阅读说明：本技术 一种快速、低成本制备蚕丝纳米纤维的方法 (A method of quick, low cost prepares silk nanofiber ) 是由 李朝旭 吴晓晨 吕莉莉 于 2019-09-12 设计创作，主要内容包括：本发明属于纳米材料制备领域,具体涉及一种绿色、快速、低成本的蚕丝纳米纤维制备方法。将天然蚕茧加至强碱的水溶液中混合,混合液在1-500r/s的搅拌速度、4-95℃温度下浸泡0.1-100h,离心洗涤、超声分散获得高产率、直径分布为2-28nm,长度分布为100-3000nm蚕丝纳米纤维的分散液。本发明操作简单,生产成本低,绿色环保,生产周期短,不涉及大型仪器设备,能够实现蚕丝纳米纤维的大规模工业化制备。(The invention belongs to field of nano material preparation, and in particular to a kind of green, quickly, inexpensive silk nanofiber preparation method.Natural silk cocoon is added in the aqueous solution of highly basic and is mixed, mixed liquor impregnates 0.1-100h at a temperature of the mixing speed of 1-500r/s, 4-95 DEG C, centrifuge washing, ultrasonic disperse obtain high yield, diameter is distributed as 2-28nm, and distribution of lengths is the dispersion liquid of 100-3000nm silk nanofiber.Operation of the present invention is simple, and production cost is low, environmentally protective, with short production cycle, is not related to large-scale instrument and equipment, can be realized the heavy industrialization preparation of silk nanofiber.)

1. a kind of method that quick, low cost prepares silk nanofiber, it is characterised in that: natural silk cocoon is added to the water of highly basic It is mixed in solution, mixed liquor impregnates 0.1-100h, centrifuge washing, ultrasound at a temperature of the mixing speed of 1-500r/s, 4-95 DEG C Dispersion obtains high yield, diameter is distributed as 2-28nm, and distribution of lengths is the dispersion liquid of 100-3000nm silk nanofiber.

2. the method that quick, low cost according to claim 1 prepares silk nanofiber, it is characterised in that: the mixing Liquid preferably at a temperature of the mixing speed of 20-100r/s, 15-40 DEG C, impregnates 12-24h, with deionized water in 4000-6000rpm Centrifuge washing, ultrasonic disperse obtain the dispersion liquid of silk nanofiber.

3. the method that quick, low cost as described in claim 1 or 2 prepares silk nanofiber, it is characterised in that: described mixed The final concentration of 0.01-10wt.% of silk cocoon in liquid is closed, the concentration of aqueous solution of highly basic is 0.1-20wt.%.

4. the method that quick, low cost according to claim 3 prepares silk nanofiber, it is characterised in that: the highly basic Aqueous solution be solution that one or more of inorganic strong alkali or organic alkali are dissolved in that water obtains.

5. the method that quick, low cost as described in claim 1 or 2 prepares silk nanofiber, it is characterised in that: the leaching Reaction solution is centrifuged 1-10min with the rate of 3000-10000rpm after bubble, collects lower sediment, disperses again in deionized water And repeat centrifugal process 2-10 times, it then collects centrifugation dispersion in a solvent, obtains silk nanofiber head product.

6. the method that quick, low cost as described in claim 5 prepares silk nanofiber, it is characterised in that: the solvent For deionized water, acetone, methanol, ethyl alcohol, n,N-Dimethylformamide, the one or more of acetonitrile.

7. the method that quick, low cost as described in claim 1 or 2 prepares silk nanofiber, it is characterised in that: described super Sound dispersion refers to the silk nanofiber head product ultrasonication 0.2-5min after centrifuge washing, obtains silk Nanowire The dispersion liquid of dimension.

8. the method that quick, low cost as described in claim 1 or 2 prepares silk nanofiber, it is characterised in that: the day Right silk cocoon is the one or more of common silk cocoon.

Technical field

The invention belongs to field of nano material preparation, and in particular to a kind of green, quickly, inexpensive silk nanofiber Preparation method.

Background technique

Silk nanofiber has many advantages, such as good biocompatibility, degradable green, from a wealth of sources, excellent in mechanical performance, It is the important research object of the advanced optical material of exploitation, the biomaterial of implantable body, high-performance composite materials.To prepare silkworm Silk nanofiber, separating silk nanofiber " from top to bottom " from natural silk fiber is a kind of common method.This Class method is usually to utilize organic solvent or strong acid, high level salt solution by the endless fully dissolved of silk fiber or hydrolysis, to destroy fibroin Active site of protein intermolecular interaction, to obtain silk micro nanometer fiber；Or by mechanical means such as ultrasonications by silkworm Silk micro nanometer fiber is directly removed from ontology crude fibre.However, the above method often is faced with, energy consumption is high, preparation process is complicated, The problems such as using poisonous and harmful solvent, and the size for removing obtained silk nanofiber is unevenly distributed, stability is poor.

Pass through the retrieval discovery to existing silk nanofiber technology of preparing document and patent, Chinese patent literature CN 104532365 B on April 27 2016 publication date, disclose a kind of preparation method of silk micro nanometer fiber, and this method is first First silk fiber is immersed in inorganic salts or weak acid or weak caustic solution, to weaken the binding force between silk nanometer fibril, later Using cell crushing instrument or other high-speed stirring apparatus processing silk fiber to obtain diameter as 50-100nm, length 10²- 10⁵The silk fiber of nm.However, this method can only handle the silk fiber (0.05-0.1wt%) of low concentration on a small quantity, machinery is broken Broken required time is long (2-6h), faces low efficiency, the problems such as energy consumption is high；And the silk fiber obtained is relatively large in diameter (diameter 50- 100nm), diameter < 30nm silk nanofiber can not be directly obtained.

108022761 A of Chinese patent literature CN on May 11 2018 publication date, discloses a kind of silk nanometer Silk at high temperature, is placed in immersion (60-120 DEG C, 4-100h) in depth congruent melting solvent by the preparation method of fiber, this method, And in conjunction with ultrasonic, centrifugation, obtaining diameter is 15-150nm, length 10²-10⁵The silk micro nanometer fiber of nm.Text Offer (ACS nano 2018,12,11860) by Silk Soaking (- 12 DEG C) 3 days in low temperature NaOH/ urea/water mixed liquid, it is rear logical Crossing dialysis and clasmatosis (300W, 30min) and obtaining mean breadth is 25-28nm, the silk nanometer of average height about 0.4nm Fiber.In addition, organic solvent such as formic acid-Calcium Chloride System (J.Mater.Chem.B 2014,2,3879) and hexafluoroisopropanol body System (Adv.Mater.2016,28,7783) is also commonly used to prepare silk nanofiber.The above method is related to mix reagent body mostly System or toxic, organic reagent (such as formic acid, hexafluoroisopropanol), and specially treated temperature (such as -12 DEG C or 60-120 DEG C) is needed, and Face energy consumption high (such as Mechanical Crushing 2-6h), low yield, can not large-scale production the problems such as.Quickly, simply, can quantify production, it is low Energy consumption, the silk nanofiber preparation method of low cost are still urgently developed.

Summary of the invention

The present invention In view of the above shortcomings of the prior art, proposes a kind of green, quickly, inexpensive silk Nanowire Tie up preparation method.

To achieve the above object, the technical solution adopted by the present invention are as follows:

A method of quick, low cost prepares silk nanofiber, natural silk cocoon is added in the aqueous solution of highly basic and is mixed It closes, mixed liquor impregnates 0.1-100h at a temperature of the mixing speed of 1-500r/s, 4-95 DEG C, and centrifuge washing, ultrasonic disperse obtain High yield, diameter are distributed as 2-28nm, and distribution of lengths is the dispersion liquid of 100-3000nm silk nanofiber.

The mixed liquor preferably at a temperature of the mixing speed of 20-100r/s, 15-40 DEG C, impregnates 12-24h, uses deionization Water obtains the dispersion liquid of silk nanofiber in 4000-6000rpm centrifuge washing, ultrasonic disperse.

The final concentration of 0.01-10wt.% (preferably 0.4-1.5wt.%) of silk cocoon, the aqueous solution of highly basic in the mixed liquor Concentration is 0.1-20wt.% (preferably 3-7wt.%).

The aqueous solution of the highly basic is the solution that one or more of inorganic strong alkali or organic alkali are dissolved in that water obtains.By force The aqueous solution of alkali includes but is not limited to inorganic strong alkali (such as sodium hydroxide, potassium hydroxide), organic alkali (such as sodium methoxide, sodium ethoxide Deng) one or more be dissolved in the solution that water obtains.

Reaction solution is (excellent with the rate centrifugation 1-10min of 3000-10000rpm (preferably 4000-6000rpm) after the immersion Select 4-6min), lower sediment is collected, disperses again in deionized water and repeats centrifugal process 2-10 times, then collect centrifugation Precipitating dispersion in a solvent, obtains silk nanofiber head product.

The solvent is deionized water, acetone, methanol, ethyl alcohol, n,N-Dimethylformamide, the one or more of acetonitrile.

The ultrasonic disperse refers to the silk nanofiber head product ultrasonication (clasmatosis after centrifuge washing Instrument (power 50-400W)) 0.2-5min, obtain the dispersion liquid of silk nanofiber.

The natural silk cocoon is the one or more of common silk cocoon.Natural silk cocoon include but is not limited to commercially available silkworm, tussah, The one or more of the common silk cocoon such as giant silkworm, castor silkworm, willow silkworm.

Beneficial effects of the present invention

For the present invention using natural silk cocoon as raw material, operating procedure is simple, and the requirement to equipment is low, and preparation process is environmentally protective, Production cost is low, does not use toxic, harmful reagent；Prepared silk nanofiber have high length-diameter ratio, even size distribution, The advantages that dispersion stability is high, and can be realized the heavy industrialization preparation of silk nanofiber.Specifically:

1. raw material (silk cocoon) of the present invention are easy to get extensively, are cheap, there is good biocompatibility and biology can drop Xie Xing, and silk cocoon is small without pretreatment process, energy consumptions such as degummings.

2. dicyandiamide solution needed for present invention reaction is strong base solution, using highly basic by fibroin partial hydrolysis, destroy Interaction force between fibroin albumen interior molecules, and ultrasonication is innovatively combined, silk is further dissociated and is obtained directly Diameter is lower than the silk nanofiber of 30nm.Compared with the conventional method, this method hydrolysis rate is fast, obtained silk nanofiber ruler Very little uniformly (such as Fig. 1), dispersion stabilization are high (such as Fig. 2)；And the present invention selects reagent not to be related to toxic, harmful reagent, production It is at low cost.

3. low to the requirement of experimental facilities in preparation process of the present invention, preparation process only needs magnetic stirring apparatus, ultrasound broken Broken instrument and centrifuge.

4. the yield of present invention preparation gained silk nanofiber is high (more than 40%), the diameter distribution of silk nanofiber For 2-28nm, even size distribution, and draw ratio are more than 1000nm (approximate length 100-3000nm, high length-diameter ratio 3- 1500)；Gained silk nanofiber stable dispersion (without layering or can wad a quilt with cotton in multi-solvents system more than 15 days at the same time It is solidifying to occur), meet subsequent applications demand.

5. it is about 24 hours (reacting under 25 degrees Celsius of room temperature) that the present invention, which handles a collection of raw material time, with existing way phase Than the operating time being substantially reduced, and the subsequent ultrasonic time also greatly shortens, conducive to accomplishing scale production.

In conclusion preparation process of the present invention is easy to operate, production cost is low, environmentally protective, with short production cycle, is not related to Large-scale instrument and equipment can be realized the heavy industrialization preparation of the high silk nanofiber of size uniformity, stability.

Detailed description of the invention

Fig. 1 is the shape appearance figure of the silk nanofiber obtained by taking silkworm silk cocoon as an example in the embodiment of the present invention 1.

Fig. 2 is the light provided in an embodiment of the present invention by the silk nanofiber dispersion of acquisition in multi-solvents after 15 days Learn photo.

Specific embodiment

Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation Example.