CN113817145B - Polyester type biodegradable shape memory copolymer based on poly epsilon-caprolactone and preparation method thereof - Google Patents
Polyester type biodegradable shape memory copolymer based on poly epsilon-caprolactone and preparation method thereof Download PDFInfo
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- 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
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- A—HUMAN NECESSITIES
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- 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
- A61L27/58—Materials at least partially resorbable by the body
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
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- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/16—Materials with shape-memory or superelastic properties
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- C08G2280/00—Compositions for creating shape memory
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Abstract
The poly-epsilon-caprolactone biodegradable shape memory copolymer is prepared by copolymerizing poly-epsilon-caprolactone, citric acid and 1, 8-octanedioate and then crosslinking and curing, has the advantages of good mechanical property, large deformation amount, high recovery rate under high-order stretching and biodegradability, and meanwhile, has the advantages of simple preparation method, convenient operation, high preparation efficiency and wide application prospect.
Description
Technical Field
The invention relates to the field of intelligent polymer materials, in particular to a polyester type biodegradable shape memory copolymer based on poly epsilon-caprolactone and a preparation method thereof.
Background
Shape memory polymers are a class of polymers that sense a stimulus from a change in an environment (e.g., temperature, force, electromagnetic, solvent, etc.) and, in response to the change, adjust a mechanical parameter (e.g., shape, position, strain, etc.) of the polymer to return to its predetermined state. Such materials are also referred to as smart materials because of their good dexterity and their important potential application in smart or smart architectures.
Biodegradable shape memory polymers differ from conventional materials in their biodegradability, i.e., the ability of the material to automatically degrade into fragments or small molecules in a physiological environment and then be excreted outside the body by digestion and metabolism of the body without leaving toxic or indigestible substances. Therefore, such materials are the most desirable materials for applications in the medical field.
Most biodegradable polymers have little or poor shape memory properties, which limits the field of application of biodegradable shape memory polymers, particularly in biomedical engineering.
At present, there are two main preparation methods for the poly epsilon-caprolactone-based biodegradable shape memory copolymer: one is to use poly epsilon-caprolactone diol as raw material to synthesize shape memory polyurethane, and the other is to copolymerize or blend poly epsilon-caprolactone with polylactic acid.
However, the general shape memory poly epsilon-caprolactone material has poor mechanical property and low recovery rate under high-power stretching, so that the application of the shape memory poly epsilon-caprolactone material is limited.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: the poly-epsilon-caprolactone biodegradable shape memory copolymer prepared by copolymerizing the poly-epsilon-caprolactone, the citric acid and the 1, 8-octanedionate as raw materials and then crosslinking and curing has good mechanical property, has the advantages of large deformation amount, high recovery rate under high-magnification stretching and biodegradability, is simple in preparation method and high in preparation efficiency, and can be applied to the medical field as a degradable intelligent material.
The first aspect of the invention provides a poly-epsilon-caprolactone biodegradable shape memory copolymer, which is prepared by copolymerizing poly-epsilon-caprolactone, citric acid and 1, 8-octanediol and then crosslinking and curing.
The second aspect of the present invention is to provide a method for preparing the poly-epsilon-caprolactone biodegradable shape memory copolymer, which is prepared by using poly-epsilon-caprolactone, citric acid and 1, 8-octanediol as raw materials.
The third aspect of the present invention provides a use of the biodegradable shape memory copolymer of polyepsilon caprolactone according to the first aspect of the present invention or the biodegradable shape memory copolymer of polyepsilon caprolactone prepared by the preparation method of the second aspect of the present invention, which can be used as a degradable intelligent material in the biomedical field, preferably in sutures, drug sustained release carriers, orthodontic appliance materials, stent materials and fixation materials.
The biodegradable shape memory copolymer of poly epsilon-caprolactone and the preparation method thereof provided by the invention have the following advantages:
(1) The biodegradable shape memory copolymer of poly-epsilon-caprolactone has the advantages of large deformation amount, high deformation recovery rate and biodegradability;
(2) The preparation method of the biodegradable shape memory copolymer of poly-epsilon-caprolactone is simple and convenient to operate;
(3) The poly epsilon-caprolactone biodegradable shape memory copolymer can be used as a degradable intelligent material to be applied to sutures, drug sustained-release carriers, orthodontic appliance materials, stent materials and fixing materials.
Drawings
FIG. 1 shows the torsional deformation-recovery process of a biodegradable shape memory copolymer of poly-epsilon-caprolactone prepared in example 1 of the present invention;
FIG. 2 shows the process of tensile deformation-recovery of a biodegradable shape memory copolymer of poly-epsilon-caprolactone produced in example 2 of the present invention;
FIG. 3 shows stress-strain curves at 50 ℃ of a biodegradable shape memory copolymer of poly-epsilon-caprolactone prepared in example 1 of the present invention;
FIG. 4 shows the temperature rise-fall DSC curve of the biodegradable shape memory copolymer of poly-epsilon-caprolactone prepared in example 2 of the present invention;
FIG. 5 shows the weight loss curves of the biodegradable shape memory co-polymer bodies of poly-epsilon-caprolactone prepared in example 1 of the present invention in phosphate buffered saline solutions of different pH values.
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent with reference to the following description.
The first aspect of the invention provides a poly-epsilon-caprolactone biodegradable shape memory copolymer, which is prepared by copolymerizing poly-epsilon-caprolactone, citric acid and 1, 8-octanediol and then crosslinking and curing.
The existing polyurethane polycaprolactone shape memory polymer is generally prepared by polymerizing low-molecular-weight polycaprolactone diol and isocyanate, and a hard phase formed by the isocyanate is used as a physical crosslinking point, so that the polyurethane polycaprolactone shape memory polymer is a thermoplastic polymer. But the mechanical property is poor, and the recovery rate under high-power stretching is low.
The poly epsilon-caprolactone copolymer is prepared by adopting poly epsilon-caprolactone, citric acid and 1, 8-octanediol as raw materials, and experiments show that the poly epsilon-caprolactone component in the poly epsilon-caprolactone biodegradable shape memory copolymer prepared by adopting the raw materials can be crystallized, the copolymer is in a plastic state below a melting point, the copolymer is in a rubber state above the melting point, and the recovery rate is high under high-power stretching.
According to the invention, the poly-epsilon-caprolactone is selected from one or more of poly-epsilon-caprolactone diol with hydroxyl groups at two ends, poly-epsilon-caprolactone with carboxyl groups at one end and carboxyl groups at the other end and poly-epsilon-caprolactone with carboxyl groups at two ends, preferably from one or two of poly-epsilon-caprolactone diol with hydroxyl groups at two ends and poly-epsilon-caprolactone with carboxyl groups at one end and hydroxyl groups at the other end, more preferably poly-epsilon-caprolactone diol with hydroxyl groups at two ends or poly-epsilon-caprolactone with carboxyl groups at one end and hydroxyl groups at the other end.
The poly-epsilon-caprolactone has excellent biocompatibility, memory and biodegradability, and tests show that the biodegradable shape memory copolymer prepared from the poly-epsilon-caprolactone with the structure has larger deformation and higher recovery rate.
The poly epsilon-caprolactone accounts for 65-95% of the mass of the copolymer, preferably accounts for 70-90% of the mass of the copolymer, and more preferably accounts for 75-80% of the mass of the copolymer.
The relative molecular mass of the poly-epsilon-caprolactone is 5000 to 100000, preferably 7000 to 60000, and more preferably 9000 to 40000.
The melting point of the poly-epsilon-caprolactone biodegradable shape memory copolymer can be regulated and controlled by changing the relative molecular mass and mass fraction of the poly-epsilon-caprolactone. The higher the relative molecular mass of the poly-epsilon-caprolactone, the higher the mass fraction of the copolymer, and the higher the melting point of the prepared poly-epsilon-caprolactone biodegradable shape memory copolymer.
The molar ratio of citric acid to 1, 8-octanediol is (0.1-10): 1, preferably (0.5-5): 1, and more preferably the molar ratio is (0.5 to 2): 1.
The poly epsilon-caprolactone biodegradable shape memory copolymer has the advantages of large deformation amount, high deformation recovery rate and biodegradability, the shape recovery temperature is 20-60 ℃, the setting temperature is-20-30 ℃, the deformation recovery degree is 90-100%, the maximum elongation rate can reach 2500%, the poly epsilon-caprolactone biodegradable shape memory copolymer can be degraded in acidic solution, neutral solution and alkaline solution, and the degradation rate in the alkaline solution is the highest and can reach more than 90%.
In the present invention, the biodegradable shape memory copolymer of poly-e-caprolactone as described in the present invention is prepared by a method comprising the steps of:
step 1, carrying out polymerization reaction on poly epsilon-caprolactone, citric acid and 1, 8-octanediol to obtain a copolymer prepolymer;
and 2, curing the copolymer prepolymer obtained in the step 1 to obtain the shape memory copolymer.
The second aspect of the present invention is to provide a method for preparing the poly-epsilon-caprolactone biodegradable shape memory copolymer of the first aspect of the present invention, wherein the preparation method is carried out by using poly-epsilon-caprolactone, citric acid and 1, 8-octanediol as raw materials.
According to the invention, the preparation method comprises the following steps:
step 1, performing polymerization reaction on poly epsilon-caprolactone, citric acid and 1, 8-octanediol to obtain a copolymer prepolymer;
and 2, curing the copolymer prepolymer obtained in the step 1 to obtain the shape memory copolymer.
This step is specifically described and illustrated below.
Step 1, performing polymerization reaction on poly epsilon-caprolactone, citric acid and 1, 8-octanediol to obtain a copolymer prepolymer.
In the invention, the poly epsilon-caprolactone, the citric acid and the 1, 8-octanediol can be simultaneously placed in the reaction vessel for polymerization reaction, or the citric acid and the 1, 8-octanediol can be placed in the reaction vessel for reaction for a certain time and then the poly epsilon-caprolactone can be added for polymerization reaction.
The poly-epsilon-caprolactone is one or more selected from poly-epsilon-caprolactone diol with hydroxyl at two ends, poly-epsilon-caprolactone with hydroxyl at one end and carboxyl at the other end and poly-epsilon-caprolactone with both carboxyl at two ends, preferably one or two selected from poly-epsilon-caprolactone diol with hydroxyl at two ends and poly-epsilon-caprolactone with carboxyl at one end and hydroxyl at the other end, more preferably poly-epsilon-caprolactone diol with hydroxyl at two ends or poly-epsilon-caprolactone with carboxyl at one end and hydroxyl at the other end.
The molar ratio of the citric acid to the 1, 8-octanediol is (0.1-10) to 1, and the molar ratio is preferably (0.5-5): 1, and more preferably the molar ratio is (0.5 to 2): 1.
The poly epsilon-caprolactone accounts for 65-95% of the mass of the copolymer, the poly epsilon-caprolactone accounts for 70-90% of the mass of the copolymer, and the poly epsilon-caprolactone accounts for 75-80% of the mass of the copolymer.
The relative molecular mass of the poly-epsilon-caprolactone is 5000 to 100000, preferably 7000 to 60000, and more preferably 9000 to 40000.
Tests show that the higher the relative molecular mass of poly-epsilon-caprolactone, the higher the melting point of the copolymer produced.
The polymerization reaction is preferably carried out in a reaction kettle, and the polymerization reaction is carried out in a protective atmosphere, wherein the protective atmosphere is argon or nitrogen, and preferably nitrogen.
When the polymerization reaction is carried out in the first mode, according to the present invention, it is preferable to carry out stirring after heating before the polymerization reaction, and stirring after heating allows the reactants to be mixed in a sufficiently molten state, and the mixture is more uniform, and is heated to 120 to 200 ℃, preferably 140 to 180 ℃, and more preferably 150 to 165 ℃.
The stirring time is 10 to 60min, preferably 20 to 40min, and more preferably 30min.
After stirring, cooling to the reaction temperature for polymerization, and experiments show that the reaction temperature of 100-180 ℃ is more favorable for controlling the reaction rate and the molecular structure of the prepared copolymer, the prepared copolymer has higher deformation recovery rate and better degradation performance, the reaction temperature is preferably 120-160 ℃, and the reaction temperature is more preferably 130-150 ℃.
The reaction time is 1 to 7 hours, preferably 2 to 5 hours, and more preferably 3 to 4 hours.
If the polymerization reaction is carried out by adopting the second mode, the citric acid and the 1, 8-octanediol are firstly added for reaction for 1 to 3 hours, and then the poly-epsilon-caprolactone is added for continuous polymerization reaction for 1 to 4 hours.
And 2, curing the copolymer prepolymer obtained in the step 1 to obtain the shape memory copolymer.
In the present invention, curing is carried out in a mold at a curing temperature of 100 to 150 ℃, preferably 110 to 140 ℃, more preferably 120 to 130 ℃.
If the curing temperature is too high, such as above 150 ℃, the cured product is easy to generate internal stress to affect the mechanical properties of the material, so that the mechanical properties of the prepared product are poor, and the deformation recovery rate is low.
The curing time is 8 to 48 hours, preferably 15 to 40 hours, and more preferably 20 to 30 hours.
Too short curing time and incomplete curing result in poor mechanical properties of the cured product, too long curing time is also not beneficial to improving the mechanical properties of the cured product, and deformation recovery rate is reduced.
The third aspect of the present invention provides a use of the biodegradable shape memory copolymer of polyepsilon caprolactone according to the first aspect of the present invention or the biodegradable shape memory copolymer of polyepsilon caprolactone prepared by the preparation method of the second aspect of the present invention, which can be used as a degradable intelligent material in the biomedical field, preferably in sutures, drug sustained release carriers, orthodontic appliance materials, stent materials and fixation materials.
The invention has the following beneficial effects:
(1) The synthesis process of the shape memory copolymer is simple and convenient to operate;
(2) The melting point of the poly-epsilon-caprolactone biodegradable shape memory copolymer is 20-60 ℃, the shape recovery temperature is 20-60 ℃, the setting temperature is-20-30 ℃, the recovery degree is 90-100 percent, and the maximum stretching rate can reach 2500 percent;
(3) The poly epsilon-caprolactone biodegradable shape memory copolymer has good degradation performance, can be degraded in alkaline solution, neutral solution and acidic solution, and has the highest degradation rate in alkaline solution which can reach more than 90%.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1
Adding citric acid and 1, 8-octanediol with the molar ratio of 1. Pouring the prepolymer into a mold, and curing for 24 hours at 120 ℃ to obtain the biodegradable shape memory copolymer product. As shown in figure 1, heating the product to 60 ℃, stretching the coiled shape, and cooling to 20 ℃ for fixing deformation; the product is heated to 45 ℃ and the original shape of the product is restored.
Example 2
Adding 1 molar ratio of 1. Pouring the prepolymer into a mold, and curing at 120 ℃ for 21 hours to obtain the biodegradable shape memory copolymer product. As shown in fig. 2, the article was stretched to 600% at room temperature, heated to 45 ℃, and the article returned to its original shape.
Examples of the experiments
Experimental example 1 stress-Strain test
The biodegradable shape memory copolymer of poly-epsilon-caprolactone prepared in example 1 was subjected to mechanical property test in the following procedure: preparing a sample into a total length of 24.70mm and a width of an end part of 7.6mm by a Ray-Ran dumbbell-shaped sample preparation machine; the middle parallel part is a dumbbell-shaped sample strip with the length of 4mm and the width of 2.7mm, the sample strip is fixed by a clamp of a material testing machine, and the actual measurement distance is 4mm. The experiment was carried out at a temperature of 50 ℃ and was stretched to 1500% at a stretching rate of 6mm/min and then returned to the original position at a rate of 6 mm/min. The stress-strain curve is shown in fig. 3.
As can be seen from fig. 3, the stress of the copolymer gradually increases as the strain increases. After stretching to a strain of 1500%, the recovery was 96%.
Experimental example 2 thermal Property test
A DSC tester is used for carrying out thermal performance test on the biodegradable shape memory copolymer of poly-epsilon-caprolactone prepared in example 2, the test temperature range is-75-120 ℃, the test temperature range is nitrogen atmosphere, the temperature rising speed is 5 ℃/min, the temperature reducing speed is 5 ℃/min, and the test result is shown in figure 4.
As can be seen from FIG. 4, the temperature increase at a rate of 5 ℃/min resulted in a melting absorption peak at 36.8 ℃ corresponding to the melting point of the copolymer; the temperature is reduced at a rate of 5 ℃/min, and a crystallization exothermic peak appears at minus 9.8 ℃, corresponding to the crystallization temperature of the copolymer.
Experimental example 3 degradation Performance test
The biodegradable shape memory copolymer of poly-e-caprolactone prepared in example 1 was subjected to a degradation performance test in phosphate buffered saline at pH 5, pH 7 and pH 9, respectively, at room temperature, and the test results are shown in fig. 5.
As can be seen from FIG. 5, the biodegradable shape memory copolymer of poly-epsilon-caprolactone prepared can be degraded to reach equilibrium basically in about 100 days. The degradation rate is the fastest in alkaline phosphate buffered saline solution with the pH value of 9, the degradation rate is the highest and can reach more than 90%, the degradation performance is good, the degradation rate is the second of the degradation rates in neutral solution with the pH value of 7, the degradation rate is the slowest in acidic solution with the pH value of 5, and the degradation rate is the lowest. The biodegradable shape memory copolymer of poly epsilon-caprolactone has good degradation performance.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (3)
1. A method for preparing poly-epsilon-caprolactone biodegradable shape memory copolymer is characterized in that,
the preparation method comprises the following steps:
step 1, performing polymerization reaction on poly epsilon-caprolactone, citric acid and 1, 8-octanediol to obtain a copolymer prepolymer;
the relative molecular mass of the poly-epsilon-caprolactone is 5000-100000, and the poly-epsilon-caprolactone is selected from one or more of poly-epsilon-caprolactone diol with two ends provided with hydroxyl, poly-epsilon-caprolactone with one end provided with hydroxyl and the other end provided with carboxyl and poly-epsilon-caprolactone with two ends both provided with carboxyl;
the mass fraction of the poly-epsilon-caprolactone in the copolymer is 65-95 percent;
the molar ratio of the citric acid to the 1, 8-octanediol is (0.1-10) to 1;
and 2, curing the copolymer prepolymer obtained in the step 1 to obtain the shape memory copolymer.
2. The production method according to claim 1, wherein, in step 1,
before the polymerization reaction, preferably heating and then stirring, heating to 120-200 ℃ and stirring for 10-60 min;
after stirring, the temperature is reduced to the reaction temperature for polymerization reaction, the reaction temperature is 100-180 ℃, and the reaction time is 1-7 h.
3. The method of claim 1, wherein in step 2,
the curing temperature is 100-150 ℃, and the curing time is 8-48 h.
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