阅读说明：本技术 一种抑菌纤维素可降解复合膜的制备方法 (Preparation method of antibacterial cellulose degradable composite membrane ) 是由 王娟 未君洪 余同林 张伟亮 贾鹏飞 张星辰 于 2019-11-19 设计创作，主要内容包括：本发明公开了一种抑菌纤维素可降解复合膜的制备方法,包括如下步骤：A、将纤维素与N-甲基吗琳-N-氧化物即NMMO的一水合物充分混合得到均匀透明的纤维素-NMMO铸膜液；B、取胍盐与己二胺,通过阶段性的升温-降温工艺控制使二者发生聚合反应,产物离子交换,制得离子液体；C、将纤维素-NMMO铸膜液利用玻璃板刮制成膜,以抑菌离子液体为凝固浴相转成膜,得到抑菌纤维素复合膜。本发明为环境友好型制备方法,制备的再生纤维素膜无毒无污染可降解,具有良好的抗菌性,可用于塑料薄膜制造业等领域。(The invention discloses a preparation method of an antibacterial cellulose degradable composite membrane, which comprises the following steps: A. fully mixing cellulose and N-methylmorpholine-N-oxide, namely NMMO monohydrate to obtain uniform and transparent cellulose-NMMO membrane casting solution; B. taking guanidine salt and hexamethylenediamine, controlling the guanidine salt and the hexamethylenediamine through a staged heating-cooling process to enable the guanidine salt and the hexamethylenediamine to generate a polymerization reaction, and performing ion exchange on a product to prepare an ionic liquid; C. and scraping the cellulose-NMMO film casting solution into a film by using a glass plate, and performing phase inversion to form the film by using the antibacterial ionic liquid as a coagulating bath to obtain the antibacterial cellulose composite film. The invention is an environment-friendly preparation method, and the prepared regenerated cellulose membrane is nontoxic, pollution-free and degradable, has good antibacterial property, and can be used in the fields of plastic film manufacturing industry and the like.)

1. A preparation method of an antibacterial cellulose degradable composite membrane is characterized by comprising the following steps: the method comprises the following steps:

A. dissolution of cellulose: fully mixing cellulose and N-methylmorpholine-N-oxide, namely NMMO monohydrate, heating for full swelling, and then dissolving under reduced pressure to obtain uniform and transparent cellulose-NMMO membrane casting solution;

B. preparing bacteriostatic ionic liquid: firstly, guanidine salt and hexamethylene diamine are taken and are subjected to polymerization reaction through the control of a staged heating-cooling process, and the obtained product and PF₆-、BF₄-、(CF₃SO₂)₂N-、CF₃SO₃Ion exchange is carried out inside to prepare the high molecular ionic liquid which is liquid at normal temperature and has good film forming property and long-term antibacterial activity;

C. preparing an antibacterial cellulose composite membrane: and scraping the cellulose-NMMO film casting solution into a film by using a glass plate, and performing phase inversion to form the film by using the antibacterial ionic liquid as a coagulating bath to obtain the antibacterial cellulose composite film.

2. The preparation method of the antibacterial cellulose degradable composite membrane according to claim 1 is characterized in that: in the step B, heating and stirring hexamethylene diamine and guanidine salt under the protection of nitrogen, keeping the temperature of 5-15 ℃ per liter for 10-20min after heating to 80-120 ℃, continuing to react for 3-9h until the temperature is raised to 160-200 ℃, and finishing the polymerization reaction; naturally cooling the polymer to 140 ℃ below zero, adding acid into the polymer, and reacting for 2-6h to prepare the high molecular ionic liquid which is liquid at normal temperature and has good film forming property and long-term antibacterial activity; the molar ratio of the hexamethylene diamine to the guanidine salt to the acid is 1 (0.8-1.2) to 0.8-1.2.

3. The preparation method of the antibacterial cellulose degradable composite membrane according to claim 1 is characterized in that: in the step B, adding 1mol of hexamethylenediamine and 1mol of guanidine hydrochloride into a dry 250mL three-necked bottle, introducing nitrogen, heating and stirring under the protection of the nitrogen, heating to 100 ℃, keeping the temperature of 10 ℃ per liter for 15min until the temperature is increased to 180 ℃, continuing to react for 6h, and finishing the polymerization reaction; and naturally cooling the polymer to 120 ℃, adding 1mol of tetrafluoroboric acid into the polymer, and reacting for 4 hours to prepare the high molecular ionic liquid which is liquid at normal temperature and has good film forming property and long-term antibacterial activity.

4. The preparation method of the antibacterial cellulose degradable composite membrane according to claim 1 is characterized in that: the guanidine salt is selected from: guanidine hydrochloride, 6-guanidinohexanoic acid hydrochloride, hexamethylenebiguanide hydrochloride, hexamethylenebioctaguanidine, 4-hydroxyisoquinolin, 1- (5-nitrofurfurylidene) aminoguanidine hydrochloride, N-ethylguanidine hydrochloride, nitrosoguanidine, 3-chlorophenylguanidine, dodecylguanidine monohydrochloride, diethylguanidine sulfate, triaminoguanidine hydrochloride, metaiodophenylguanidine sulfate, hexamethyleneguanidine hydrochloride sulfaguanidine, hexamethyleneguanidine phosphate, aminoguanidine bicarbonate, biguanide nitrate, chloroguanidine, methylguanidine, hydrogenphosphate, N- (3, 4-dichlorophenyl) guanidine, polyaminopropylbiguanide, hexamethylene1, 6-dicyandiamide, monoguanidine phosphate, cimetidine, dodecylguanidine acetate, and triguanidine phosphate.

5. The preparation method of the antibacterial cellulose degradable composite membrane according to claim 1 is characterized in that: the acid is selected from: tetrafluoroboric acid, hexafluorophosphoric acid, fluorosulfonic acid, sulfuric acid, nitric acid, trifluoroacetic acid, oxalic acid, succinic acid, adipic acid, KMD acid, methanesulfonic acid, p-toluenesulfonic acid, citric acid, aspartic acid, acetic acid, propionic acid, chloric acid.

Technical Field

The invention relates to the technical field of chemical industry, in particular to a bacteriostatic cellulose membrane and a preparation method thereof.

Background

Cellulose is the most precious natural renewable resource of human beings, according to statistics, hundreds of millions of tons of cellulose can be produced by natural biosynthesis in the world every year, petroleum cannot be compared with the cellulose, and the cellulose has the advantages of biodegradability, environmental protection, stable chemical properties and the like, can be applied to multiple fields of food, packaging, life science, textile, light industry, chemical industry and the like as an ideal material, and plays a very important role in national economy. Early cellulose was formed into films by the cuprammonium process or the viscose process, but these two processes were complex, costly and severely polluting. In recent years, LiCl/DMAc, N have appeared₂O₄DMF, ionic liquids, urea/NaOH, N-methylmorpholine-N-oxide (NMMO), and the like.

NMMO is used as a novel cellulose solvent, has extremely strong cellulose dissolving capacity, is pollution-free, and the prepared cellulose membrane has biodegradability. However, the surface of the produced cellulose membrane can grow bioactive substances and cause biological pollution of the membrane, so that the cellulose membrane with antibacterial performance needs to be developed.

Chitosan/cellulose composite membranes were studied by Ninggang et al (Chitosan cellulose composite membranes and methods of preparation and use, China patent: CN104892969A, 2015-09-09), but the cellulose/chitosan composite membranes prepared by this method have the disadvantages of poor compatibility, poor mechanical properties, and insignificant antibacterial properties.

Disclosure of Invention

The invention aims to solve the technical problem of providing a preparation method of an antibacterial cellulose degradable composite membrane.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows.

A preparation method of an antibacterial cellulose degradable composite membrane comprises the following steps:

A. dissolution of cellulose: fully mixing cellulose and N-methylmorpholine-N-oxide, namely NMMO monohydrate, heating for full swelling, and then dissolving under reduced pressure to obtain uniform and transparent cellulose-NMMO membrane casting solution;

B. preparing bacteriostatic ionic liquid: firstly, guanidine salt and hexamethylene diamine are taken and are subjected to polymerization reaction through the control of a staged heating-cooling process, and the obtained product and PF₆-、BF₄-、(CF₃SO₂)₂N-、CF₃SO₃Ion exchange is carried out inside to prepare the high molecular ionic liquid which is liquid at normal temperature and has good film forming property and long-term antibacterial activity;

C. preparing an antibacterial cellulose composite membrane: and scraping the cellulose-NMMO film casting solution into a film by using a glass plate, and performing phase inversion to form the film by using the antibacterial ionic liquid as a coagulating bath to obtain the antibacterial cellulose composite film.

In the step B, the hexamethylene diamine and the guanidine salt are heated and stirred under the protection of nitrogen, and after the hexamethylene diamine and the guanidine salt are heated to 80-120 ℃, the temperature is kept at 5-15 ℃ per liter for 10-20min until the temperature is raised to 160-200 ℃, the reaction is continued for 3-9h, and the polymerization reaction is finished; naturally cooling the polymer to 140 ℃ below zero, adding acid into the polymer, and reacting for 2-6h to prepare the high molecular ionic liquid which is liquid at normal temperature and has good film forming property and long-term antibacterial activity; the molar ratio of the hexamethylene diamine to the guanidine salt to the acid is 1 (0.8-1.2) to 0.8-1.2.

As a preferred technical scheme, in the step B, 1mol of hexamethylenediamine and 1mol of guanidine hydrochloride are added into a dry 250mL three-necked bottle, nitrogen is introduced, the mixture is heated and stirred under the protection of the nitrogen, after the mixture is heated to 100 ℃, the temperature of 10 ℃ per liter is kept for 15min until the temperature is increased to 180 ℃, the reaction is continued for 6h, and the polymerization reaction is finished; and naturally cooling the polymer to 120 ℃, adding 1mol of tetrafluoroboric acid into the polymer, and reacting for 4 hours to prepare the high molecular ionic liquid which is liquid at normal temperature and has good film forming property and long-term antibacterial activity.

As a preferred embodiment of the present invention, the guanidine salt is selected from: guanidine hydrochloride, 6-guanidinohexanoic acid hydrochloride, hexamethylenebiguanide hydrochloride, hexamethylenebioctaguanidine, 4-hydroxyisoquinolin, 1- (5-nitrofurfurylidene) aminoguanidine hydrochloride, N-ethylguanidine hydrochloride, nitrosoguanidine, 3-chlorophenylguanidine, dodecylguanidine monohydrochloride, diethylguanidine sulfate, triaminoguanidine hydrochloride, metaiodophenylguanidine sulfate, hexamethyleneguanidine hydrochloride sulfaguanidine, hexamethyleneguanidine phosphate, aminoguanidine bicarbonate, biguanide nitrate, chloroguanidine, methylguanidine, hydrogenphosphate, N- (3, 4-dichlorophenyl) guanidine, polyaminopropylbiguanide, hexamethylene1, 6-dicyandiamide, monoguanidine phosphate, cimetidine, dodecylguanidine acetate, and triguanidine phosphate.

As a preferred embodiment of the present invention, the acid is selected from: tetrafluoroboric acid, hexafluorophosphoric acid, fluorosulfonic acid, sulfuric acid, nitric acid, trifluoroacetic acid, oxalic acid, succinic acid, adipic acid, KMD acid, methanesulfonic acid, p-toluenesulfonic acid, citric acid, aspartic acid, acetic acid, propionic acid, chloric acid.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in: the invention is pollution-free and environment-friendly, and the process developed by the invention is simple and convenient to operate, and the prepared regenerated cellulose membrane is non-toxic, pollution-free, degradable, has good antibacterial property, and can be used in the fields of plastic film manufacturing industry and the like. Particularly, the macromolecular ionic liquid antibacterial agent is the pioneer in the research field, and has good practical effect when being applied to a cellulose membrane.

Detailed Description

The following examples illustrate the invention in detail. The raw materials and various devices used in the invention are conventional commercially available products, and can be directly obtained by market purchase.