CN100392172C - Preparation method of cyclodextrin polymer mimic enzyme functional fiber - Google Patents

Abstract

A preparation method of a cyclodextrin polymer imitating enzyme functional fiber, which is characterized in that the cyclodextrin polymer obtained after the polymerization of cyclodextrin monomers is used as an imitating enzyme to graft onto the cellulose fiber to make a fiber with certain catalytic properties. Functional cyclodextrin polymer imitating enzyme functional fiber, compared with the prior art, the advantages of the present invention are: 1) the cyclodextrin polymer in the cyclodextrin polymer imitating enzyme functional fiber has multiple recognition functions, and its Monomer cyclodextrins have a unique synergistic effect, so cyclodextrin polymers can better simulate the recognition and catalytic functions of enzymes on substrates; 2) weaving and tailoring cyclodextrin polymers to simulate enzyme functional fibers, Made into various forms, it is convenient to use and recycle; 3) In addition, the method can solve the problems of recycling and separation of cyclodextrin polymers when used as enzyme-like catalysts.

Description

Preparation method of cyclodextrin polymer mimic enzyme functional fiber

technical field

The invention relates to a cyclodextrin and its derivatives, in particular to a preparation method of a cyclodextrin polymer imitating enzyme functional fiber.

Background technique

Compared with ordinary chemical catalysts, enzyme catalysis has the advantages of high efficiency, specificity and mild reaction conditions, but natural enzymes are too sensitive to the environment, require harsh operating conditions, are easily inactivated, and are expensive. People try to inherit the advantages of enzymes , to change the shortcoming of its variability and inactivation, and start the simulation study of enzyme function. Such enzyme model molecules currently used to construct simulated enzymes include cyclodextrin, crown ether, cryptin, cage ether, porphyrin, etc. Cyclodextrin is an ideal enzyme model. The characteristic of cyclodextrin catalysis is that the substrate molecules participating in the reaction are first encapsulated by cyclodextrin molecules, and then react with them, which is very similar to enzymatic reactions. Therefore, cyclodextrin It has been used in many applications as an enzyme-like catalyst. Cyclodextrin polymer is a product obtained by polymerizing cyclodextrin monomers. Cyclodextrin polymers can have multiple recognition functions. Better simulate the recognition and catalytic functions of enzymes on substrates. Therefore, the cyclodextrin polymer can also be used as an enzyme-like catalyst. However, the same as when cyclodextrin is used as an enzyme-mimicking catalyst, when cyclodextrin polymer is used as an enzyme-mimicking catalyst, it will also encounter the problem of separating and recovering cyclodextrin from the product.

There have been many studies on cyclodextrin as an enzyme-mimicking catalyst, but the cyclodextrin polymer obtained after the polymerization of cyclodextrin monomers is grafted onto cellulose fibers as a mimetic enzyme to make a cyclodextrin with a certain catalytic function. Dextrin polymers mimic enzyme functional fibers to solve the problems of recycling cyclodextrin polymers and separating them from products when they are used as enzyme-like catalysts, which are the subject of research.

Contents of the invention

The purpose of the present invention is to provide a preparation method of a cyclodextrin polymer imitating enzyme functional fiber. The cyclodextrin polymer obtained after the polymerization of the cyclodextrin monomer is grafted onto the cellulose fiber as an imitating enzyme to form Cyclodextrin polymers with certain catalytic functions mimic enzyme functional fibers.

A preparation method of a cyclodextrin polymer imitating enzyme functional fiber, characterized in that the following steps are adopted:

A) Cyclodextrin is added to 30% sodium hydroxide aqueous solution at a weight ratio of 1:1 to 3, stirred and reacted at room temperature for 10 to 15 hours, and then cyclodextrin and The molar ratio of epichlorohydrin is 1:1~8. Add epichlorohydrin and react for 20~30 hours. When the reaction reaches the gel point, add an appropriate amount of acetone to stop the reaction, and add absolute ethanol to the solution until it becomes a white solid. Precipitate, filter, and vacuum-dry to obtain cyclodextrin prepolymer;

B) Throwing the cellulose fibers into 2% _Na2CO3 solution at a weight ratio of 1:20-50, reacting at 70-100°C for 1-3 hours, then taking them out, _washing them and drying them; The treated cellulose fibers are put into 0.1% NaOH solution to swell for 0.5 to 2 hours in a weight ratio of 1:10 to 50, and then taken out;

C) Put the swollen cellulose fibers into an aqueous solution containing 8% epichlorohydrin and 5% NaOH in a weight ratio of 1:50 to 100, and stir and vibrate for 1 to 5 hours at 30 to 60°C Add an appropriate amount of distilled water to wash until neutral, filter with suction, and dry to obtain epoxidized cellulose fibers;

D) cellulose fiber: cyclodextrin prepolymer: 40% NaOH alkaline solution is mixed in a weight ratio of 1: 1～3: 30～50, and the epoxidized cellulose fiber after the suction filtration is directly put into the dissolved cyclodextrin In the alkaline solution of fine prepolymer, control the reaction temperature at 40-50°C, stir and shake for 2-4 hours;

E) After the product after the above polymerization reaction is dried, the cyclodextrin polymer mimic enzyme functional fiber is obtained.

The cyclodextrin is any one of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, or a mixture thereof. Cellulosic fibers are fibers, or fabrics of fibers.

Compared with the prior art, the present invention has the following prominent advantages: 1) The cyclodextrin polymer in the cyclodextrin polymer imitating enzyme functional fiber has multiple recognition functions, and at the same time, its monomer cyclodextrin has a unique synergy Therefore, the cyclodextrin polymer can better simulate the substrate recognition and catalytic function of the enzyme; 2) The cyclodextrin polymer simulates the enzyme function fiber to weave, cut, and make various forms, which are convenient to use and recycle ; 3) In addition, adopting this method can solve the problem of cyclodextrin polymer recycling and product separation when used as imitation enzyme catalyst.

Detailed ways

Example 1:

A preparation method of a cyclodextrin polymer imitating enzyme functional fiber, characterized in that the following steps are adopted:

A) Cyclodextrin is added to 30% sodium hydroxide aqueous solution at a weight ratio of 1:1, stirred and reacted at room temperature for 10 hours, and then reacted at 40°C according to the moles of cyclodextrin and epichlorohydrin Add epichlorohydrin at a ratio of 1:1 and react for 20 hours. When the reaction reaches the gel point, add an appropriate amount of acetone to stop the reaction, and add absolute ethanol to the solution until a white solid precipitates, filter, and dry in vacuum to obtain a cyclopaste Fine prepolymer;

B) Put the cellulose fiber into 2% Na ₂ CO ₃ solution at a weight ratio of 1:20, react at 70°C for 1 hour, then take it out, wash it, and dry it; the treated cellulose fiber is pressed The weight ratio is 1:50, put it into 0.1% NaOH solution and swell for 2 hours, then take it out;

C) Put the swollen cellulose fibers into an aqueous solution containing 8% epichlorohydrin and 5% NaOH in a weight ratio of 1:50, stir and vibrate for 1 hour at 30°C; then add appropriate amount of distilled water for washing to neutral, suction filtered, and dried to obtain epoxidized cellulose fibers;

D) cellulose fiber: cyclodextrin prepolymer: 40% NaOH alkaline solution is mixed in a weight ratio of 1: 1: 30, and the epoxidized cellulose fiber after the suction filtration is directly put into the dissolved cyclodextrin prepolymer In the alkaline solution, control the reaction temperature at 50°C, stir and vibrate for 2 hours;

E) After the product after the above polymerization reaction is dried, the cyclodextrin polymer mimic enzyme functional fiber is obtained.

As the cyclodextrin, α-cyclodextrin was used.

Example 2:

A preparation method of a cyclodextrin polymer imitating enzyme functional fiber, characterized in that the following steps are adopted:

A) Cyclodextrin is added to 30% sodium hydroxide aqueous solution at a weight ratio of 1:3, stirred and reacted at room temperature for 15 hours, and then reacted at 30°C according to the moles of cyclodextrin and epichlorohydrin Add epichlorohydrin at a ratio of 1:8, react for 30 hours, when the reaction reaches the gel point, add an appropriate amount of acetone to stop the reaction, and add absolute ethanol to the solution until a white solid precipitates, filter, and vacuum dry to obtain a cyclopaste Fine prepolymer;

B) Put the cellulose fibers into 2% Na ₂ CO ₃ solution at a weight ratio of 1:50, react at 100°C for 3 hours, then take them out, wash them, and dry them; Put it into 0.1% NaOH solution with a weight ratio of 1:10 and swell for 0.5 hours, then take it out;

C) Put the swollen cellulose fibers into an aqueous solution containing 8% epichlorohydrin and 5% NaOH in a weight ratio of 1:100, stir and vibrate for 5 hours at 60°C; then add appropriate amount of distilled water for washing to neutral, suction filtered, and dried to obtain epoxidized cellulose fibers;

D) cellulose fiber: cyclodextrin prepolymer: 40% NaOH alkaline solution is mixed in a weight ratio of 1: 3: 50, and the epoxidized cellulose fiber after the suction filtration is directly put into the dissolved cyclodextrin prepolymer In the alkaline solution, control the reaction temperature at 40°C, stir and shake for 4 hours;

E) After the product after the above polymerization reaction is dried, the cyclodextrin polymer mimic enzyme functional fiber is obtained.

As the cyclodextrin, β-cyclodextrin was used.

Example 3:

A preparation method of a cyclodextrin polymer imitating enzyme functional fiber, characterized in that the following steps are adopted:

A) Cyclodextrin is added to 30% sodium hydroxide aqueous solution at a weight ratio of 1:2, stirred and reacted at room temperature for 13 hours, and then reacted at 35°C according to the moles of cyclodextrin and epichlorohydrin Add epichlorohydrin at a ratio of 1:4, react for 25 hours, when the reaction reaches the gel point, add an appropriate amount of acetone to stop the reaction, and add absolute ethanol to the solution until a white solid precipitates, filter, and dry in vacuum to obtain a cyclopaste Fine prepolymer;

B) Put the cellulose fibers into 2% _Na2CO3 solution at a weight ratio of 1:35, react at 85°C for 2h, then take _them out, wash them, and dry them; The weight ratio is 1:30, put it into 0.1% NaOH solution and swell for 1 hour, then take it out;

C) Put the swollen cellulose fibers into an aqueous solution containing 8% epichlorohydrin and 5% NaOH in a weight ratio of 1:75, stir and vibrate for 3 hours at 45°C; then add appropriate amount of distilled water for washing to neutral, suction filtered, and dried to obtain epoxidized cellulose fibers;

D) cellulose fiber: cyclodextrin prepolymer: 40% NaOH alkaline solution is mixed in a weight ratio of 1: 2: 40, and the epoxidized cellulose fiber after the suction filtration is directly put into the dissolved cyclodextrin prepolymer In the alkaline solution, control the reaction temperature at 50°C, stir and vibrate for 3 hours;

E) After the product after the above polymerization reaction is dried, the cyclodextrin polymer mimic enzyme functional fiber is obtained.

As the cyclodextrin, γ-cyclodextrin was used.

Claims (2)

1. A preparation method of a cyclodextrin polymer imitating enzyme functional fiber, characterized in that the following steps are adopted: A) Cyclodextrin is added to 30% sodium hydroxide aqueous solution at a weight ratio of 1:1 to 3, stirred and reacted at room temperature for 10 to 15 hours, and then cyclodextrin and The molar ratio of epichlorohydrin is 1:1~8. Add epichlorohydrin and react for 20~30 hours. When the reaction reaches the gel point, add an appropriate amount of acetone to stop the reaction, and add absolute ethanol to the solution until it becomes a white solid. Precipitate, filter, and vacuum-dry to obtain cyclodextrin prepolymer; B) Throwing the cellulose fibers into 2% _Na2CO3 solution at a weight ratio of 1:20-50, reacting at 70-100°C for 1-3 hours, then taking them out, _washing them and drying them; The treated cellulose fibers are put into 0.1% NaOH solution to swell for 0.5 to 2 hours in a weight ratio of 1:10 to 50, and then taken out; C) Put the swollen cellulose fibers into an aqueous solution containing 8% epichlorohydrin and 5% NaOH in a weight ratio of 1:50 to 100, and stir and vibrate for 1 to 5 hours at 30 to 60°C Add an appropriate amount of distilled water to wash until neutral, filter with suction, and dry to obtain epoxidized cellulose fibers; D) Cellulose fiber: cyclodextrin prepolymer: 40% NaOH alkali solution is mixed in a weight ratio of 1:1～3:30～50, and the epoxidized cellulose fiber after the suction filtration is directly put into the dissolved cyclodextrin In the alkaline solution of fine prepolymer, control the reaction temperature at 40-50°C, stir and shake for 2-4 hours; E) After the product after the above polymerization reaction is dried, the cyclodextrin polymer mimic enzyme functional fiber is obtained. 2. The method according to claim 1, characterized in that the cyclodextrin is any one of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, or a mixture thereof.