阅读说明：本技术 一种植物系抗菌再生纤维素纤维的制备方法 (Preparation method of plant-based antibacterial regenerated cellulose fiber ) 是由 张锁江 周乐 聂毅 高红帅 王斌琦 张赛 于 2020-06-11 设计创作，主要内容包括：本发明公开了一种植物系抗菌再生纤维素纤维的制备方法。针对抗菌再生纤维素纤维制备过程中基底纤维传统工艺的重污染、高能耗以及抗菌剂毒性大、生物相容性差等问题,提出采用离子液体分步溶解天然纤维素和天然植物系抗菌剂,通过湿法或者干喷湿法纺丝制备抗菌再生纤维,实现再生纤维素纤维的清洁绿色化生产和再生纤维素纤维抗菌和舒适度的双重功效。(The invention discloses a preparation method of plant-based antibacterial regenerated cellulose fibers. Aiming at the problems of heavy pollution, high energy consumption, high toxicity of an antibacterial agent, poor biocompatibility and the like of a traditional process of a substrate fiber in the preparation process of the antibacterial regenerated cellulose fiber, the method adopts ionic liquid to dissolve natural cellulose and a natural plant antibacterial agent step by step, prepares the antibacterial regenerated fiber through wet method or dry-spray wet method spinning, and realizes the clean and green production of the regenerated cellulose fiber and the dual effects of antibiosis and comfort of the regenerated cellulose fiber.)

1. A preparation method of plant-based antibacterial regenerated cellulose fibers is characterized by comprising the following steps: adding cellulose into ionic liquid at high temperature, cooling to low temperature after complete dissolution, adding a plant-based antibacterial agent, obtaining spinning stock solution after complete dissolution and deaeration, and spinning by a wet method or a dry-jet wet method by taking water as a coagulating bath to obtain the antibacterial regenerated cellulose fiber.

2. The method for preparing the plant-based antibacterial regenerated cellulose fiber according to claim 1, wherein the cellulose is at least one of natural cellulose or microcrystalline cellulose in cotton pulp, wood pulp, corncobs, straws, hemp fiber, bamboo fiber and short linters, and the polymerization degree is 200-1000; the cellulose accounts for 0.1-20 w% of the ionic liquid.

3. The method for preparing plant-based antibacterial regenerated cellulose fibers according to claim 1, wherein the ionic liquid is selected from 1-R₂-3-R₁Imidazolium chloride salt, 1-R₂-3-R₁Imidazole acetate, 1-R₂-3-R₁Imidazole phosphoric acid dimethyl (or ethyl, butyl) ester, 1-R₂-3-R₁Imidazole carbonic acid dimethyl (or ethyl, butyl) ester, 1-R₂Pyridinium chloride salt, 1-R₂3-methylpyridinium chloride salt, 1-R₂-1, 5-diazabicyclo [4.3.0]-5-nonene phosphoric acid dimethyl (or ethyl, butyl) ester, 1-R₂-1, 5-diazabicyclo [4.3.0]-5-nonene acetate, 1-allyl-3-methylimidazole chloride, 1-ethyl (or butyl) -3-methylimidazole levulinate, choline acetate, choline amino acid, or a combination of at least 1 of them; wherein R is₁＝C_nH_2n+1N takes a value of 1-20; r₂＝C_mH_2m+1And m takes a value of 1-20 (n, m are positive integers).

4. The method for preparing a plant-based antibacterial regenerated cellulose fiber according to claim 1, wherein the plant-based antibacterial agent is plant essential oil having antibacterial effect, oregano, cinnamon, thyme, tea tree, chamomile, sweet marjoram, lavender, eucalyptus, lemon grass, aloe, mint, thyme, stevia, lemon verbena, basil, sage, lavender, rosemary, saffron, parsley, yarrow essential oil, and sweet wormwood wax oil extracted from artemisia annua, artemisia argyi, artemisia alba, artemisia japonica; the plant antibacterial agent accounts for 1 to 1000 percent of the weight of the cellulose.

5. The method for preparing the plant-based antibacterial regenerated cellulose fiber according to claim 1, wherein the high temperature is 70-150 ℃, and the low temperature is 25-70 ℃; the dissolving and defoaming are carried out by mechanically stirring in a reaction kettle, vacuum dissolving and defoaming or extruding by a double screw rod.

6. An antibacterial regenerated cellulose fiber, characterized in that, the antibacterial regenerated cellulose fiber prepared by any one of the methods of claims 1-5 has high washing fastness and the bacteriostasis rate to escherichia coli and staphylococcus aureus is over 85 percent.

Technical Field

The invention relates to a preparation method of an antibacterial regenerated cellulose fiber, and belongs to the technical field of functional regenerated cellulose fibers.

Background

Along with the development of social economy and the improvement of living standard of people, people pay more and more attention to the influence of microorganisms on health, health care consciousness is increasingly strengthened, textiles with the functions of antibiosis and deodorization are popular with consumers at home and abroad, and the requirements of antibiosis household textiles and medical textiles are increasingly increased. The antibacterial fiber is a fiber which is added with an antibacterial agent on the surface or inside by adopting a physical or chemical method to enable the antibacterial fiber to have an antibacterial function, and can be applied to the fields of household textiles, bandages, gauze and the like. Common antibacterial agents are classified into three major classes, inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents. The inorganic antibacterial agent mainly takes silver solution as a main material, and patent CN 201711109406.3 'a nano-silver antibacterial cellulose fiber with a sandwich structure' reports that the nano-silver antibacterial cellulose fiber is prepared by dipping cellulose fiber with the nano-silver solution; patent CN 201811011918.0 "a method for preparing an antibacterial cellulose fiber" adopts nano silver or medical zinc oxide as an antibacterial agent and adds an ionic liquid cellulose spinning solution to prepare a regenerated cellulose fiber doped with a metal antibacterial agent, but the textile of the silver antibacterial agent is easy to fall off in the using process to affect the antibacterial performance, and the nano silver is easy to permeate into the human body through skin contact to cause harm to the human body. The patent CN 201611206940.1 'an antibacterial fiber and a preparation method thereof' invents that a quaternary ammonium salt antibacterial agent is grafted on a substrate fiber to prepare the antibacterial fiber by reaction, but the preparation process has great pollution to the environment, and the quaternary ammonium salt antibacterial agent is easy to react with an organic cleaning agent in the washing process to lose the antibacterial property; the natural plant antibacterial agent is an organic high molecular substance with antibacterial function extracted from natural plants, has wide sources, good biocompatibility and high safety to human bodies, and the preparation of the antibacterial fiber by adopting the natural plant antibacterial agent is an important direction for future development.

The currently industrialized antibacterial fiber is mainly a synthetic fiber, the raw materials of which mainly come from non-renewable resources such as coal, petroleum and the like, and the synthetic fiber has poor sustainable development and low biocompatibility in the long run and is far inferior to the regenerated fiber prepared by taking natural cellulose as the raw material. The regenerated cellulose fiber is an important bio-based chemical fiber, takes natural plant cellulose which is renewable, easy to degrade and large in reserve as a raw material, is known as breathable fabric due to the properties of good hygroscopicity, good dyeing property, strong air permeability, excellent drapability, silk-like luster and the like, and is applied to the high-end textile field. With the increasing exhaustion of petroleum resources and the deep implementation of sustainable development strategy, the production of regenerated cellulose fibers from natural cellulose has a very important significance for the efficient utilization of resources. For the research on the antibacterial regenerated cellulose fiber, the substrate fiber mainly takes viscose fiber as a main fiber, and the viscose process has heavy pollution and high energy consumption; the selection of the antibacterial agent mainly takes metal antibacterial agents such as silver, copper and the like, and has high cost and poor biocompatibility and comfort.

Based on the current research situation, on the basis of preparing the regenerated cellulose fiber by dissolving cellulose with the ionic liquid in the early stage, creatively proposes that the base fiber is prepared by adopting a green and clean production process based on the ionic liquid, natural plant antibacterial agents with better biocompatibility, such as various plant essential oils of origanum vulgaris, cinnamon, aloe essential oil, sweet wormwood wax oil and the like, are added into the ionic liquid-cellulose spinning solution, and the raw materials of the cellulose and the plant antibacterial agents in the nature are fully utilized, so that the dual effects of clean and green production of the regenerated cellulose fiber, and antibacterial property and comfort of the regenerated cellulose fiber are realized.

Disclosure of Invention

Aiming at the problems of heavy pollution, high energy consumption, high toxicity of an antibacterial agent, poor biocompatibility and the like of a traditional process of a substrate fiber in the preparation process of the antibacterial regenerated cellulose fiber, the invention provides a method for preparing the antibacterial regenerated fiber by dissolving natural cellulose and a natural plant antibacterial agent by using an ionic liquid and spinning by a wet method or a dry-spray wet method, and realizes the clean and green production of the regenerated cellulose fiber and the dual effects of antibiosis and comfort of the regenerated cellulose fiber.

The invention comprises the following contents:

adding cellulose into ionic liquid at high temperature, cooling to low temperature after complete dissolution, adding a plant-based antibacterial agent, obtaining spinning stock solution after complete dissolution and deaeration, and spinning by a wet method or a dry-jet wet method by taking water as a coagulating bath to obtain the antibacterial regenerated cellulose fiber.

The cellulose is at least one of natural cellulose and microcrystalline cellulose in cotton pulp, wood pulp, corncobs, straws, fibrilia, bamboo fiber and short linter, and the polymerization degree is 200-1000; the cellulose accounts for 0.1-20 w% of the ionic liquid.

The ionic liquid is selected from 1-R₂-3-R₁Imidazolium chloride salt, 1-R₂-3-R₁Imidazole acetate, 1-R₂-3-R₁Imidazole phosphoric acid dimethyl (or ethyl, butyl) ester, 1-R₂-3-R₁Imidazole carbonic acid dimethyl (or ethyl, butyl) ester, 1-R₂Pyridinium chloride salt, 1-R₂3-methylpyridinium chloride salt, 1-R₂-1, 5-diazabicyclo [4.3.0]-5-nonene phosphoric acid dimethyl (or ethyl, butyl) ester, 1-R₂-1, 5-diazabicyclo [4.3.0]-5-nonene acetate, 1-allyl-3-methylimidazole chloride, 1-ethyl (or butyl) -3-methylimidazole levulinate, choline acetate, choline amino acid, or a combination of at least 1 of them; wherein R is₁＝C_nH_2n+1N takes a value of 1-20; r₂＝C_mH_2m+1And m takes a value of 1-20 (n, m are positive integers).

The plant antibacterial agent is plant essential oil with antibacterial effect, such as origanum vulgaris, cinnamon, thyme, tea tree, chamomile, sweet marjoram, lavender, eucalyptus, lemon grass, aloe, mint, thyme, stevia, lemon verbena, basil, sage, lavender, rosemary, saffron, parsley, milfoil essential oil, and sweet wormwood wax oil extracted from Artemisia annua, Artemisia argyi, Artemisia japonica, and Artemisia japonica; the plant antibacterial agent accounts for 1 to 1000 percent of the weight of the cellulose.

The high temperature is 70-150 ℃, and the low temperature is 25-70 ℃; the dissolving and defoaming are carried out by mechanically stirring in a reaction kettle, vacuum dissolving and defoaming or extruding by a double screw rod.

The antibacterial regenerated cellulose fiber prepared by the method has high washing fastness, and the bacteriostasis rate to escherichia coli and staphylococcus aureus is over 85 percent.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the antibacterial agent adopts a plant natural antibacterial agent, has good biocompatibility and high safety, not only realizes the antibacterial safety, but also fully utilizes natural resources;

(2) the ionic liquid is adopted to dissolve the cellulose at high temperature step by step and dissolve the plant natural antibacterial essential oil at low temperature, so that the high-efficiency dissolution of the cellulose is realized, the influence of high temperature on the stability of the plant antibacterial agent is reduced, and the characteristics of natural resources are fully utilized;

(3) the regenerated cellulose-natural plant antibacterial agent with water as a coagulating bath improves the adhesion between the plant antibacterial agent and the regenerated fiber, and improves the washing fastness of the antibacterial fiber and the durability of the antibacterial effect;

(4) the prepared antibacterial fiber has high washing fastness, has the bacteriostasis rate of over 85 percent on staphylococcus aureus and escherichia coli, and can be used in the fields of medical textiles such as protective clothing, bandages and the like and antibacterial and deodorant household textiles.

Detailed Description

Example 1

Adding 1g of microcrystalline cellulose into 10g of 1-allyl-3-methylimidazolium chloride ionic liquid at 90 ℃, cooling to 50 ℃ after complete dissolution, adding 0.2g of aloe essential oil, mechanically stirring in a reaction kettle, dissolving in vacuum and defoaming completely to obtain spinning stock solution, and spinning by a dry spray wet method by taking water as a coagulating bath to obtain the antibacterial regenerated cellulose fiber, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are 87.2% and 89.5% respectively.

Example 2

Adding 10g of wood pulp cellulose into 1000g of choline acetate ionic liquid at 80 ℃, cooling to 40 ℃ after complete dissolution, adding 10g of oregano essential oil, extruding, dissolving and defoaming by using a double screw to obtain spinning stock solution, and performing wet spinning by using water as a coagulating bath to obtain the antibacterial regenerated cellulose fiber, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are 97.2% and 99.5% respectively.

Example 3

Adding 10g of straw cellulose into 500g of 1, 5-diazabicyclo [4.3.0] -5 nonene acetate ionic liquid at 100 ℃, cooling to 60 ℃ after complete dissolution, adding 30g of sweet wormwood wax oil, extruding, dissolving and defoaming by using a double screw to obtain spinning stock solution, and spinning by using water as a coagulating bath through a dry-jet wet method to obtain the antibacterial regenerated cellulose fiber, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are 93.2% and 95.6% respectively.

Example 4

Adding 1g of short-staple cellulose into 10g of 1-ethyl-3-methylimidazolium acetate ionic liquid at 100 ℃, cooling to 70 ℃ after complete dissolution, adding 5g of sweet wormwood wax oil, mechanically stirring in a reaction kettle, dissolving in vacuum and defoaming completely to obtain spinning stock solution, and performing wet spinning by taking water as a coagulating bath to obtain the antibacterial regenerated cellulose fiber, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are 97.2% and 99.5% respectively.

Example 5

Adding 10g of cellulose in fibrilia into 1000g of choline lysine salt ionic liquid at 90 ℃, cooling to 60 ℃ after complete dissolution, adding 30g of cinnamon essential oil, extruding, dissolving and defoaming by using a double screw to obtain spinning stock solution, and spinning by using water as a coagulating bath through a dry spraying wet method to obtain the antibacterial regenerated cellulose fiber, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are 95.2% and 94.7% respectively.

Example 6

Adding 10g of wood pulp cellulose into 1000g of choline acetate ionic liquid at 120 ℃, cooling to 70 ℃ after complete dissolution, adding 60g of thyme essential oil, extruding, dissolving and defoaming by using a double screw to obtain spinning stock solution, and performing wet spinning by using water as a coagulating bath to obtain the antibacterial regenerated cellulose fiber, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are 99.4% and 99.8% respectively.

Example 7

Adding 1g of linter cotton cellulose into 10g of 1-ethyl-3-methylimidazol levulinate ionic liquid at 110 ℃, reducing the temperature to 60 ℃ after complete dissolution, adding 0.6g of rosemary essential oil, mechanically stirring in a reaction kettle, dissolving in vacuum and defoaming completely to obtain spinning stock solution, and spinning by a dry-spray-wet method by taking water as a coagulating bath to obtain the antibacterial regenerated cellulose fiber, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are 86.4% and 87.9% respectively.

Example 8

Adding 10g of corncob cellulose into 1000g of choline proline salt ionic liquid at 80 ℃, cooling to 40 ℃ after complete dissolution, adding 15g of thyme essential oil, extruding, dissolving and defoaming by using double screws to obtain spinning stock solution, and performing wet spinning by using water as a coagulating bath to obtain the antibacterial regenerated cellulose fiber, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are respectively 98.5% and 99.7%.

Example 9

Adding 10g of wood pulp cellulose into 500g of 1, 5-diazabicyclo [4.3.0] -5 nonene diethyl phosphate ionic liquid at 120 ℃, cooling to 70 ℃ after complete dissolution, adding 40g of sweet wormwood wax oil, extruding, dissolving and defoaming by using double screws to obtain spinning stock solution, and spinning by using water as a coagulating bath through a dry-jet wet method to obtain the antibacterial regenerated cellulose fiber, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are respectively 98.3% and 99.1%.

Example 10

Adding 1g of cotton pulp cellulose into 10g of 1-ethyl-3-methylimidazolium acetate ionic liquid at 110 ℃, cooling to 50 ℃ after complete dissolution, adding 0.4g of lavender essential oil, mechanically stirring in a reaction kettle, dissolving in vacuum and defoaming completely to obtain spinning stock solution, and performing wet spinning by taking water as a coagulating bath to obtain the antibacterial regenerated cellulose fiber, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are 88.7.2% and 89.5% respectively.

Example 11

Adding 10g of cellulose in bamboo fibers into 1000g of 1-ethyl-3-methylimidazolium carbonate ionic liquid at 90 ℃, reducing the temperature to 40 ℃ after complete dissolution, adding 25g of tea tree essential oil, extruding, dissolving and defoaming by using double screws to obtain spinning stock solution, and spinning by using water as a coagulating bath through a dry-jet wet method to obtain the antibacterial regenerated cellulose fibers, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are 91.2% and 92.7% respectively.

Example 12

Adding 10g of microcrystalline cellulose into 1000g of choline acetate ionic liquid at 80 ℃, cooling to 30 ℃ after complete dissolution, adding 50g of mint essential oil, extruding, dissolving and defoaming by using a double screw to obtain spinning stock solution, and performing wet spinning by using water as a coagulating bath to obtain the antibacterial regenerated cellulose fiber, wherein the antibacterial rates to escherichia coli and staphylococcus aureus are respectively 98.9% and 99.5%.

Various technical features of the above embodiments can be combined arbitrarily, and the above description in this specification is only for illustrative purposes of the present invention, and should not be construed as limiting the scope of the present invention. All simple changes or combinations of features, principles, configurations, etc. described in the present patent application are intended to be included within the scope of the present patent application. Those skilled in the art to which the invention relates may effect numerous modifications, alterations, improvements, additions or substitutions to the specific embodiments described, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.