阅读说明：本技术 大体积且不易破碎的晶胶材料及其制备方法与应用 (large-volume and non-breakable crystal glue material and preparation method and application thereof ) 是由 张旭锋 孙丽芬 于 2019-09-06 设计创作，主要内容包括：本发明涉及晶胶材料技术领域,公开了一种大体积且不易破碎的晶胶材料及其制备方法与应用。以丙烯酰胺和/或甲基丙烯酸羟乙酯为聚合物基质,通过对普通的预冻法进行改良,确保形成孔径大小均匀的大体积晶胶。同时,通过将纳米纤维素作为一种增强剂引入体系中增强其机械性能。成功地制备出体积达500mL且保持良好机械性能的大体积晶胶,为大规模的分离工程/生物技术应用提供了优越的条件。此外,将聚乙烯亚胺接枝到晶胶上得到功能性材料,该材料对胆红素具有良好的吸附性能。(The invention relates to the technical field of crystal glue materials, and discloses a large-volume crystal glue material which is not easy to break, and a preparation method and application thereof. Acrylamide and/or hydroxyethyl methacrylate are/is used as a polymer matrix, and a common prefreezing method is improved to ensure that the large-volume crystal gel with uniform pore size is formed. Meanwhile, the mechanical property of the nano-crystalline cellulose is enhanced by introducing the nano-crystalline cellulose into a system as a reinforcing agent. The large-volume crystal gel with the volume of 500mL and good mechanical property is successfully prepared, and excellent conditions are provided for large-scale separation engineering/biotechnology application. In addition, the polyethyleneimine is grafted to the crystal glue to obtain a functional material, and the material has good adsorption performance on bilirubin.)

1. A bulky and non-breakable crystalline gel material, characterized in that said crystalline gel material is prepared by pre-freezing an olefin liquid in distilled water containing ice crystals and then copolymerizing at-12 ℃.

2. The bulky crystalline colloidal material being less likely to break according to claim 1, wherein the pre-freezing is followed by copolymerization with nanocellulose as a reinforcing agent.

3. A preparation method of a large-volume and non-breakable crystal glue material is characterized by comprising the following steps:

S1, dissolving an olefin liquid and a cross-linking agent in distilled water containing ice crystals;

S2, freezing the mixed liquid obtained in the step S1 to freeze;

S3, adding an initiator and a catalyst into the frozen mixed liquid obtained in the step S2 at room temperature, stirring, removing bubbles, reacting at-12 ℃, thawing at room temperature after the reaction is finished, and washing with a large amount of distilled water to obtain the crystal glue material.

4. The method of claim 3, wherein in step S2, allyl glycidyl ether is added to the mixture obtained in step S1, and the mixture is stirred until it is completely dissolved and then cooled to ice.

5. The method for preparing a bulky and non-breakable crystalline colloidal material according to claim 3 or 4, wherein in step S2, nanocellulose is added before freezing and then frozen to ice; the nano-cellulose comprises one or more of bacterial cellulose, microfibrillated cellulose and cellulose nanocrystals.

6. The bulk non-breakable polyethyleneimine crystal gel is characterized in that the polyethyleneimine crystal gel is prepared by pre-freezing olefin liquid in distilled water containing ice crystals, copolymerizing the olefin liquid with allyl glycidyl ether at-12 ℃, and then reacting the copolymer with polyethyleneimine at 70 ℃.

7. The high-volume non-breakable polyethyleneimine crystal gel according to claim 6, wherein allyl glycidyl ether and nanocellulose are sequentially added after prefreezing, and then copolymerization is carried out.

8. A method for preparing a bulky and non-breakable polyethyleneimine crystal gel according to claim 4, further comprising the step of S4: and (4) soaking the crystal glue material prepared in the step (S3) in a sodium carbonate buffer solution, then adding a polyethyleneimine solution, reacting at 70 ℃, and washing with distilled water after the reaction is finished to obtain the polyethyleneimine crystal glue.

9. The method for preparing a bulky and non-breakable crystalline silica gel material according to claim 8, wherein in step S2, nanocellulose is added before freezing and then frozen to ice; in step S3, washing with 0.5mol/L NaCl and then with distilled water; in step S4, after the reaction is finished, the reaction product is washed by distilled water, then soaked in 0.5mol/L HCl solution and washed by distilled water to be neutral, and finally soaked in 0.5mol/L NaOH solution and washed by distilled water to be neutral.

10. Use of a bulky non-breakable polyethyleneimine crystal according to claim 6 or 7 for adsorption of bilirubin.

Technical Field

The invention relates to the technical field of crystal glue materials, in particular to a large-volume crystal glue material which is not easy to break and a preparation method thereof.

Background

The macroporous monolithic material has the advantages of high mass transfer speed, strong permeability, stable performance and the like by using the unique interconnected macroporous structure, is widely applied to tissue engineering, cell scaffolds, bioreactors and chromatographic separation, and is a substitute material of next-generation high-performance biological separation chromatographic media. The pores in the macroporous monolith can be created by different methods: porogens, foam porogens, freeze drying, and crystal gel methods were used. Compared with other preparation methods, the freezing crystal glue method is easier to generate highly interpenetrating three-dimensional macropores, prepares a firm material with unique performance, and is more popular in many biomedical applications. Macroporous monoliths, which are typically composed of synthetic polymers (e.g., polyacrylamide, polymethacrylate, polystyrene), natural polymers (e.g., agarose, cellulose), or inorganic materials (e.g., silica), are now widely used for the separation of proteins and small molecules. The large pore size of the frozen crystal gel integrated material is 10-100 mu m, and can process non-clear and viscous samples, including blood, plasma and fermentation liquor, and plant and animal extracts, which provides an opportunity for designing hemoperfusion products. In addition, due to the high concentration of the polymer on the pore wall, the macroporous integral material has high mechanical strength, high compressibility and high elasticity.

However, the work done to date has been done in a laboratory or small scale, producing gels of still small size (volumes of a few milliliters), and with non-uniform pore size distribution across the sample. Preparing large volumes of gel remains a significant challenge in the preparation of larger samples due to uneven heat transfer making freeze kinetics and ice crystal formation conditions difficult to determine. However, for larger scale separation or engineering/biotechnology applications, large volume gels are not the second choice, and therefore, there is a need to provide a large volume gel material and a method for preparing the same.

Disclosure of Invention

In view of the above, the present invention provides a large-sized and non-breakable crystal glue material to overcome at least one of the above disadvantages of the prior art, and solves the problem that the existing crystal glue material cannot satisfy the large-scale separation or engineering/biotechnology application.

In order to solve the technical problems, the invention adopts the following technical scheme:

A high-volume and non-breakable crystal gel material is prepared by pre-freezing olefin liquid in distilled water containing ice crystals and then copolymerizing at-12 ℃, and the volume of the crystal gel material can reach 500 ml.

the invention provides a large-volume and non-breakable crystal gel material for the first time, and the large-volume and non-breakable crystal gel material is prepared by improving a common pre-freezing method, so that most of ice crystals are reserved in the pre-freezing process, the heat transfer is relatively quick, the large-volume crystal gel with uniformly distributed pore diameters can be finally formed, and the problem of internal collapse caused by overlarge pore diameters in a large sample due to extremely non-uniform heat transfer is avoided. The olefin liquid is acrylamide and/or hydroxyethyl methacrylate.

In order to further improve the mechanical strength of the crystal gel material, the crystal gel material is prepared by pre-freezing olefin liquid in distilled water containing ice crystals, adding nano-cellulose serving as a reinforcing agent, and copolymerizing at-12 ℃, so that the nano-cellulose serving as a reinforcing agent is introduced into a polymer matrix to enhance the mechanical strength of the crystal gel. The nano-cellulose comprises one or more of bacterial cellulose, microfibrillated cellulose and cellulose nanocrystals. Experiments prove that the mechanical property of the crystal glue can be obviously improved by adding a small amount of bacterial cellulose, mainly because strong hydrogen bonds are formed between hydroxyl on the surface of the bacterial cellulose and a polymer matrix, and therefore, the bacterial cellulose is preferably used as a reinforcing agent to be added into the polymer matrix.

The invention also provides a preparation method of the crystal glue material with large volume and difficult breakage, which comprises the following steps:

S1, dissolving an olefin liquid and a cross-linking agent into distilled water containing ice crystals;

S2, freezing the mixed liquid obtained in the step S1 to freeze;

s3, adding an initiator and a catalyst into the frozen mixed liquid obtained in the step S2 at room temperature, stirring, removing bubbles, reacting at-12 ℃, thawing at room temperature after the reaction is finished, and washing with a large amount of distilled water to obtain the crystal glue material.

the invention provides a method for preparing a crystal glue material which is large in volume and not easy to break for the first time. The common pre-freezing method is improved, most of ice crystals are reserved in the pre-freezing process, so that heat transfer is relatively fast, large-volume crystal gel with uniform pore size distribution can be finally formed, and the problem of internal collapse caused by overlarge pore size in a large sample due to extremely non-uniform heat transfer is avoided.

In step S2, allyl glycidyl ether is added to the mixed solution obtained in step S1, stirred until completely dissolved, and then cooled to ice. Epoxy groups are introduced to serve as functional groups through allyl glycidyl ether, and subsequent modification and application of the epoxy groups can be facilitated after introduction.

In step S2, the nanocellulose is added before freezing and then frozen to ice. The nanocellulose is introduced into the polymer matrix as a reinforcing agent to enhance the mechanical strength of the crystal glue. The nano-cellulose comprises one or more of bacterial cellulose, microfibrillated cellulose and cellulose nanocrystals. Experiments prove that the mechanical property of the crystal glue can be obviously improved by adding a small amount of bacterial cellulose, mainly because strong hydrogen bonds are formed between hydroxyl on the surface of the bacterial cellulose and a polymer matrix.

In step S3, the sample was washed with 0.5mol/L NaCl and then with distilled water. The high salt concentration is beneficial to promoting the elution of some foreign ions on the crystal glue material and improving the washing effect.

The olefin liquid is acrylamide and/or hydroxyethyl methacrylate, the crosslinking agent is N, N-methylene bisacrylamide, the initiator is ammonium persulfate or potassium persulfate, and the catalyst is N, N, N, N-tetramethyl ethylenediamine.

As the crystal glue material which is large in volume and not easy to break is further refined, the invention also provides a large-volume and not easy to break polyethyleneimine crystal glue, wherein the polyethyleneimine crystal glue is prepared by olefin liquid which is pre-frozen in distilled water containing ice crystals, then is copolymerized with allyl glycidyl ether at the temperature of-12 ℃, and then is reacted with polyethyleneimine at the temperature of 70 ℃, and the volume of the crystal glue material can reach 500 ml.

On the basis of retaining most of ice crystals in the pre-freezing process to finally prepare a large-volume crystal glue material with uniformly distributed pore diameters, the epoxy group introduced by allyl glycidyl ether is used for grafting polyethyleneimine to prepare the large-volume and non-breakable polyethyleneimine crystal glue. The olefin liquid is acrylamide and/or hydroxyethyl methacrylate.

In order to further improve the mechanical strength of the polyethyleneimine crystal gel, the polyethyleneimine crystal gel is prepared by pre-freezing olefin liquid in distilled water containing ice crystals, sequentially adding allyl glycidyl ether and nanocellulose for copolymerization at-12 ℃, and reacting with polyethyleneimine at 70 ℃, so that the nanocellulose is introduced into a polymer matrix as a reinforcing agent to reinforce the mechanical strength of the crystal gel. The nano-cellulose comprises one or more of bacterial cellulose, microfibrillated cellulose and cellulose nanocrystals. Experiments prove that the mechanical property of the crystal glue can be obviously improved by adding a small amount of bacterial cellulose, mainly because strong hydrogen bonds are formed between hydroxyl on the surface of the bacterial cellulose and a polymer matrix, and therefore, the bacterial cellulose is preferably used as a reinforcing agent to be added into the polymer matrix.

The invention also provides a preparation method of the bulky and non-breakable polyethyleneimine crystal glue, which comprises the preparation steps of preparing the bulky and non-breakable crystal glue material, and also comprises the step S4: and (4) soaking the crystal glue material prepared in the step (S3) in a sodium carbonate buffer solution, then adding a polyethyleneimine solution, reacting at 70 ℃, and washing with distilled water after the reaction is finished to obtain the polyethyleneimine crystal glue.

In step S4, after the reaction is finished, the reaction product is washed by distilled water, then soaked in 0.5mol/L HCl solution and washed by distilled water to be neutral, and finally soaked in 0.5mol/L NaOH solution and washed by distilled water to be neutral.

The invention also provides application of the large-volume non-breakable polyethyleneimine crystal gel in bilirubin adsorption, and the polyethyleneimine crystal gel has good adsorption performance on bilirubin.

Compared with the prior art, the invention has the following beneficial effects: the invention provides a method for preparing a crystal glue which is large in volume and not easy to break for the first time. Firstly, by improving the common pre-freezing method, most of ice crystals are reserved in the pre-freezing process, so that the heat transfer is relatively fast, the large-volume crystal gel with uniform pore size distribution can be finally formed, and the problem of internal collapse caused by overlarge pore size in a large sample due to extremely non-uniform heat transfer is avoided. Secondly, the mechanical strength of the crystal gel is enhanced by introducing nanocellulose (bacterial cellulose, microfibrillated cellulose, cellulose nanocrystals) as a reinforcing agent into the polymer matrix. Experiments prove that the mechanical property of the crystal glue can be obviously improved by adding a small amount of bacterial cellulose, mainly because strong hydrogen bonds are formed between hydroxyl on the surface of the bacterial cellulose and a polymer matrix. Finally, successfully preparing a sample with large volume and good mechanical property, characterizing the sample, and thickening the hole wall by adding the bacterial cellulose according to the result of a scanning electron microscope; the results of the compression test showed that the mechanical properties increased significantly with increasing amounts of bacterial cellulose. In addition, Polyethyleneimine (PEI) is fixed through reaction with an epoxy group on the crystal gel, and the material is used for adsorbing bilirubin in physiological saline, and the result shows that the adsorption behavior of the material on bilirubin accords with Langmuir adsorption and quasi-second-order kinetic models, which indicates that the adsorption is monomolecular adsorption, and the maximum adsorption amount is up to 76 mg/g.

Drawings

FIG. 1 is a scanning electron micrograph of a crystalline colloidal material obtained in method example 3.

FIG. 2 is a scanning electron micrograph of the colloidal crystalline material obtained in method example 4.

FIG. 3 is a scanning electron micrograph of a colloidal crystalline material obtained according to method example 5.

FIG. 4 is a scanning electron micrograph of the colloidal crystalline material obtained in comparative example 3.

Fig. 5 is a graph of stress versus strain variation for method examples 3, 4, 5.

Fig. 6 is a graph showing the adsorption curves of the crystal glue material of example 4 of the product prepared by using different amounts of the bacterial cellulose dispersion (BC).

Detailed Description

In order to make the implementation objects, technical solutions and advantages of the present invention clearer, the present invention will be further described with reference to the accompanying drawings. The technical solutions in the embodiments of the present invention are part of the embodiments of the present invention, and not all of the embodiments of the present invention. The following examples are illustrative and are intended to be illustrative of the invention and are not to be construed as limiting the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Product example 1

A high-volume and non-breakable crystal gel material is prepared by pre-freezing olefin liquid in distilled water containing ice crystal and copolymerizing at-12 ℃.

Product example 2

A large-volume and non-breakable crystal gel material is prepared by pre-freezing olefin liquid in distilled water containing ice crystals, adding nano cellulose as a reinforcing agent, and copolymerizing at-12 ℃.

Product example 3

A high-volume non-breakable polyethyleneimine crystal gel is prepared by pre-freezing olefin liquid in distilled water containing ice crystals, adding allyl glycidyl ether to copolymerize at-12 ℃, and reacting with polyethyleneimine at 70 ℃.

Product example 4

The polyethyleneimine crystal gel is prepared by pre-freezing olefin liquid in distilled water containing ice crystals, sequentially adding allyl glycidyl ether and nanocellulose, copolymerizing at-12 ℃, and reacting with polyethyleneimine at 70 ℃.

Method example 1

A method for preparing the bulky and non-breakable crystalline colloidal material of product example 2: dissolving 5g of acrylamide and 1.5g N, N-methylene bisacrylamide in 95mL of distilled water containing ice crystals (prefreezing), adding 1.8mL of allyl glycidyl ether, placing the mixture in a high-speed stirrer to be stirred until the mixture is completely dissolved (the rotating speed is 600r/min), adding 5mL of bacterial cellulose dispersion liquid (BC), stirring for 3-5min (the rotating speed is 600r/min), placing the mixture in a low-temperature test box (-20 ℃) to be frozen to ice, taking out the frozen mixture, adding 0.1g of ammonium persulfate and 0.1mL of N, N, N, N-tetramethylethylenediamine at room temperature, stirring for 5min (the rotating speed is 600r/min), ultrasonically removing bubbles, pouring the frozen mixture into a mold, placing the mold in the low-temperature test box (-12 ℃) and reacting for 24 h. The tube was thawed at room temperature and washed with copious amounts of distilled water.

Method example 2

A method for preparing the bulky and non-breakable crystalline colloidal material of product example 2: dissolving 5g of hydroxyethyl methacrylate and 1.5g N, N-methylene bisacrylamide in 85mL of distilled water containing ice crystals (prefreezing), adding 1.8mL of allyl glycidyl ether, placing the mixture in a high-speed stirrer to be stirred until the mixture is completely dissolved (the rotating speed is 600r/min), adding 15mL of bacterial cellulose dispersion liquid (BC), stirring for 3-5min (the rotating speed is 600r/min), placing the mixture in a low-temperature test box (20 ℃ below zero) to be frozen to ice, taking out the frozen mixture, adding 0.1g of ammonium persulfate and 0.1mL of N, N, N, N-tetramethylethylenediamine at room temperature, stirring for 5min (the rotating speed is 600r/min), ultrasonically removing bubbles, pouring the frozen mixture into a mold, placing the mold in the low-temperature test box (12 ℃ below zero), and reacting for 24 h. The tube was thawed at room temperature and washed with copious amounts of distilled water.

Method example 3

A method for preparing the bulky and non-breakable crystalline colloidal material of product example 2: dissolving 2.5g of acrylamide, 2.5g of hydroxyethyl methacrylate and 1.5g N, N-methylene bisacrylamide in 95mL of distilled water containing ice crystals (prefreezing), adding 1.8mL of allyl glycidyl ether, stirring the mixture under a high-speed stirrer until the mixture is completely dissolved (the rotating speed is 600r/min), adding 5mL of bacterial cellulose dispersion (BC), stirring the mixture for 3 to 5min (the rotating speed is 600r/min), freezing the mixture in a low-temperature test box at (-20 ℃) until the mixture is frozen, taking out the mixture, adding 0.1g of ammonium persulfate and 0.1mL of N, N, N, N-tetramethylethylenediamine at room temperature, stirring the mixture for 5min (the rotating speed is 600r/min), ultrasonically removing bubbles, pouring the mixture into a mold, placing the mold in the low-temperature test box at (-12 ℃) and reacting for 24 h. The tube was thawed at room temperature and washed with copious amounts of distilled water.

Method example 4

A method for preparing the bulky and non-breakable crystalline colloidal material of product example 2: dissolving 2.5g of acrylamide, 2.5g of hydroxyethyl methacrylate and 1.5g N, N-methylene bisacrylamide in 85mL of distilled water containing ice crystals (prefreezing), adding 1.8mL of allyl glycidyl ether, stirring the mixture under a high-speed stirrer until the mixture is completely dissolved (the rotating speed is 600r/min), adding 15mL of bacterial cellulose dispersion (BC), stirring the mixture for 3 to 5min (the rotating speed is 600r/min), freezing the mixture in a low-temperature test box at (-20 ℃) until the mixture is frozen, taking out the mixture, adding 0.1g of ammonium persulfate and 0.1mL of N, N, N, N-tetramethylethylenediamine at room temperature, stirring the mixture for 5min (the rotating speed is 600r/min), ultrasonically removing bubbles, pouring the mixture into a mold, placing the mold in the low-temperature test box at (-12 ℃) and reacting for 24 h. The tube was thawed at room temperature and washed with copious amounts of distilled water.

Method example 5

A method for preparing the bulky and non-breakable crystalline colloidal material of product example 2: dissolving 2.5g of acrylamide, 2.5g of hydroxyethyl methacrylate and 1.5g N, N-methylene bisacrylamide in 75mL of distilled water containing ice crystals (prefreezing), adding 1.8mL of allyl glycidyl ether, stirring the mixture under a high-speed stirrer until the mixture is completely dissolved (the rotating speed is 600r/min), adding 25mL of bacterial cellulose dispersion (BC), stirring the mixture for 3 to 5min (the rotating speed is 600r/min), freezing the mixture in a low-temperature test box at (-20 ℃) until the mixture is frozen, taking out the mixture, adding 0.1g of ammonium persulfate and 0.1mL of N, N, N, N-tetramethylethylenediamine at room temperature, stirring the mixture for 5min (the rotating speed is 600r/min), ultrasonically removing bubbles, pouring the mixture into a mold, placing the mold in the low-temperature test box at (-12 ℃) and reacting for 24 h. The tube was thawed at room temperature and washed with copious amounts of distilled water.

Method example 6

a method for preparing the bulky and non-breakable crystalline colloidal material of product example 2: dissolving 2.5g of acrylamide, 2.5g of hydroxyethyl methacrylate and 1.5g N, N-methylene bisacrylamide in 95mL of distilled water containing ice crystals (prefreezing), adding 1.8mL of allyl glycidyl ether, stirring the mixture under a high-speed stirrer until the mixture is completely dissolved (the rotating speed is 600r/min), adding 5mL of microfibrillated cellulose dispersion (MFC), stirring the mixture for 3 to 5min (the rotating speed is 600r/min), freezing the mixture in a low-temperature test box at (-20 ℃) until the mixture is frozen, taking out the mixture, adding 0.1g of ammonium persulfate and 0.1mL of N, N, N, N-tetramethyl ethylenediamine at room temperature, stirring the mixture for 5min (the rotating speed is 600r/min), ultrasonically removing bubbles, pouring the mixture into a mold, placing the mold in the low-temperature test box at (-12 ℃) and reacting for 24 hours. The tube was thawed at room temperature and washed with copious amounts of distilled water.

Method example 7

A method for preparing the bulky and non-breakable crystalline colloidal material of product example 2: dissolving 2.5g of acrylamide, 2.5g of hydroxyethyl methacrylate and 1.5g N, N-methylene bisacrylamide in 85mL of distilled water containing ice crystals (prefreezing), adding 1.8mL of allyl glycidyl ether, stirring the mixture under a high-speed stirrer until the mixture is completely dissolved (the rotating speed is 600r/min), adding 15mL of microfibrillated cellulose dispersion (MFC), stirring the mixture for 3 to 5min (the rotating speed is 600r/min), freezing the mixture in a low-temperature test box at (-20 ℃) until the mixture is frozen, taking out the mixture, adding 0.1g of ammonium persulfate and 0.1mL of N, N, N, N-tetramethyl ethylenediamine at room temperature, stirring the mixture for 5min (the rotating speed is 600r/min), ultrasonically removing bubbles, pouring the mixture into a mold, placing the mold in the low-temperature test box at (-12 ℃) and reacting for 24 hours. The tube was thawed at room temperature and washed with copious amounts of distilled water.

Method example 8

A method for preparing the bulky and non-breakable crystalline colloidal material of product example 2: dissolving 5g of acrylamide, 2.5g of hydroxyethyl methacrylate and 1.5g N, N-methylene bisacrylamide in 95mL of distilled water containing ice crystals (prefreezing), adding 1.8mL of allyl glycidyl ether, stirring the mixture in a high-speed stirrer until the mixture is completely dissolved (the rotating speed is 600r/min), adding 5mL of Cellulose Nanocrystal (CNC), stirring the mixture for 3 to 5min (the rotating speed is 600r/min), freezing the mixture in a low-temperature test box at (-20 ℃) until the mixture is frozen, taking out the mixture, adding 0.1g of ammonium persulfate and 0.1mL of N, N, N, N-tetramethyl ethylenediamine at room temperature, stirring the mixture for 5min (the rotating speed is 600r/min), ultrasonically removing bubbles, pouring the mixture into a mold, placing the mold in a low-temperature test box at (-12 ℃) and reacting for 24 hours. The tube was thawed at room temperature and washed with copious amounts of distilled water.

Method example 9

A method for preparing the bulky and non-breakable crystalline colloidal material of product example 2: dissolving 5g of acrylamide, 2.5g of hydroxyethyl methacrylate and 1.5g N, N-methylene bisacrylamide in 85mL of distilled water containing ice crystals (prefreezing), adding 1.8mL of allyl glycidyl ether, stirring the mixture in a high-speed stirrer until the mixture is completely dissolved (the rotating speed is 600r/min), adding 15mL of Cellulose Nanocrystal (CNC), stirring the mixture for 3 to 5min (the rotating speed is 600r/min), freezing the mixture in a low-temperature test box at (-20 ℃) until the mixture is frozen, taking out the mixture, adding 0.1g of ammonium persulfate and 0.1mL of N, N, N, N-tetramethyl ethylenediamine at room temperature, stirring the mixture for 5min (the rotating speed is 600r/min), ultrasonically removing bubbles, pouring the mixture into a mold, placing the mold in a low-temperature test box at (-12 ℃) and reacting for 24 h. The tube was thawed at room temperature and washed with copious amounts of distilled water.

Comparative example 1

Example 1 was performed in the same manner as above except that distilled water did not contain ice crystals during the prefreezing.

Comparative example 2

Example 2 was performed in the same manner as above except that the distilled water did not contain ice crystals during the prefreezing.

Comparative example 3

method example 4 was followed except that no bacterial cellulose was added. Dissolving 2.5g of acrylamide, 2.5g of hydroxyethyl methacrylate and 1.5g N, N-methylene bisacrylamide in 100mL of distilled water containing ice crystals (prefreezing), adding 1.8mL of allyl glycidyl ether, stirring the mixture under a high-speed stirrer until the mixture is completely dissolved (the rotating speed is 600r/min), placing the mixture in a low-temperature test box (-20 ℃) to freeze until the mixture is frozen, taking out the mixture, adding 0.1g of ammonium persulfate and 0.1mL of N, N, N, N-tetramethyl ethylenediamine at room temperature, stirring the mixture for 5min (the rotating speed is 600r/min), ultrasonically removing bubbles, pouring the mixture into a middle-placed mould, placing the mixture in the low-temperature test box (-12 ℃) and reacting for 24 h. The tube was thawed at room temperature and washed with copious amounts of distilled water.

The determination method comprises the following steps:

1. the crystal glue materials prepared by the method examples 3-5 and the comparative example 3 are made into samples, and are respectively measured by a scanning electron microscope, and the obtained scanning electron microscope images are respectively shown in figures 1-4.

2. Respectively carrying out compression tests on the crystal glue materials prepared by the method examples 3-5, wherein the test results are shown in FIG. 5;

The addition of the bacterial cellulose thickens the hole wall according to the result of a scanning electron microscope; the results of the compression test showed that the mechanical properties increased significantly with increasing amounts of bacterial cellulose.

Method example 10

A method for preparing the bulky and non-breakable polyethyleneimine crystal glue of product example 4:

Preparation of crystal glue material

Dissolving 2.5g of acrylamide, 2.5g of hydroxyethyl methacrylate and 1.5g N, N-methylene bisacrylamide in 85mL of distilled water containing ice crystals (prefreezing), adding 1.8mL of allyl glycidyl ether, stirring the mixture under a high-speed stirrer until the mixture is completely dissolved (the rotating speed is 600r/min), adding 15mL of microfibrillated cellulose dispersion (MFC), stirring the mixture for 3 to 5min (the rotating speed is 600r/min), freezing the mixture in a low-temperature test box at (-20 ℃) until the mixture is frozen, taking out the mixture, adding 0.1g of ammonium persulfate and 0.1mL of N, N, N, N-tetramethyl ethylenediamine at room temperature, stirring the mixture for 5min (the rotating speed is 600r/min), ultrasonically removing bubbles, pouring the mixture into a mold, placing the mold in the low-temperature test box at (-12 ℃) and reacting for 24 hours. The tube was thawed at room temperature and washed with copious amounts of distilled water.

Bis, linking polyethyleneimine

The crystal gel is washed by 0.5mol/L NaCl and then by distilled water. The mixture was soaked in 0.5mol/L sodium carbonate buffer (pH 10.5) at room temperature for 2 h. Then, a 10% polyethyleneimine solution (pH 10.6) was added, and the reaction was carried out at 70 ℃ for 8 hours. Washing with distilled water, soaking in 0.5mol/L HCl solution for 2h, and washing with distilled water to neutrality; then soaking the mixture in 0.5mol/L NaOH solution for 2 hours, and washing the mixture with distilled water to be neutral.

Third, the adsorption evaluation of the polyethyleneimine crystal glue to bilirubin

Freeze-drying the above materials in a freeze-drying machine, weighing a certain mass, adding bilirubin solution with initial concentration of 0.1-1mol/L, and oscillating at 37 deg.C for 2h for adsorption. The supernatant was taken and the absorbance A was measured at 435 nm. The maximum adsorption was calculated by a Langmuir adsorption curve (as shown in fig. 6).

It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.