of an anhydrous THF solution containing 0.2uL of 1.8-diazabicycloundecen-7-ene were mixed, and the mixture was stirred in an oil bath at 45 ℃ for 24 hours. And cooling, centrifuging and washing to obtain the cellulose grafted polybenzisonitrile polymer, wherein the water contact angle is 152 degrees, and the material has obvious selective absorption of 99 percent on the dansyl chloride modified D-phenylalanine methyl ester fluorescent probe.
Example 3:
in this example, the method for chiral separation of the multifunctional cellulose-based material is as follows:
(1) triethylamine (2.38ml, 17.01mmol) and p-toluenesulfonyl chloride (1.63g, 8.54mmol) were added to filter paper (1.0g), and the mixture was reacted at 30 ℃ for 24 hours, precipitated, washed, and separated by suction filtration to obtain p-toluenesulfonylated filter paper.
(2) Weighing 1.0g of the p-toluenesulfonylated filter paper, placing the p-toluenesulfonylated filter paper into a polymerization bottle, adding 10mL of N, N-dimethylacetamide and NaN3(2.0g), reacting for 24 hours in an oil bath at 80 ℃, washing for 1-3 times in ethanol, and drying in vacuum to obtain the azide chemical fiber filter paper.
(3) D-menthol modified benzilonitrile monomer a (0.855g,3.00mmol), alkyne-terminated palladium (II) catalyst b (0.017mg,0.03mmol) were dissolved in anhydrous THF (2.5 mL). The reaction was stirred for 6h at 55 ℃ in an oil bath. And cooling, centrifuging and washing to obtain a yellow solid D-menthol modified poly (phenylisonitrile) helical polymer, wherein the polymerization degree is 100, and the molecular weight is 31.7kDa and the molecular weight distribution is 1.29.
(4) Azide filter paper (0.304g), D-menthol-modified polybenzonitrile (1.574g, GPC: Mn. RTM. 31793), cuprous chloride (0.1mg, 1.01. mu. mol), and 5ml of an anhydrous THF solution containing 0.2uL of 1.8-diazabicycloundecen-7-ene were mixed and reacted with stirring at 55 ℃ in an oil bath for 12 hours. Cooling, centrifuging and washing to obtain the cellulose grafted polybenzisonitrile polymer, coating the cellulose grafted polybenzisonitrile polymer on a glass plate, wherein the water contact angle of the surface of a film layer is 148 degrees, and the material has obvious selective absorption of 99.9 percent on a dansyl chloride modified D-phenylalanine methyl ester fluorescent probe.
Example 4:
in this example, the method for chiral separation of the multifunctional cellulose-based material is as follows:
(1) triethylamine (10ml) and p-toluenesulfonyl chloride (6.0g) were added to a solution of ethyl cellulose (5.0g) in N, N-dimethylacetamide (200g), and the mixture was reacted at 45 ℃ for 24 hours, followed by precipitation, washing, suction filtration and separation to obtain p-toluenesulfonylated ethyl cellulose.
(2) Weighing 4.0g of p-toluenesulfonylated ethylcellulose, placing the p-toluenesulfonylated ethylcellulose into a polymerization bottle, adding 10mL of N, N-dimethylacetamide and NaN3(5.0g), reacting for 24 hours under 90 ℃ oil bath, washing for 1-3 times in ethanol, and drying in vacuum to obtain the azido ethylcellulose.
(3) D-menthol modified benzilonitrile monomer a (0.17g,0.6mmol), alkyne-terminated palladium (II) catalyst b (0.017mg,0.03mmol) were dissolved in tetrahydrofuran (2.5 mL). The reaction was stirred for 6h at 55 ℃ in an oil bath. And cooling, centrifuging and washing to obtain the D-menthol modified poly (phenylisonitrile) helical polymer with yellow solid and the polymerization degree of 20.
(4) Azoic cellulose (0.304g, GPC: Mn 29.08kDa), D-menthol-modified polybenzonitrile, cuprous chloride (0.1mg, 1.01. mu. mol), and 5ml of a tetrahydrofuran solution containing 0.2uL of 1.8-diazabicycloundecen-7-ene were mixed and reacted with stirring at 55 ℃ in an oil bath for 12 hours. Cooling, centrifuging and washing to obtain the ethyl cellulose grafted polybenzisonitrile polymer, coating the ethyl cellulose grafted polybenzisonitrile polymer on a glass plate, wherein the water contact angle of the surface of a film layer reaches 150 degrees, and the material has obvious selective absorption of 99 percent on a dansyl chloride modified D-alanine methyl ester fluorescent probe.
Example 5:
in this example, the method for chiral separation of the multifunctional cellulose-based material is as follows:
(1) triethylamine (10ml) and p-toluenesulfonyl chloride (6.0g) were added to a solution of ethyl cellulose (5.0g) in N, N-dimethylacetamide (200g), and the mixture was reacted at 35 ℃ for 24 hours, followed by precipitation, washing, suction filtration and separation to obtain p-toluenesulfonylated ethyl cellulose.
(2) Weighing 4.0g of p-toluenesulfonylated ethylcellulose, placing the p-toluenesulfonylated ethylcellulose into a polymerization bottle, adding 10mL of N, N-dimethylacetamide and NaN3(5.0g), reacting for 24 hours under 90 ℃ oil bath, washing for 1-3 times in ethanol, and drying in vacuum to obtain the azido ethylcellulose.
(3) D-menthol modified benzilonitrile monomer a (0.425g,1.5mmol), alkyne-terminated palladium (II) catalyst b (0.017mg,0.03mmol) were dissolved in tetrahydrofuran (2.5 mL). The reaction was stirred for 6h at 55 ℃ in an oil bath. And cooling, centrifuging and washing to obtain the D-menthol modified poly (phenylisonitrile) helical polymer with yellow solid and the polymerization degree of 50.
(4) Azoic cellulose (0.304g, GPC: Mn 29.08kDa), D-menthol-modified polybenzonitrile, cuprous chloride (0.1mg, 1.01. mu. mol), and 5ml of a tetrahydrofuran solution containing 0.2uL of 1.8-diazabicycloundecen-7-ene were mixed and reacted with stirring at 55 ℃ in an oil bath for 12 hours. Cooling, centrifuging and washing to obtain the ethyl cellulose grafted polybenzisonitrile polymer, coating the ethyl cellulose grafted polybenzisonitrile polymer on a glass plate, wherein the water contact angle of the surface of a film layer reaches 150 degrees, and the material has obvious selective absorption of 99 percent on a dansyl chloride modified D-alanine methyl ester fluorescent probe.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be within the scope of the present invention, and the technical solution and the inventive concept thereof according to the present invention should be equally replaced or changed, such as increasing the number of coating layers or pressing several layers of paper together, etc.

Claims (4)

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-reaction azide group through chemical reagent treatment, then connecting a hydrophobic spiral polymer containing an alkynyl end group 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;
the method 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; the hydrophobic spiral polymer containing alkynyl end groups is D-menthol modified poly (phenylisonitrile);
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.
2. The method of claim 1, wherein:
in step 1, the substrate comprises various forms of cellulose and derivatives thereof such as cotton, paper, wood, filter paper, fabric, foam and microspheres; 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.
3. The method of claim 1, 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.
4. A chirally separated multifunctional cellulose-based material prepared by the preparation method of any one of claims 1 to 3.
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