CN114891328A - Preparation method and application of polymer blend with water-induced two-way shape memory effect - Google Patents
Preparation method and application of polymer blend with water-induced two-way shape memory effect Download PDFInfo
- Publication number
- CN114891328A CN114891328A CN202210303337.4A CN202210303337A CN114891328A CN 114891328 A CN114891328 A CN 114891328A CN 202210303337 A CN202210303337 A CN 202210303337A CN 114891328 A CN114891328 A CN 114891328A
- Authority
- CN
- China
- Prior art keywords
- water
- induced
- shape memory
- lactide
- blend
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/42—Proteins; Polypeptides; Degradation products thereof; Derivatives thereof, e.g. albumin, gelatin or zein
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/26—Mixtures of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/43504—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates
- C07K14/43563—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects
- C07K14/43586—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects from silkworms
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P21/00—Preparation of peptides or proteins
- C12P21/06—Preparation of peptides or proteins produced by the hydrolysis of a peptide bond, e.g. hydrolysate products
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/16—Materials with shape-memory or superelastic properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/30—Materials or treatment for tissue regeneration for muscle reconstruction
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
Abstract
The invention provides a preparation method and application of a polymer blend with a water-induced two-way shape memory effect, which is a blend prepared by a solution blending method according to certain mass percent by using a poly-L-lactide (PLLA) -based polymer and Silk Fibroin (SF) mainly with a beta-folded structure. Compared with the prior art, the invention has the following characteristics: (1) by introducing SF mainly comprising a beta-folded structure, the blend has a water-induced two-way shape memory effect, the reversible transition temperature is 40-70 ℃, and the reversible shape recovery rate is more than 95%; wherein the reversible transition temperature of 40 ℃ is close to the temperature of a human body, so that the blend has potential application prospect in the medical fields of artificial muscles, drug carriers and the like; (2) the introduction of SF improves the hydrophilicity and biocompatibility of PLLA-based polymers, and endows the blend with excellent bioactivity; (3) 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 two-way shape memory effect, and belongs to the field of novel intelligent and multifunctional materials.
Background
Two-way shape memory polymers (2W-SMPs), which are polymers that impart a temporary shape under the action of external force and external stimuli (e.g., temperature, water, light, etc.), return to the original shape when receiving the external stimuli again, and are reversibly transformed into the temporary shape and the original shape by the external stimuli again after being shaped for the first time. The reversible conversion characteristic of the shape enables the 2W-SMPs to be widely applied to the biomedical fields of artificial muscles, intelligent drug carriers and the like. At present, the two-way shape memory effect of shape memory polymers is usually realized through melting-crystallization transformation, and only responds to thermal stimulation, but certain specific parts of a human body cannot be directly heated, so that the traditional thermally-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 water molecules are widely present in the body and are most safe to the human body. Research shows that most of the water-induced shape memory polymers only have one-way shape memory effect, and polymer material systems with water-induced two-way shape memory effect are rarely reported. The reported water-induced 2W-SMPs are mostly polymer composite materials with a special bilayer 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 bonding force between polymer materials forming the bilayer structure are weaker, so that the compatibility and the bonding force have adverse effects on various service performances such as mechanical property of the materials, and the application of the materials in the biomedical field is limited.
Disclosure of Invention
The invention aims to: aiming at the problems of the existing water-induced 2W-SMPs, Silk Fibroin (SF) mainly having a beta-folded structure is introduced into a poly L-lactide-based polymer through a simple solution blending method to prepare a blend with better water-induced two-way shape memory property, bioactivity and biocompatibility, the transition temperature range of the blend is 40-70 ℃, 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 a water-induced two-way shape memory effect comprises the following steps of blending a poly-L-lactide-based polymer and a silk fibroin solution mainly comprising a beta-sheet structure: dissolving a poly L-lactide-based polymer in trichloromethane to obtain a poly L-lactide-based polymer trichloromethane solution, weighing silk fibroin according to the mass percentage of silk fibroin accounting for 2-20% of the poly L-lactide-based polymer, adding trichloromethane for ultrasonic dispersion, dropwise adding the ultrasonic silk fibroin solution into the polymer solution, stirring at room temperature to uniformly disperse the silk fibroin in the polymer solution, and drying the film in a vacuum drying oven at 40 ℃ for 24 hours after the trichloromethane is completely volatilized to obtain the 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 and glycolide epsilon-caprolactone.
Furthermore, the poly L-lactide-based polymer is a multi-block copolymer prepared by mixing at least two of epsilon-caprolactone and ethylene glycol or glycerol to generate hydroxyl-terminated prepolymer, L-lactide or glycolide and succinic acid to generate carboxyl-terminated prepolymer and then passing through 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 epsilon-caprolactone.
Further, the preparation method of the silk fibroin comprises the following steps: the silk cocoon is degummed by sodium bicarbonate/lauryl sodium sulfate mixed solution, disodium hydrogen phosphate-citric acid buffer solution of papain, lithium bromide solution is dissolved, dialyzed, frozen and dried to prepare white silk fibroin powder mainly with beta-folded structure.
Further, the silkworm cocoon adopts the following components in a volume ratio of 0.02 wt% of sodium bicarbonate to 0.25 wt% of sodium dodecyl sulfate of 1:1, degumming by using a mixed solution with a bath ratio of 1: 50, degumming temperature of 100 ℃, degumming time of 30min and degumming times of 2 times.
Further, the silkworm cocoon is degummed by using 0.3 wt% of papain and pH 6 disodium hydrogen phosphate-citric acid buffer solution, wherein the bath ratio is 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 dissolving time is 4h, and the dissolving temperature is 60 ℃.
Further, dialyzing the degummed and dissolved silk fibroin for 3 days by using a dialysis bag with the molecular weight cutoff of 3500, replacing distilled water every 8 hours to obtain a gel product, and freeze-drying and grinding the product to obtain white silk fibroin powder mainly with a beta-folded structure.
The application of the polymer blend with the water-induced two-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 takes beta-folding as a main part, when the SF is placed in water with different temperatures, the SF can generate strong hydrogen bond action with water molecules, and the SF secondary structure can be induced to be transformed by the existence of the water molecules;
(2) the polymer blend has the advantages of simple preparation method, easy realization, excellent biological activity and biocompatibility;
(3) the polymer blend has a water-induced two-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 is an infrared spectrum 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 a water-induced two-way shape memory effect comprises a poly-L-lactide-based polymer and SF with a beta-sheet structure as the main component.
(2) The poly L-lactide-based polymer can be a poly L-lactide homopolymer or a random copolymer synthesized by mixing at least two of L-lactide, glycolide and epsilon-caprolactone and carrying out random copolymerization; or a multi-block copolymer synthesized by mixing at least two of the prepolymer and the prepolymer which are subjected to hydroxyl end capping by the reaction of epsilon-caprolactone and ethylene glycol or glycerol, the prepolymer which is subjected to carboxyl end capping by the reaction of L-lactide or glycolide and succinic acid and a coupling agent or a chain extender.
(3) The SF mainly with a beta-folding structure is prepared by an enzymolysis method, and the specific preparation process is as follows: degumming silkworm cocoon with sodium bicarbonate/sodium dodecyl sulfate mixed solution for 2 times, degumming with disodium hydrogen phosphate-citric acid buffer solution of papain for 1 time, dialyzing dissolved SF with dialysis bag with molecular weight cutoff of 3500 for 3 days, replacing distilled water every 8h to obtain gel product, freeze drying, and grinding to obtain SF white powder with beta-folded structure as main component.
(4) The preparation method of the blend is a solution blending method: dissolving the poly L-lactide-based polymer in chloroform to obtain a polymer solution. SF is weighed according to a certain percentage and added with trichloromethane for ultrasonic dispersion. Dropwise adding the SF solution after ultrasonic treatment into the polymer solution, stirring at room temperature to uniformly disperse the SF in the polymer solution, placing the film in a vacuum drying oven at 40 ℃ for drying for 24 hours after the chloroform is completely volatilized, and obtaining the blend film
(5) The blend water-induced two-way shape memory effect test comprises the following specific steps: the blend was shaped under dry conditions (T1), shape-recovered under water bath conditions (T1), reversibly deformed when placed again under dry conditions (T1), and shape-recovered when placed again under water bath conditions (T1). And recording the angle change of each time, and calculating the shape recovery rate and the shape fixing rate.
Example 1
A. Preparing SF by an enzymolysis method: a1: 1 mixed solution of sodium bicarbonate (0.02 wt%) and sodium dodecyl sulfate (0.25 wt%) in an amount of 500ml is added to 10g of cut silkworm cocoon, boiled for 30min and taken out. Repeatedly washing with deionized water to prevent sodium dodecyl sulfate residue, repeatedly degumming for 2 times, and drying the degummed SF at 60 deg.C. Preparing a 3 wt% papain pH 6 disodium hydrogen phosphate-citric acid buffer solution, adding 1g dried SF into each 10ml solution, degumming in a water bath at 60 ℃ for 1h, washing with deionized water, and drying at 60 ℃. 1g of dried SF was added to 10ml of a lithium bromide solution (9.3mol/L) and dissolved in a water bath at 60 ℃ for 4 hours. Cooling the dissolved SF solution to 40 ℃, pouring into a dialysis bag (molecular weight cut-off is 3500), dialyzing with deionized water for 3d, replacing the deionized water every 8h to obtain white gel, freeze-drying, and grinding to obtain SF white powder.
B. Method for preparing the polymer blend: 1g of PLLA was dissolved in 10ml of chloroform, and stirred until dissolved, to obtain a PLLA solution. SF is weighed according to 8 wt% of PLLA dosage, 5ml of trichloromethane is added for ultrasonic dispersion for 1 h. Dropwise adding the SF solution after ultrasonic treatment into the PLLA solution by using a dropper, stirring at room temperature for 2 hours, placing the mixture in a fume hood with an opening, placing the film in a drying oven after the trichloromethane is completely volatilized, and drying at 40 ℃. FIG. 1 is an infrared spectrum of PLLA, (8%) SF/PLLA blend with a wavenumber of 1624cm -1 And 1520cm -1 Two new absorption peaks appear, and both belong to the characteristic absorption peaks of an amide I band and an amide II band of a beta-folding structure in an SF secondary structure.
C. The bending method was used to test the water-induced two-way shape memory effect of the composite (FIGS. 2a, 2 b). The method comprises the following steps: placing the sample in a 60 ℃ oven for 15min, applying external force to bend and deform the sample by 180 degrees, keeping the external force, taking out the sample, cooling to room temperature, standing for 15min, unloading, slightly recovering the sample to the negative direction of the X axis, and recording the position of the sample as X 1 Record the angle θ at which the sample is held f (ii) a Step two: the sample was returned to 60 ℃ water for 15min and then taken out, the sample was returned in the negative X-axis direction, and the position of the sample at this time was designated as X 2 Record X 1 And X 2 Angle between is theta 0 (θ n-1 ). Step three: placing the recovered sample in 60 deg.C oven again, taking out after 15min, allowing the sample to reversely recover, i.e. recovering to positive direction of X axis, and recording the position of the sample as X 3 This is the complete first reversible recovery cycle, X 2 And X 3 The angle between them is the first reversible angle, denoted as θ 1 (θ n). And repeating the second step and the third step, and observing that the sample continues to perform reversible recovery within the last reversible recovery angle. According to the formula R f (％)＝(180-θ f ) /180X 100 and R r (％)＝θ n /θ n-1 X 100 calculation of sample shape fixation Rate (R) f ) And shape recovery ratio (R) of Nth order r ). Under the condition of water stimulation at 60 ℃, R f ＝98％，R r All kept above 95%, and the blend (8%) SF/PLLA has the angular transformation shown in FIG. 2 c.
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 is weighed according to 6 wt% of the PLLA dosage, 5ml of trichloromethane is added for ultrasonic dispersion for 1 hour. Dropwise adding the SF solution after ultrasonic treatment into the PLLA solution by using a dropper, stirring for 1h, placing the mixture in a fume hood with an opening, placing the film in a drying box after the trichloromethane is completely volatilized, and drying at 40 ℃.
B. And testing the water-induced two-way shape memory effect of the composite material by a bending method. The method comprises the following steps: placing the sample in an oven at 40 deg.C for 15min, and applying external force to make the sample reach the desired temperatureBending and deforming the sample by 180 degrees, keeping external force, taking out the sample, cooling to room temperature, standing for 15min, unloading, slightly recovering the sample to the negative direction of the X axis, and recording the position of the sample as X 1 Record the angle θ at which the sample is held f (ii) a Step two: the sample was returned to 40 ℃ water for 15min and then taken out, the sample was returned in the negative X-axis direction, and the position of the sample at this time was designated as X 2 Record X 1 And X 2 Angle between is theta 0 . Step three: putting the recovered sample in an oven at 40 ℃ again, taking out after 15min, allowing the sample to reversely recover, i.e. recovering to the positive direction of the X axis, and recording the position of the sample as X 3 This is the complete first reversible recovery cycle, X 2 And X 3 The angle between them is the first reversible angle, denoted as θ 1 . And then repeating the second step and the third step, observing that the sample continues to perform reversible recovery within the last reversible recovery angle, and performing reversible recovery according to a formula R f (％)＝(180-θ f ) /180X 100 and R r (％)＝θ n /θ n-1 X 100 calculation of sample shape retention (R) r ) And shape recovery ratio (R) of Nth order r ). Under the condition of water stimulation at 40 ℃, R f ＝99％，R r All are kept above 95%.
The invention provides a preparation method of a polymer blend with a water-induced two-way shape memory effect. The blend is prepared by a solution blending method according to certain mass percent by using a poly L-lactide (PLLA) base polymer and Silk Fibroin (SF) mainly comprising a beta-folding structure. Compared with the prior art, the invention has the following characteristics: (1) by introducing SF mainly comprising a beta-folded structure, the blend has a water-induced two-way shape memory effect, the reversible transition temperature is 40-70 ℃, and the reversible shape recovery rate is more than 95%; wherein the reversible transition temperature of 40 ℃ is close to the temperature of a human body, so that the blend has potential application prospect in the medical fields of artificial muscles, drug carriers and the like; (2) the introduction of SF improves the hydrophilicity and biocompatibility of PLLA-based polymers, and endows the blend with excellent bioactivity; (3) the preparation method of the blend is simple and easy to realize.
Claims (10)
1. A preparation method of a polymer blend with a water-induced two-way shape memory effect is characterized by comprising the following steps: blending poly L-lactide-based polymer and silk fibroin solution mainly with beta-folding structure: dissolving a poly L-lactide-based polymer in trichloromethane to obtain a poly L-lactide-based polymer trichloromethane solution, weighing silk fibroin according to the mass percentage of silk fibroin accounting for 2-20% of the poly L-lactide-based polymer, adding trichloromethane for ultrasonic dispersion, dropwise adding the ultrasonic silk fibroin solution into the polymer solution, stirring at room temperature to uniformly disperse the silk fibroin in the polymer solution, and drying the film in a vacuum drying oven at 40 ℃ for 24 hours after the trichloromethane is completely volatilized to obtain the blend film.
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 random copolymer prepared by random copolymerization of at least two of poly L-lactide or L-lactide and glycolide epsilon-caprolactone.
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 multi-block copolymer prepared by reacting epsilon-caprolactone with ethylene glycol or glycerol to generate a hydroxyl-terminated prepolymer, reacting L-lactide or glycolide with succinic acid to generate a carboxyl-terminated prepolymer, and mixing at least two of the hydroxyl-terminated prepolymer and the carboxyl-terminated prepolymer with a coupling agent or a chain extender.
4. 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.
5. The method of preparing a polymer blend with water-induced two-way shape memory effect according to claim 1, wherein: the preparation method of the silk fibroin comprises the following steps: the silk cocoon is degummed by sodium bicarbonate/lauryl sodium sulfate mixed solution, disodium hydrogen phosphate-citric acid buffer solution of papain, lithium bromide solution is dissolved, dialyzed, frozen and dried to prepare white silk fibroin powder mainly with beta-folded structure.
6. The method for preparing a polymer blend with water-induced two-way shape memory effect according to claim 5, wherein: the silkworm cocoon adopts 0.02 wt% sodium bicarbonate and 0.25 wt% sodium dodecyl sulfate according to the volume ratio of 1:1, degumming by using a mixed solution with a bath ratio of 1: 50, degumming temperature of 100 ℃, degumming time of 30min and degumming times of 2 times.
7. The method for preparing a polymer blend with water-induced two-way shape memory effect according to claim 5, wherein: degumming the silkworm cocoons by using a 0.3 wt% papain-containing disodium hydrogen phosphate-citric acid buffer solution with the pH value of 6, wherein the bath ratio is 1: 10, degumming time is 1h, degumming temperature is 60 ℃, and degumming times are 1 time.
8. The method for preparing a polymer blend with water-induced two-way shape memory effect according to claim 5, wherein: the concentration of the lithium bromide solution is 9.3mol/L, the dissolving time is 4h, and the dissolving temperature is 60 ℃.
9. The method for preparing a polymer blend with water-induced two-way shape memory effect according to claim 5, wherein: dialyzing the degummed and dissolved silk fibroin for 3 days by using a dialysis bag with the molecular weight cutoff of 3500, replacing distilled water every 8h to obtain a gel product, and freeze-drying and grinding the product to obtain white silk fibroin powder mainly with a beta-folded structure.
10. The application of a polymer blend with a water-induced two-way shape memory effect is characterized in that: has wide application prospect in the medical fields of artificial muscles, drug carriers and the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210303337.4A CN114891328B (en) | 2022-03-24 | 2022-03-24 | Preparation method and application of polymer blend with water-induced double-way shape memory effect |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210303337.4A CN114891328B (en) | 2022-03-24 | 2022-03-24 | Preparation method and application of polymer blend with water-induced double-way shape memory effect |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114891328A true CN114891328A (en) | 2022-08-12 |
| CN114891328B CN114891328B (en) | 2023-08-01 |
Family
ID=82715805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210303337.4A Active CN114891328B (en) | 2022-03-24 | 2022-03-24 | Preparation method and application of polymer blend with water-induced double-way shape memory effect |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114891328B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081925A (en) * | 2007-06-01 | 2007-12-05 | 哈尔滨工程大学 | Alternating magnetic field driven shape memory biological degradable polymer and preparation method thereof |
| CN101205367A (en) * | 2007-12-06 | 2008-06-25 | 复旦大学 | Total-fibroin albumen composite material and preparation method thereof |
| CN102863750A (en) * | 2012-09-28 | 2013-01-09 | 哈尔滨工程大学 | Biodegradable polymer composite material having multistep shape memory effect, preparation method thereof and molded part manufacturing and shape recovery method |
| CN103613652A (en) * | 2013-11-15 | 2014-03-05 | 苏州大学 | Method for purifying silk fibroin |
| JP2017517344A (en) * | 2014-06-10 | 2017-06-29 | エシコン・エンド−サージェリィ・エルエルシーＥｔｈｉｃｏｎ Ｅｎｄｏ−Ｓｕｒｇｅｒｙ， ＬＬＣ | Method and apparatus for sealing stapled tissue |
| CN106943621A (en) * | 2017-04-21 | 2017-07-14 | 芜湖扬展新材料科技服务有限公司 | A kind of fibroin albumen composite biological tissues repair materials and preparation method thereof |
-
2022
- 2022-03-24 CN CN202210303337.4A patent/CN114891328B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081925A (en) * | 2007-06-01 | 2007-12-05 | 哈尔滨工程大学 | Alternating magnetic field driven shape memory biological degradable polymer and preparation method thereof |
| CN101205367A (en) * | 2007-12-06 | 2008-06-25 | 复旦大学 | Total-fibroin albumen composite material and preparation method thereof |
| CN102863750A (en) * | 2012-09-28 | 2013-01-09 | 哈尔滨工程大学 | Biodegradable polymer composite material having multistep shape memory effect, preparation method thereof and molded part manufacturing and shape recovery method |
| CN103613652A (en) * | 2013-11-15 | 2014-03-05 | 苏州大学 | Method for purifying silk fibroin |
| JP2017517344A (en) * | 2014-06-10 | 2017-06-29 | エシコン・エンド−サージェリィ・エルエルシーＥｔｈｉｃｏｎ Ｅｎｄｏ−Ｓｕｒｇｅｒｙ， ＬＬＣ | Method and apparatus for sealing stapled tissue |
| CN106943621A (en) * | 2017-04-21 | 2017-07-14 | 芜湖扬展新材料科技服务有限公司 | A kind of fibroin albumen composite biological tissues repair materials and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张蕾;周松;程抱昌;: "生物材料在纤维环修复中的研究现实及挑战", 中国组织工程研究, no. 06 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114891328B (en) | 2023-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110698697B (en) | Preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance | |
| CN107556482B (en) | A kind of injectable high intensity chitin based aquagel and its preparation method and application | |
| CN107043465A (en) | A kind of urea groups pyrimidone modified gelatin injectable self-healing hydrogel and preparation method thereof | |
| CN101798403B (en) | Method for preparing chitosan/polyving alcohol/polylactic acid blended dense membrane | |
| CN108186555B (en) | Shape memory hydrogel with calcium ion complexing and redox dual responses and preparation method thereof | |
| CN110396124B (en) | Self-assembling polypeptides and their use as hemostatic agents | |
| CN106632949A (en) | Oligochitosan or derivative-modified polyurethane fiber dressing and preparation method thereof | |
| CN114891328B (en) | Preparation method and application of polymer blend with water-induced double-way shape memory effect | |
| CN107417901A (en) | A kind of bionical toughness reinforcing bioelastomer and preparation method thereof | |
| EP1659143A1 (en) | Temperature-responsive hydrogel | |
| CN110564123B (en) | Polylactic acid/bioglass composite material and preparation method thereof | |
| CN105418861A (en) | Crosslinking hydrogel based on polyamino acid molecules and preparation method thereof | |
| CN113248743A (en) | Biocompatible degradable three-dimensional cellulose gel and preparation method and application thereof | |
| CN102558581B (en) | Method for preparing high-strength solid chitosan microcarriers | |
| CN103709411A (en) | Amphipathic triblock copolymer containing morpholine-2,5-diketone derivative copolymer as well as preparation method and application thereof | |
| CN114133686B (en) | Molybdenum disulfide/polyvinyl alcohol composite hydrogel and preparation method of molybdenum disulfide | |
| CN110433332A (en) | A kind of artificial bone renovating material of 3D printing and preparation method thereof | |
| CN114848906B (en) | SF/SiO 2 Composite material | |
| CN109880152B (en) | Preparation method of oriented communicated porous biomedical stent, stent prepared by preparation method and application of stent in preparation of medical products | |
| CN109232915B (en) | Bioactive simulated cartilage hydrogel with high mechanical property and preparation method and application thereof | |
| AU2021104933A4 (en) | Tissue engineering applications of a tunable hydrogel of mammalian extracellular matrix | |
| CN116251233B (en) | High-adhesion hydrogel for promoting meniscus injury repair and preparation method thereof | |
| CN101914199B (en) | Polyester and preparation method thereof | |
| CN116444807B (en) | Lipoic acid-based self-healing supermolecular elastomer and preparation method and application thereof | |
| CN107875444B (en) | Preparation method of biodegradable hydrogel scaffold material for cardiac repair |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |