CN114891328B - Preparation method and application of polymer blend with water-induced double-way shape memory effect - Google Patents
Preparation method and application of polymer blend with water-induced double-way shape memory effect Download PDFInfo
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Abstract
The invention provides a preparation method and application of a polymer blend with a water-induced double-way shape memory effect, which is a blend prepared by a solution blending method according to a certain mass percentage by using a poly L-lactide (PLLA) based polymer and a Silk Fibroin (SF) with a beta-sheet structure as a main component. Compared with the prior art, the invention has the following characteristics: (1) SF mainly with a beta-sheet structure is introduced to enable the blend to have a water-induced double-way shape memory effect, the reversible transformation temperature is 40-70 ℃, and the reversible shape recovery rate is more than 95%; the reversible temperature of 40 ℃ approaches to the temperature of a human body, so that the blend has potential application prospects in the medical fields of artificial muscles, drug carriers and the like; (2) The introduction of SF improves the hydrophilicity and biocompatibility of the PLLA-based polymer, and endows the blend with excellent bioactivity; the preparation method of the blend is simple and easy to realize.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method and application of a polymer blend with a water-induced double-way shape memory effect, and belongs to the field of novel intelligent and multifunctional materials.
Background
The double-pass shape memory polymer (2W-SMPs) is a polymer which is endowed with a temporary shape under the action of external force and external stimulus (such as temperature, water, light and the like), is recovered to an original shape when receiving the external stimulus again, and can realize reversible conversion between the temporary shape and the original shape through the external stimulus again after the first shaping. The reversible transformation characteristic of the shape makes the 2W-SMPs widely applied to the biomedical fields such as artificial muscles, intelligent drug carriers and the like. At present, the two-way shape memory effect of the shape memory polymer is usually realized through melt-crystallization transformation, and only can respond to thermal stimulation, but the shape memory polymer cannot be directly heated at certain specific parts of a human body, so that the traditional heat-induced 2W-SMPs cannot meet the application requirements of specific medical fields. In recent years, water-induced shape memory polymers have been widely studied because of the wide presence of water molecules in the body and the safest use for the human body. Studies have shown that most water-induced shape memory polymers have only one-way shape memory effects, whereas polymer material systems with water-induced two-way shape memory effects have been rarely reported. The reported water-induced 2W-SMPs are mostly polymer composite materials with a bilayer special structure, and the bilayer structure has two problems, namely, the preparation process of the materials is complex; on the other hand, the compatibility and the binding force between polymer materials forming the bilayer structure are weaker, so that adverse effects are generated on various service performances such as mechanical properties of the materials, and the application of the materials in the biomedical field is limited.
Disclosure of Invention
The invention aims at: aiming at the problems of the existing water-induced 2W-SMPs, the Silk Fibroin (SF) mainly with a beta-sheet structure is introduced into the poly L-lactide-based polymer by a simple solution blending method to prepare a blend with good water-induced double-pass shape memory characteristic, bioactivity and biocompatibility, the transition temperature of the blend ranges from 40 ℃ to 70 ℃, and the blend is expected to be applied to the medical fields of artificial muscles, intelligent drug carriers and the like.
The technical scheme of the invention is as follows:
a preparation method of a polymer blend with water-induced double-way shape memory effect comprises the steps of blending a poly L-lactide-based polymer and a silk fibroin solution mainly with a beta-sheet structure: dissolving poly L-lactide based polymer in chloroform to obtain poly L-lactide based polymer chloroform solution, weighing silk fibroin according to the mass percentage of silk fibroin accounting for 2% -20% of poly L-lactide based polymer, adding chloroform for ultrasonic dispersion, dropwise adding the silk fibroin solution after ultrasonic into the polymer solution, stirring at room temperature to uniformly disperse the silk fibroin in the polymer solution, thoroughly volatilizing the chloroform, and drying the film in a vacuum drying oven at 40 ℃ for 24 hours to obtain a blend film.
Further, the poly L-lactide-based polymer is a random copolymer prepared by random copolymerization of at least two of poly L-lactide or L-lactide, glycolide epsilon-caprolactone.
Further, the poly L-lactide-based polymer is a multiblock copolymer prepared by reacting epsilon-caprolactone with ethylene glycol or glycerol to generate hydroxyl-terminated prepolymer, reacting L-lactide or glycolide with succinic acid to generate carboxyl-terminated prepolymer, and mixing at least two of them with a coupling agent or a chain extender.
Further, the poly L-lactide-based polymer is a blend of at least two of poly L-lactide, polyglycolide, and poly ε -caprolactone.
Further, the preparation method of the silk fibroin comprises the following steps: the silkworm cocoons are sequentially degummed by adopting a sodium bicarbonate/sodium dodecyl sulfate mixed solution and a disodium hydrogen phosphate-citric acid buffer solution of papain, and are dissolved in a lithium bromide solution, dialyzed and freeze-dried to prepare silk fibroin white powder mainly with a beta-sheet structure.
Further, the silkworm cocoons adopt 0.02wt% of sodium bicarbonate and 0.25wt% of sodium dodecyl sulfate in a volume ratio of 1: degumming the mixed solution of 1, wherein the bath ratio is 1:50, degumming temperature 100 ℃, degumming time 30min and degumming times 2 times.
Further, cocoons were degummed with 0.3wt% papain in ph=6 disodium hydrogen phosphate-citric acid buffer solution, bath ratio 1:10, degumming time is 1h, degumming temperature is 60 ℃, and degumming times are 1 time.
Further, the concentration of the lithium bromide solution is 9.3mol/L, the dissolution time is 4 hours, and the dissolution temperature is 60 ℃.
Further, the degummed and dissolved silk fibroin is dialyzed for 3 days by a dialysis bag with the molecular weight cut-off of 3500, distilled water is replaced every 8 hours to obtain a gel product, and the product is freeze-dried and ground to obtain silk fibroin white powder with a beta-sheet structure as a main component.
The application of the polymer blend with the water-induced double-way shape memory effect has wide application prospect in the medical fields of artificial muscles, drug carriers and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts an enzymolysis method to prepare SF, the prepared SF secondary structure is mainly beta-folded, when SF is placed in water with different temperatures, strong hydrogen bonding action can be generated with water molecules, and the existence of the water molecules can induce the SF secondary structure to be transformed;
(2) The polymer blend has the advantages of simple preparation method, easy realization and excellent bioactivity and biocompatibility;
(3) The polymer blend has the water-induced double-way shape memory effect and large deformation, wherein the response temperature of 40 ℃ is close to the body temperature of a human body, so that the blend is expected to be applied to the fields of artificial muscles, intelligent drug carriers and the like.
Drawings
FIG. 1 shows the IR spectra of PLLA and (8%) SF/PLLA;
FIG. 2 is a schematic representation of (8%) SF/PLLA 60℃water-induced two-way shape memory.
Detailed Description
The following describes the implementation of the present invention by way of practical examples:
(1) A polymer blend with water-induced two-way shape memory effect comprising a poly L-lactide-based polymer, and SF based on beta-sheet structure.
(2) The poly L-lactide-based polymer can be poly L-lactide homopolymer or can be a random copolymer synthesized by mixing at least two of L-lactide, glycolide and epsilon-caprolactone and random copolymerization; or the segmented copolymer is synthesized by reacting epsilon-caprolactone with glycol or glycerol to generate hydroxyl end-capped prepolymer, reacting L-lactide or glycolide with succinic acid to generate carboxyl end-capped prepolymer, and mixing at least two of the hydroxyl end-capped prepolymer and the carboxyl end-capped prepolymer with a coupling agent or a chain extender.
(3) The SF mainly with a beta-sheet structure is prepared by an enzymolysis method, and the specific preparation process is as follows: degumming cocoons sequentially with a sodium bicarbonate/sodium dodecyl sulfate mixed solution for 2 times, degumming with a disodium hydrogen phosphate-citric acid buffer solution of papain for 1 time, dialyzing the degummed and dissolved SF for 3 days by using a dialysis bag with the molecular weight cut-off of 3500, replacing distilled water every 8 hours to obtain a gel product, freeze-drying the product, and grinding to obtain SF white powder with a beta-sheet structure as a main component.
(4) The preparation method of the blend is a solution blending method: the poly L-lactide-based polymer was dissolved in chloroform to obtain a polymer solution. And weighing SF according to a certain percentage, and adding chloroform for ultrasonic dispersion. Dropwise adding SF solution after ultrasonic into the polymer solution, stirring at room temperature to uniformly disperse SF in the polymer solution, completely volatilizing chloroform, and drying the film in a vacuum drying oven at 40 ℃ for 24 hours to obtain a blend film
(5) The blend water-induced double-pass shape memory effect test comprises the following specific steps: the blend is shaped under the drying condition (T1), returns to the shape under the water bath condition (T1), is placed under the drying condition (T1) again to be deformed reversibly, and is placed under the water bath condition (T1) again to return to the shape. Each angular change was recorded and the shape recovery rate and shape fixation rate were calculated.
Example 1
A. Preparing SF by an enzymolysis method: 10g of chopped cocoons was added to a 1:1 mixed solution of 500ml sodium bicarbonate (0.02 wt%) and sodium dodecyl sulfate (0.25 wt%), boiled for 30min and removed. Repeatedly washing with deionized water to prevent sodium dodecyl sulfate residue, repeatedly degumming for 2 times, and oven drying SF 60 deg.C after degumming. 3wt% papain buffer solution of pH=6disodium hydrogen phosphate-citric acid is prepared, 1g of dried SF is added to 10ml of the solution, water bath degumming is carried out at 60 ℃ for 1h, deionized water is washed, and the solution is dried at 60 ℃. 1g of dried SF was added to 10ml of lithium bromide solution (9.3 mol/L) and dissolved in a water bath at 60℃for 4 hours. Cooling the dissolved SF solution to 40 ℃, pouring the SF solution into a dialysis bag (molecular weight cut-off 3500), dialyzing the SF solution for 3d by using deionized water, replacing the deionized water every 8 hours to obtain white gel, freeze-drying and grinding to obtain SF white powder.
B. A method for preparing a polymer blend: 1g of PLLA was dissolved in 10ml of chloroform and stirred until dissolved to obtain a PLLA solution. SF was weighed according to 8wt% of PLLA, and 5ml of chloroform was added for ultrasonic dispersion for 1h. Dropping the ultrasonic SF solution into PLLA solution drop by using a dropper, stirring at room temperature for 2 hours, placing the solution in a fume hood, placing the film in a drying oven after chloroform is thoroughly volatilized, and drying at 40 ℃. FIG. 1 shows an infrared spectrum of a (8%) SF/PLLA blend with a wave number of 1624cm -1 And 1520cm -1 Two new absorption peaks appear at the position, and the two new absorption peaks are respectively attributed to characteristic absorption peaks of an amide I band and an amide II band of a beta-sheet structure in an SF secondary structure.
C. The composites were tested for water-induced two-way shape memory effect by bending (fig. 2a,2 b). Step one: placing the sample in an oven at 60 ℃ for 15min, applying external force to bend and deform the sample by 180 DEG, taking out the sample after external force is kept, cooling to room temperature, standing for 15min, unloading, slightly recovering the sample in the X-axis negative direction, and recording the position of the sample as X at the moment 1 Recording the angle theta of sample holding at this time f The method comprises the steps of carrying out a first treatment on the surface of the Step two: the sample is put back into water with the temperature of 60 ℃ for 15min and then taken out, the sample returns to the X-axis negative direction, and the position of the sample is marked as X 2 Record X 1 And X is 2 The angle between them is theta 0 (θ n-1 ). Step three: the recovered sample is placed in an oven at 60 ℃ again, the sample is taken out after 15min, the sample is recovered reversely, namely recovered towards the positive direction of the X axis, and the position of the sample at the moment is recoveredPut as X 3 This is the complete first reversible recovery cycle, X 2 And X is 3 The angle between them is the angle of the first reversible recovery, which is marked as theta 1 (θn). And then repeating the second and third steps, and observing that the sample continues to carry out reversible recovery within the angle of the last reversible recovery. According to formula R f (％)＝(180-θ f ) 180×100 and R r (％)＝θ n /θ n-1 100 calculation of sample shape fixation Rate (R f ) And the nth shape recovery (R r ). R under the condition of 60 ℃ water stimulation f ＝98％，R r All maintained above 95% and the blend (8%) SF/PLLA angle shift was shown in FIG. 2c.
Example 2
A. The preparation method of the polylactic acid-silk fibroin composite film comprises the following steps: 1g of PLLA was dissolved in 10ml of chloroform and stirred until dissolved to obtain a PLLA solution. SF was weighed to 6wt% of PLLA, and 5ml of chloroform was added for 1 hour of ultrasonic dispersion. Dropping the ultrasonic SF solution into the PLLA solution drop by using a dropper, stirring for 1h, placing the solution in a fume hood, placing the film in a drying oven after chloroform is thoroughly volatilized, and drying at 40 ℃.
B. The bending method is used for testing the water-induced double-pass shape memory effect of the composite material. Step one: placing the sample in a 40 ℃ oven for 15min, applying external force to bend and deform the sample by 180 DEG, taking out the sample after external force is kept, cooling to room temperature, standing for 15min, unloading, slightly recovering the sample in the X-axis negative direction, and recording the position of the sample as X 1 Recording the angle theta of sample holding at this time f The method comprises the steps of carrying out a first treatment on the surface of the Step two: the sample is put back into water with the temperature of 40 ℃ for 15min and then taken out, the sample returns to the X-axis negative direction, and the position of the sample is marked as X 2 Record X 1 And X is 2 The angle between them is theta 0 . Step three: the recovered sample is placed in an oven at 40 ℃ again, the sample is taken out after 15min, the sample is recovered reversely, namely recovered towards the positive direction of the X axis, and the position of the sample is marked as X at the moment 3 This is the complete first reversible recovery cycle, X 2 And X is 3 The angle between them is the angle of the first reversible recovery, which is marked as theta 1 . Then repeating the second stepThirdly, observing that the sample continues to be reversibly recovered within the last reversible recovery angle, and according to the formula R f (％)＝(180-θ f ) 180×100 and R r (％)＝θ n /θ n-1 100 calculation of sample shape retention (R r ) And the nth shape recovery (R r ). R under the condition of water stimulation at 40 DEG C f ＝99％，R r All remain above 95%.
The invention provides a preparation method of a polymer blend with a water-induced double-pass shape memory effect. The polymer is a blend prepared by a solution blending method according to a certain mass percentage by using a poly L-lactide (PLLA) based polymer and a Silk Fibroin (SF) with a beta-sheet structure as a main component. Compared with the prior art, the invention has the following characteristics: (1) SF mainly with a beta-sheet structure is introduced to enable the blend to have a water-induced double-way shape memory effect, the reversible transformation temperature is 40-70 ℃, and the reversible shape recovery rate is more than 95%; the reversible temperature of 40 ℃ approaches to the temperature of a human body, so that the blend has potential application prospects in the medical fields of artificial muscles, drug carriers and the like; (2) The introduction of SF improves the hydrophilicity and biocompatibility of the PLLA-based polymer, and endows the blend with excellent bioactivity; the preparation method of the blend is simple and easy to realize.
Claims (8)
1. A method for preparing a polymer blend with a water-induced double-pass shape memory effect, which is characterized by comprising the following steps: blending a poly L-lactide-based polymer and a silk fibroin solution with a beta-sheet structure as a main component: dissolving a poly L-lactide-based polymer in chloroform to obtain a poly L-lactide-based polymer chloroform solution, weighing silk fibroin according to the mass percentage of silk fibroin accounting for 2% -20% of the poly L-lactide-based polymer, adding chloroform for ultrasonic dispersion, dropwise dripping the silk fibroin solution after ultrasonic into the polymer solution, stirring at room temperature to uniformly disperse the silk fibroin in the polymer solution, thoroughly volatilizing the chloroform, and drying the film in a vacuum drying oven at 40 ℃ for 24 hours to obtain a blend film; the poly L-lactide-based polymer is a random copolymer prepared by random copolymerization of at least two of poly L-lactide or L-lactide and glycolide epsilon-caprolactone; the preparation method of the silk fibroin comprises the following steps: the silkworm cocoons are sequentially degummed by adopting a sodium bicarbonate/sodium dodecyl sulfate mixed solution and a disodium hydrogen phosphate-citric acid buffer solution of papain, and are dissolved in a lithium bromide solution, dialyzed and freeze-dried to prepare silk fibroin white powder mainly with a beta-sheet structure.
2. The method of preparing a polymer blend with water-induced two-way shape memory effect according to claim 1, wherein: the poly L-lactide-based polymer is a segmented copolymer prepared by reacting epsilon-caprolactone with glycol or glycerol to generate hydroxyl end-capped prepolymer, reacting L-lactide or glycolide with succinic acid to generate carboxyl end-capped prepolymer, and mixing at least two of the pre-polymers with a coupling agent or a chain extender.
3. The method of preparing a polymer blend with water-induced two-way shape memory effect according to claim 1, wherein: the poly L-lactide-based polymer is a blend of at least two of poly L-lactide, polyglycolide, and poly epsilon-caprolactone.
4. The method of preparing a polymer blend with water-induced two-way shape memory effect according to claim 1, wherein: cocoons were prepared using 0.02wt% sodium bicarbonate, 0.25wt% sodium dodecyl sulfate 1 by volume: degumming the mixed solution of 1, wherein the bath ratio is 1:50, degumming temperature 100 ℃, degumming time 30min and degumming times 2 times.
5. The method of preparing a polymer blend with water-induced two-way shape memory effect according to claim 1, wherein: cocoons were degummed with 0.3wt% papain ph=6 disodium hydrogen phosphate-citric acid buffer solution, bath ratio 1:10, degumming time is 1h, degumming temperature is 60 ℃, and degumming times are 1 time.
6. The method of preparing a polymer blend with water-induced two-way shape memory effect according to claim 1, wherein: the concentration of the lithium bromide solution is 9.3mol/L, the dissolution time is 4 hours, and the dissolution temperature is 60 ℃.
7. The method of preparing a polymer blend with water-induced two-way shape memory effect according to claim 1, wherein: dialyzing degummed and dissolved silk fibroin for 3 days by using a dialysis bag with 3500 molecular weight cutoff, replacing distilled water every 8 hours to obtain a gel product, freeze-drying the product, and grinding to obtain silk fibroin white powder with a beta-sheet structure as a main component.
8. Use of a polymer blend having a water-induced two-way shape memory effect, characterized by: use of a polymer blend with water-induced two-way shape memory effect prepared by the process of any one of claims 1-7 in the medical field.
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