CN114989622A - Isocyanate/silk fibroin composite film and preparation method thereof - Google Patents
Isocyanate/silk fibroin composite film and preparation method thereof Download PDFInfo
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- CN114989622A CN114989622A CN202210836245.2A CN202210836245A CN114989622A CN 114989622 A CN114989622 A CN 114989622A CN 202210836245 A CN202210836245 A CN 202210836245A CN 114989622 A CN114989622 A CN 114989622A
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Abstract
The invention discloses an isocyanate/silk fibroin composite film and a preparation method thereof, which comprises the steps of boiling mulberry silkworm cocoons by alkaline deionized water for degumming, dissolving by a calcium chloride/ethanol/deionized water system, dialyzing and concentrating to prepare silk fibroin aqueous solution; uniformly mixing hexamethylene diisocyanate trimer with the silk fibroin aqueous solution to obtain isocyanate/silk fibroin mixed aqueous solution; and then the mixed aqueous solution is transferred to a silica gel mold by adopting a solution casting method to prepare the isocyanate/silk fibroin composite film, so that the isocyanate/silk fibroin composite film has the characteristics of high light transmittance, good thermal stability, excellent tensile strength, good toughness after being dried in water, excellent repeated bending performance and the like, the technical problem of poor mechanical property of the existing silk fibroin film is solved, the defects that the silk fibroin film is fragile and fragile after being dried in water are overcome, and the isocyanate/silk fibroin composite film is expected to be used as a flexible substrate material to meet the application requirements of high mechanical property, humidity and other complex environments.
Description
Technical Field
The invention belongs to the field of preparation of composite films, and particularly relates to an isocyanate/silk fibroin composite film and a preparation method thereof.
Background
The mulberry silk is an environment-friendly biomass material, is a structural protein continuous long fiber formed by silkworm during spinning, and has the characteristics of wide source, low cost, excellent processability and sustainable development and utilization. In recent years, single-form mulberry silk can be prepared into silk fibroin aqueous solution by selecting a proper salt solution system, and then silk fibroin nanofibers, composite membranes, hydrogels, aerogels and other various morphological structures are formed by reprocessing the silk fibroin aqueous solution, so that the application requirements of different fields are met. The silk fibroin film has the characteristics of simple and efficient preparation process, large-scale production and the like, and shows a huge market application prospect in the fields of flexible substrate materials and the like. Compared with the traditional polymer composite material as a substrate, the silk fibroin film has the defects of non-renewable resources, difficult biodegradation, easy waste accumulation and the like, and has a series of unique advantages of sustainable development, environmental protection and the like. However, in the current mulberry silk reprocessing production process, the original structure of the mulberry silk is often destroyed, so that the mechanical property of the silk fibroin film prepared is deteriorated, and the practical application requirements of the silk fibroin film in multiple fields and high performance are difficult to meet. In addition, the silk fibroin film is not brittle after being dried in water in complex environments such as humidity, and further practical application of the silk fibroin film is limited. Therefore, how to further improve the mechanical properties of the silk fibroin film material and overcome the defect that the silk fibroin film material is brittle after being dried in water is a technical problem to be overcome at present.
In conclusion, the silk fibroin film has the characteristics of simple and efficient preparation process, large-scale production, sustainable development, environmental friendliness and the like, and shows huge market development and application prospects. However, the silk fibroin film prepared from the silk fibroin aqueous solution at present has the defects of deteriorated mechanical properties, brittleness after being dried in water and the like, so that the practical application of the silk fibroin film is greatly hindered, and the technical problem which is difficult to overcome at present is solved.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, a first object of the present invention is to provide an isocyanate/silk fibroin composite film;
the second purpose of the invention is to provide a preparation method of the isocyanate/silk fibroin composite film.
To achieve the above objects, the present invention provides a method for synthesizing pantolactone, comprising the steps of:
an isocyanate/silk fibroin composite film comprises the following raw materials in parts by weight: 0.3-0.9 part of isocyanate and 9.1-9.7 parts of silk fibroin.
Further, the raw materials of the composite film comprise: 0.7 part of isocyanate and 9.3 parts of silk fibroin, wherein the thickness of the composite film is 13.8 mu m, and the maximum tensile strength is 38.2 MPa.
Further, the isocyanate was hexamethylene diisocyanate trimer having a molecular weight of 168.19.
Further, the specific steps are as follows:
1) boiling mulberry silkworm cocoons with alkaline deionized water for degumming, dissolving in a calcium chloride/ethanol/deionized water system, dialyzing and concentrating to obtain a silk fibroin aqueous solution;
2) dropwise adding hexamethylene diisocyanate trimer into the silk fibroin aqueous solution obtained in the step 1), and uniformly stirring in a water bath to obtain an isocyanate/silk fibroin mixed aqueous solution;
3) ultrasonically dispersing the isocyanate/silk fibroin mixed aqueous solution in the step 2), transferring the mixture into a silica gel mold by a solution casting method, and preparing the isocyanate/silk fibroin composite film in a constant-temperature drying oven.
Further, the specific steps of obtaining the silk fibroin aqueous solution in the step 1) are as follows:
boiling and degumming by using alkaline deionized water: taking 15-20 parts of mulberry silkworm cocoons, adding the mulberry silkworm cocoons into a mixture with the concentration of 2-4 wt% and the bath ratio of 1: 50 of sodium carbonate aqueous solution; boiling to degum for 15-30min at 100 deg.C, replacing sodium carbonate water solution for 3-4 times, further washing with deionized water at room temperature, and drying in a constant temperature drying oven at 50 deg.C for 12-24 hr to obtain degummed Bombyx Bombycis;
dissolving a calcium chloride/ethanol/deionized water system: placing degummed mulberry silkworm cocoons in a molar ratio of 1: 2: 8, stirring the solution in a calcium chloride/ethanol/deionized water system at the constant temperature of 50-70 ℃ for 1.5-3h to obtain a fibroin/calcium chloride/ethanol/deionized water solution, transferring the fibroin/calcium chloride/ethanol/deionized water solution to a centrifugal test tube, centrifuging the solution in a centrifuge at the rotation speed of 6000-12000r/min for 10-20min, and collecting supernatant to a beaker;
and (3) dialysis and concentration: transferring the supernatant into a dialysis bag with the molecular weight cutoff of 8000-14000Da, dialyzing in deionized water for 4-6 days, and then transferring the supernatant into a polyethylene glycol aqueous solution with the concentration of 10-20 wt% for reverse dialysis for 1-3h to obtain the silk fibroin aqueous solution.
Further, alkaline deionized water boiling degumming: 15 parts of mulberry silkworm cocoon, 2 wt% of sodium carbonate aqueous solution, boiling for degumming for 4 times, 20min for degumming, 50 ℃ for a constant-temperature drying oven and 18h for drying;
dissolving a calcium chloride/ethanol/deionized water system: the temperature of the constant-temperature water bath kettle is 60 ℃, the stirring time is 2h, the rotating speed of a centrifugal machine is 8000r/min, and the centrifugation time is 15 min;
and (3) dialyzing and concentrating: the dialysis time was 6 days, the concentration of the aqueous solution of polyethylene glycol was 15 wt%, and the reverse dialysis time was 2 hours.
Further, the specific steps for obtaining the isocyanate/silk fibroin mixed aqueous solution in the step 2) are as follows:
0.3-0.9 part of hexamethylene diisocyanate trimer is dropwise added into 9.7-9.1 parts of silk fibroin aqueous solution with the concentration of 2.5-5.5 wt% by using a rubber head dropper, the mass ratio of the hexamethylene diisocyanate trimer to the silk fibroin is 3-9 wt% respectively, and then the mixture is stirred in a constant temperature water bath kettle at the temperature of 30-50 ℃ for 0.5-2 hours.
Further, 0.7 part of hexamethylene diisocyanate trimer, 9.3 parts of silk fibroin, 4.5 wt% of silk fibroin aqueous solution, 7 wt% of hexamethylene diisocyanate trimer and silk fibroin, 30 ℃ of a constant temperature water bath and 1h of stirring time.
Further, the specific steps for preparing the isocyanate/silk fibroin composite film in the step 3) are as follows:
ultrasonically dispersing the isocyanate/silk fibroin mixed aqueous solution for 0.5-1h under the condition of 100W of power, transferring 1.10-2.30 parts of the mixed aqueous solution into a silica gel mold with the size of 3cm multiplied by 5cm, and then placing the silica gel mold in a constant-temperature drying box at the temperature of 50-80 ℃ for drying for 12-24h to form a layer of transparent film, namely an isocyanate/silk fibroin composite film, at the bottom of the mold.
Further, the ultrasonic power is 100W, the ultrasonic dispersion time is 0.5h, the isocyanate/silk fibroin mixed aqueous solution is 1.70 parts, the temperature of the constant-temperature drying oven is 70 ℃, and the drying time is 12 h.
By adopting the scheme, the invention has the following beneficial effects:
1. the invention discloses a preparation method of an isocyanate/silk fibroin composite film, which solves the technical problem of insufficient mechanical properties of the traditional silk fibroin film material, and prepares a silk fibroin aqueous solution by boiling silkworm cocoons with alkaline deionized water for degumming, dissolving in a calcium chloride/ethanol/deionized water system, dialyzing and concentrating; uniformly mixing isocyanate (hexamethylene diisocyanate trimer) with the silk fibroin aqueous solution to obtain an isocyanate/silk fibroin mixed aqueous solution; and then transferring the isocyanate/silk fibroin mixed aqueous solution into a silica gel mould by adopting a solution casting method to prepare the isocyanate/silk fibroin composite film, wherein the thickness of the isocyanate/silk fibroin composite film is 13.8 mu m, the light transmittance is 95.8%, the thermal decomposition temperature is 282.4 ℃, and the maximum tensile strength is 38.2 Mpa.
2. Compared with a pure silk fibroin film, the tensile strength of the isocyanate/silk fibroin composite film prepared by the invention is improved by about 205.6%, the technical problem of mechanical property deterioration of the existing silk fibroin film material is effectively improved, the preparation of the silk fibroin high-strength composite film material is realized, and the actual application requirement of the silk fibroin high-strength composite film material as a flexible substrate material with high mechanical property can be met.
3. The invention solves the technical problem that the traditional silk fibroin film material is brittle after being dried in water, and the invention prepares the isocyanate/silk fibroin composite film by uniformly mixing isocyanate (hexamethylene diisocyanate trimer) and silk fibroin aqueous solution and adopting a solution casting method through the technical scheme of a composite strategy of isocyanate (hexamethylene diisocyanate trimer) and silk fibroin, wherein the isocyanate/silk fibroin composite film has the characteristics of good toughness and excellent repeated bending property after being dried in water, and the like, and is expected to be used as a flexible substrate material to meet the application requirements under complex environments such as humidity and the like.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a flow chart of the preparation of the isocyanate/silk fibroin composite film of the present invention.
FIG. 2 is the surface topography of the isocyanate/silk fibroin composite film of the present invention.
FIG. 3 shows the cross-sectional shape and thickness of the isocyanate/silk fibroin composite film of the present invention.
Fig. 4 shows the light transmittance and thermal stability of the isocyanate/silk fibroin composite film and the silk fibroin film of the present invention.
Fig. 5 shows the mechanical properties of the isocyanate/silk fibroin composite film and the silk fibroin film of the present invention.
Fig. 6 is a comparative graph of the isocyanate/silk fibroin composite film and the silk fibroin film of the present invention immersed in deionized water for testing.
Fig. 7 is a comparison graph of a bending test of the isocyanate/silk fibroin composite film and the silk fibroin film of the present invention after being immersed in deionized water and dried.
Detailed Description
The present invention will now be described in detail with reference to the drawings and examples, which are not intended to limit the invention in any way, except as specifically stated, reagents, methods and apparatus are conventional in the art.
Example 1: preparation of isocyanate/silk fibroin composite film
The preparation flow is shown in figure 1;
product 1: the method comprises the following specific steps:
1) boiling mulberry silkworm cocoons with alkaline deionized water for degumming, dissolving in a calcium chloride/ethanol/deionized water system, dialyzing and concentrating to prepare a silk fibroin aqueous solution;
boiling and degumming by using alkaline deionized water: taking 15 parts of mulberry silkworm cocoons, adding the mulberry silkworm cocoons into a mixture with the concentration of 2 wt% and the bath ratio of 1: 50 of sodium carbonate aqueous solution; then, boiling and degumming for 4 times at 100 ℃ (replacing sodium carbonate aqueous solution each time and boiling and degumming for 20 min); further fully washing with deionized water at room temperature, and drying in a constant temperature drying oven at 50 deg.C for 18h to obtain degummed Bombyx mori cocoons;
dissolving a calcium chloride/ethanol/deionized water system: placing the degummed silkworm cocoons into a calcium chloride/ethanol/deionized water system (the molar ratio is 1: 2: 8), and stirring for 2 hours in a constant-temperature water bath kettle at 60 ℃ to obtain a silk fibroin/calcium chloride/ethanol/deionized water solution; then, transferring the supernatant into a centrifugal test tube, centrifuging for 15min in a centrifugal machine with the rotating speed of 8000r/min, and collecting the supernatant into a beaker;
and (3) dialysis and concentration: transferring the supernatant into a dialysis bag with the molecular weight cutoff of 8000-14000Da, and dialyzing in deionized water for 6 days; then transferring the silk fibroin into a polyethylene glycol aqueous solution with the concentration of 15 wt% for reverse dialysis for 2h to obtain a silk fibroin aqueous solution;
2) preparing the silk fibroin aqueous solution obtained in the step 1) into a solution with the concentration of 4.5 wt%, and uniformly stirring the solution for 1h in a constant-temperature water bath kettle at the temperature of 30 ℃ to further obtain the silk fibroin aqueous solution;
3) ultrasonically dispersing the silk fibroin aqueous solution in the step 2), transferring the solution into a silica gel mold by a solution casting method, and preparing a silk fibroin film in a constant-temperature drying oven;
ultrasonically dispersing a silk fibroin aqueous solution for 0.5h under the condition that the power is 100W, and transferring 1.6 parts of the silk fibroin aqueous solution into a silica gel mold of 3cm multiplied by 5 cm; then, the silk fibroin film is placed in a constant-temperature drying box at the temperature of 70 ℃ for drying for 12 hours, and a layer of transparent film, namely the silk fibroin film, can be formed at the bottom of the die.
Product 2: the method comprises the following specific steps:
1) boiling mulberry silkworm cocoons with alkaline deionized water for degumming, dissolving in a calcium chloride/ethanol/deionized water system, dialyzing and concentrating to prepare a silk fibroin aqueous solution;
boiling and degumming by using alkaline deionized water: taking 15 parts of mulberry silkworm cocoons, adding the mulberry silkworm cocoons into a mixture with the concentration of 2 wt% and the bath ratio of 1: 50 of sodium carbonate aqueous solution; then, boiling and degumming for 4 times at 100 ℃ (replacing sodium carbonate aqueous solution each time and boiling and degumming for 20 min); further fully washing with deionized water at room temperature, and drying in a constant temperature drying oven at 50 deg.C for 18h to obtain degummed Bombyx Bombycis;
dissolving a calcium chloride/ethanol/deionized water system: placing the degummed silkworm cocoons into a calcium chloride/ethanol/deionized water system (the molar ratio is 1: 2: 8), and stirring for 2 hours in a constant-temperature water bath kettle at 60 ℃ to obtain a silk fibroin/calcium chloride/ethanol/deionized water solution; then, transferring the supernatant into a centrifugal test tube, centrifuging for 15min in a centrifugal machine with the rotating speed of 8000r/min, and collecting the supernatant into a beaker;
and (3) dialysis and concentration: transferring the supernatant into a dialysis bag with the molecular weight cutoff of 8000-14000Da, and dialyzing in deionized water for 6 days; then transferring the silk fibroin into a polyethylene glycol aqueous solution with the concentration of 15 wt% for reverse dialysis for 2h to obtain a silk fibroin aqueous solution;
2) dropwise adding isocyanate (hexamethylene diisocyanate trimer) into the silk fibroin aqueous solution obtained in the step 1), and uniformly stirring in a water bath to obtain an isocyanate/silk fibroin mixed aqueous solution;
0.7 part of isocyanate (hexamethylene diisocyanate trimer) is respectively added into an aqueous solution containing 9.3 parts of silk fibroin dropwise by a rubber head dropper, the concentration of the aqueous solution of the silk fibroin is 4.5 wt%, and the mass ratio of the isocyanate (hexamethylene diisocyanate trimer) to the silk fibroin is 7 wt%; then, uniformly stirring the mixture in a constant-temperature water bath kettle at the temperature of 30 ℃ for 1 hour;
3) ultrasonically dispersing the isocyanate/silk fibroin mixed aqueous solution in the step 2), transferring the mixture into a silica gel mold by a solution casting method, and preparing an isocyanate/silk fibroin composite film in a constant-temperature drying oven;
ultrasonically dispersing the isocyanate/silk fibroin mixed aqueous solution for 0.5h under the condition that the power is 100W, and transferring 1.6 parts of the isocyanate/silk fibroin mixed aqueous solution into a silica gel mold of 3cm multiplied by 5 cm; then, the film is placed in a constant-temperature drying oven at 70 ℃ for drying for 12 hours, and a layer of transparent film, namely the isocyanate/silk fibroin composite film, can be formed at the bottom of the die.
Product 3: the method comprises the following specific steps:
1) boiling mulberry silkworm cocoons with alkaline deionized water for degumming, dissolving in a calcium chloride/ethanol/deionized water system, dialyzing and concentrating to prepare a silk fibroin aqueous solution;
boiling and degumming by using alkaline deionized water: taking 20 parts of mulberry silkworm cocoons, adding the mulberry silkworm cocoons into a mixture with the concentration of 4 wt% and the bath ratio of 1: 50 of sodium carbonate aqueous solution; then boiling and degumming for 3 times at 100 deg.C (replacing sodium carbonate aqueous solution each time and boiling and degumming for 30 min); further fully washing with deionized water at room temperature, and drying in a constant temperature drying oven at 50 deg.C for 12 hr to obtain degummed Bombyx Bombycis;
dissolving a calcium chloride/ethanol/deionized water system: placing the degummed silkworm cocoons into a calcium chloride/ethanol/deionized water system (the molar ratio is 1: 2: 8), and stirring for 3 hours in a constant-temperature water bath kettle at 50 ℃ to obtain a silk fibroin/calcium chloride/ethanol/deionized water solution; then, transferring the supernatant to a centrifugal test tube, centrifuging for 20min in a centrifuge with the rotating speed of 6000r/min, and collecting the supernatant to a beaker;
and (3) dialysis and concentration: transferring the supernatant into a dialysis bag with the molecular weight cutoff of 8000-14000Da, and dialyzing in deionized water for 4 days; then transferring the solution to a polyethylene glycol aqueous solution with the concentration of 10 wt% for reverse dialysis for 3h to obtain a silk fibroin aqueous solution;
2) dropwise adding isocyanate (hexamethylene diisocyanate trimer) into the silk fibroin aqueous solution obtained in the step 1), and uniformly stirring in a water bath to obtain an isocyanate/silk fibroin mixed aqueous solution;
0.9 part of isocyanate (hexamethylene diisocyanate trimer) is respectively added into an aqueous solution containing 9.1 parts of silk fibroin dropwise by a rubber head dropper, the concentration of the aqueous solution of the silk fibroin is 4.5 wt%, and the mass ratio of the isocyanate (hexamethylene diisocyanate trimer) to the silk fibroin is 9 wt%; then, uniformly stirring the mixture in a constant-temperature water bath kettle at the temperature of 50 ℃ for 2 hours;
3) ultrasonically dispersing the isocyanate/silk fibroin mixed aqueous solution in the step 2), transferring the mixture into a silica gel mold by a solution casting method, and preparing an isocyanate/silk fibroin composite film in a constant-temperature drying oven;
ultrasonically dispersing the isocyanate/silk fibroin mixed aqueous solution for 1h under the condition of 100W of power, and transferring 2.3 parts of the isocyanate/silk fibroin mixed aqueous solution into a silica gel mold of 3cm multiplied by 5 cm; then, the film is placed in a constant-temperature drying oven at the temperature of 80 ℃ for drying for 18h, and a layer of transparent film, namely the isocyanate/silk fibroin composite film, can be formed at the bottom of the die.
Example 2: surface appearance, cross-sectional appearance, size and mechanical property test of isocyanate/silk fibroin composite film
1. Experimental Material
The silk fibroin film prepared under the condition of the product 2 in the embodiment 1, an isocyanate/silk fibroin composite film and a pure silk fibroin film.
2. Experimental methods
2.1 surface morphology, Cross-sectional morphology and size
The method is carried out at the temperature of 25 ℃, and a femina Chinese scanning electron microscope is adopted to carry out surface appearance, section appearance observation and section size measurement of the isocyanate/silk fibroin composite film.
2.2 mechanical Property testing
The method is carried out under the conditions that the temperature is 25 ℃, the initial clamping distance is 1cm, the stretching speed is 10mm/min, and the sizes of the isocyanate/silk fibroin composite film and the pure fibroin film are both 3cm multiplied by l cm, and a Japanese Shimadzu AGS-XShimadzu universal material tensile testing machine is adopted;
elongation at break (. epsilon.) τ And%) was calculated according to the following formula:
ε τ -elongation at break (%);
L 0 -initial grip distance (mm);
l-grip distance (mm) at break of the sample;
tensile Strength (. delta.) τ MPa) is calculated according to the following formula:
δ τ -tensile strength (MPa);
f-breaking stress (N);
b-sample width (mm);
d-sample thickness (mm).
3. Results of the experiment
As can be seen from fig. 2 and 3, the isocyanate/silk fibroin composite film is colorless and transparent, the surface appearance thereof is a flat and compact structure, the cross-sectional structure is slightly rough, and the thickness thereof is 13.8 μm;
as can be seen from FIG. 4a, the transmittance of the isocyanate/silk fibroin composite film is as high as 95.8% in the wavelength range of 300-800 nm; as shown in FIG. 4b, the initial decomposition temperature of the pure silk fibroin film is 244.4 ℃, while the thermal decomposition temperature of the isocyanate/silk fibroin composite film is about 282.4 ℃, which is greatly increased by 38 ℃;
as can be seen from fig. 5, the maximum tensile strength of the pure silk fibroin film is about 12.5Mpa, while the maximum tensile strength of the isocyanate/silk fibroin composite film is about 38.2Mpa, which is a substantial increase of 205.6%, showing excellent tensile strength.
Example 3: comparative experiment for testing bending performance of isocyanate/silk fibroin composite film and silk fibroin film immersed in deionized water and dried
1. Experimental Material
The silk fibroin film prepared under the condition of the product 2 in the embodiment 1, an isocyanate/silk fibroin composite film and a pure silk fibroin film.
2. Experimental methods
2.1 immersion in deionized Water
And (2) immersing the pure silk fibroin film and the isocyanate/silk fibroin composite film which are cut into proper sizes in 25mL of deionized water at the temperature of 25 ℃, and observing and recording the macroscopic difference of the pure silk fibroin film and the isocyanate/silk fibroin composite film.
2.2 bending Property test
Soaking the pure silk fibroin film and the isocyanate/silk fibroin composite film which are immersed in the deionized water of 2.1 in the deionized water test for 0.5h, and drying in a constant-temperature drying box at 70 ℃ for 12 h; and then, respectively carrying out repeated bending performance tests on the dried pure silk fibroin film and the isocyanate/silk fibroin composite film by using white plastic tweezers.
3. Results of the experiment
As shown in fig. 6, the pure silk fibroin film will curl when immersed in deionized water, but the isocyanate/silk fibroin composite film will not curl when immersed in deionized water;
as shown in fig. 7, after being immersed in deionized water and dried, the pure silk fibroin film is brittle and fragile, and has no bending property, while the isocyanate/silk fibroin composite film still maintains the characteristics of high strength, good toughness and the like, and has repeated bending property;
in conclusion, the isocyanate/silk fibroin composite film prepared by the invention effectively solves the technical problem of poor mechanical property of the existing silk fibroin film, overcomes the defects of brittleness and fragility of the existing silk fibroin film after being dried in water, and is expected to be used as a flexible substrate material to meet the application requirements of high mechanical property, humidity and other complex environments.
Finally, the description is as follows: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The isocyanate/silk fibroin composite film is characterized by comprising the following raw materials in parts by weight: 0.3-0.9 part of isocyanate and 9.1-9.7 parts of silk fibroin.
2. The isocyanate/silk fibroin composite film according to claim 1, wherein the raw material composition of the composite film comprises: 0.7 part of isocyanate and 9.3 parts of silk fibroin, wherein the thickness of the composite film is 13.8 mu m, and the maximum tensile strength is 38.2 MPa.
3. The isocyanate/silk fibroin composite film according to claim 2, wherein the isocyanate is hexamethylene diisocyanate trimer having a molecular weight of 168.19.
4. The preparation method of the isocyanate/silk fibroin composite film as claimed in claim 3, which is characterized by comprising the following specific steps:
1) boiling silkworm cocoons with alkaline deionized water for degumming, dissolving with a calcium chloride/ethanol/deionized water system, dialyzing and concentrating to obtain a silk fibroin aqueous solution;
2) dropwise adding hexamethylene diisocyanate trimer into the silk fibroin aqueous solution obtained in the step 1), and uniformly stirring in a water bath to obtain an isocyanate/silk fibroin mixed aqueous solution;
3) ultrasonically dispersing the isocyanate/silk fibroin mixed aqueous solution in the step 2), transferring the isocyanate/silk fibroin mixed aqueous solution into a silica gel mould by a solution casting method, and preparing the isocyanate/silk fibroin composite film in a constant-temperature drying oven.
5. The method for preparing the isocyanate/silk fibroin composite film according to claim 4, wherein the specific steps of obtaining the silk fibroin aqueous solution in the step 1) are as follows:
boiling and degumming by using alkaline deionized water: taking 15-20 parts of silkworm cocoons, adding the silkworm cocoons into a liquor with the concentration of 2-4 wt% and the bath ratio of 1: 50 of sodium carbonate aqueous solution; boiling to degum for 15-30min at 100 deg.C, replacing sodium carbonate water solution for 3-4 times, further washing with deionized water at room temperature, and drying in a constant temperature drying oven at 50 deg.C for 12-24 hr to obtain degummed Bombyx Bombycis;
dissolving a calcium chloride/ethanol/deionized water system: placing degummed mulberry silkworm cocoons in a molar ratio of 1: 2: 8, stirring the solution in a calcium chloride/ethanol/deionized water system at the constant temperature of 50-70 ℃ for 1.5-3h to obtain a fibroin/calcium chloride/ethanol/deionized water solution, transferring the fibroin/calcium chloride/ethanol/deionized water solution to a centrifugal test tube, centrifuging the solution in a centrifuge at the rotation speed of 6000-12000r/min for 10-20min, and collecting supernatant to a beaker;
and (3) dialyzing and concentrating: transferring the supernatant into a dialysis bag with the molecular weight cutoff of 8000-14000Da, dialyzing in deionized water for 4-6 days, and then transferring the supernatant into a polyethylene glycol aqueous solution with the concentration of 10-20 wt% for reverse dialysis for 1-3h to obtain the silk fibroin aqueous solution.
6. The method for preparing the isocyanate/silk fibroin composite film according to claim 5, wherein the alkaline deionized water boiling degumming: 15 parts of mulberry silkworm cocoon, 2 wt% of sodium carbonate aqueous solution, boiling for degumming for 4 times, 20min for degumming, 50 ℃ for a constant-temperature drying oven and 18h for drying;
dissolving a calcium chloride/ethanol/deionized water system: the temperature of the constant-temperature water bath kettle is 60 ℃, the stirring time is 2h, the rotating speed of a centrifugal machine is 8000r/min, and the centrifugation time is 15 min;
and (3) dialysis and concentration: the dialysis time was 6 days, the concentration of the aqueous solution of polyethylene glycol was 15 wt%, and the reverse dialysis time was 2 hours.
7. The method for preparing the isocyanate/silk fibroin composite film according to claim 4, wherein the specific steps of obtaining the isocyanate/silk fibroin mixed aqueous solution in the step 2) are as follows:
0.3-0.9 part of hexamethylene diisocyanate tripolymer is dropwise added into 9.7-9.1 parts of aqueous solution of silk fibroin with the concentration of 2.5-5.5 wt% by a rubber head dropper, the mass ratio of the hexamethylene diisocyanate tripolymer to the silk fibroin is 3-9 wt% respectively, and then the mixture is stirred in a constant temperature water bath kettle at 30-50 ℃ for 0.5-2 h.
8. The method for preparing an isocyanate/silk fibroin composite film according to claim 7, wherein the hexamethylene diisocyanate trimer is 0.7 parts, the silk fibroin is 9.3 parts, the concentration of the silk fibroin aqueous solution is 4.5 wt%, the mass ratio of the hexamethylene diisocyanate trimer to the silk fibroin is 7 wt%, the temperature of the constant temperature water bath is 30 ℃, and the stirring time is 1 hour.
9. The method for preparing the isocyanate/silk fibroin composite film according to claim 4, wherein the specific steps for preparing the isocyanate/silk fibroin composite film in the step 3) are as follows:
ultrasonically dispersing the isocyanate/silk fibroin mixed aqueous solution for 0.5-1h under the condition of 100W of power, transferring 1.10-2.30 parts of the mixed aqueous solution into a silica gel mold with the size of 3cm multiplied by 5cm, and then placing the silica gel mold in a constant-temperature drying box at the temperature of 50-80 ℃ for drying for 12-24h to form a layer of transparent film, namely an isocyanate/silk fibroin composite film, at the bottom of the mold.
10. The method for preparing the isocyanate/silk fibroin composite film according to claim 9, wherein the ultrasonic power is 100W, the ultrasonic dispersion time is 0.5h, the isocyanate/silk fibroin mixed aqueous solution is 1.70 parts, the temperature of a constant-temperature drying oven is 70 ℃, and the drying time is 12 h.
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