CN107286363B - Response method for rapidly recovering solvent type porous shape memory polycaprolactone - Google Patents
Response method for rapidly recovering solvent type porous shape memory polycaprolactone Download PDFInfo
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- CN107286363B CN107286363B CN201710618394.0A CN201710618394A CN107286363B CN 107286363 B CN107286363 B CN 107286363B CN 201710618394 A CN201710618394 A CN 201710618394A CN 107286363 B CN107286363 B CN 107286363B
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2207/00—Foams characterised by their intended use
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
Abstract
The invention discloses a response method of a fast recovery solvent type porous shape memory polycaprolactone, wherein the porous polycaprolactone has a shape memory function of fast recovery within 1 s; the response method adopts a solution casting method, and the molecular chain of polycaprolactone can form a micro-nano flaky structure connected with each other along with the slow volatilization of the solvent of the N, N-dimethylformamide solution of polycaprolactone, thereby forming the porous polycaprolactone. The shape memory effect of the porous polycaprolactone material can be shaped, and the porous polycaprolactone material can be quickly recovered within 1s when being immersed in an organic solvent (ethyl acetate) at room temperature. The organic solvent can rapidly enter the porous structure to act with the micro-nano polycaprolactone sheet structure to form wrinkles, and the residual stress generated when the polycaprolactone is deformed is rapidly released, so that the sample can rapidly recover the initial shape. The method has simple preparation process and low cost, and does not introduce other impurities.
Description
Technical Field
The invention belongs to the technical field of novel high polymer materials, and particularly relates to a response method for quickly recovering solvent type porous shape memory polycaprolactone.
Background
Shape memory polymers are a stimulus-responsive smart material with the ability to "remember" its original shape. Shape memory polymers have become a further area of intense research beyond shape memory alloys due to their unique shape memory function. Compared with the shape memory alloy, the shape memory polymer has the advantages of light weight, low production cost, easy processing, easy performance regulation, large recoverable strain, wide recoverable response temperature range and the like; in addition, it can generate recovery response to various stimulation modes (such as heat, light, PH, solvent, and electromagnetism), but the solvent response type shape memory polymer studied at present can realize faster recovery deformation when the shape memory polymer is in the micro-nanometer scale, but the problem of too long recovery response time (generally in the small scale) is common in the bulk material.
Polycaprolactone is widely used in the biomedical field because of its good biocompatibility and biodegradability. At present, polycaprolactone is generally mixed with other substances such as chitosan, tricalcium phosphate, hydroxyapatite, keratin and the like, and then a freeze drying method is adopted to prepare a porous structure for the orthopedic support.
Disclosure of Invention
The invention provides a response method of a fast recovery solvent type porous shape memory polycaprolactone, which aims to solve the problems of complex hole making process, high cost, low production efficiency and difficult control in the prior art (such as freeze drying and the like). In addition, the solvent response type shape memory polymer material depends on the migration rate of the solvent in the material in the process of shape recovery, so that the response time of the material is too long, and the material can be recovered usually within several hours or even tens of hours, which greatly limits the application of the shape memory material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a response method of fast recovery solvent type porous shape memory polycaprolactone is characterized in that the response method is a solution casting method and comprises the following steps:
s01, dissolving polycaprolactone in N, N-dimethylformamide, and stirring until the polycaprolactone is completely dissolved to obtain a polycaprolactone solution;
s02, pouring the polycaprolactone solution obtained in the step S01 into a mold, then putting the mold into an oven, and drying to obtain the porous polycaprolactone.
Further, in the S01, when the polycaprolactone is dissolved in the N, N-dimethylformamide, the solution is stirred at the temperature of 20-60 ℃ until the solution is transparent.
Further, in the S01, the mass concentration of polycaprolactone is 5-30%.
Further, the porous polycaprolactone obtained in the step S02 is shaped by applying an acting force, so that the porous polycaprolactone in the temporary shape is obtained.
Further, the shaping temperature range is 10-60 ℃.
Furthermore, when the porous polycaprolactone in the temporary shape is immersed in the ethyl acetate solvent, the solvent and the micro-nano-scale polycaprolactone sheet structure act to quickly generate wrinkles, so that the porous polycaprolactone returns to the initial shape.
Further, the recovery time is 0-1s (excluding 1 s).
Further, the recovery temperature is 10-60 ℃.
A fast recovery solvent type porous shape memory polycaprolactone, wherein polycaprolactone molecular chains form micro-nano flaky structures in N, N-dimethylformamide solution, and the micro-nano flaky structures are connected with each other to form a porous structure, so that porous polycaprolactone is obtained.
Further, the porous polycaprolactone is shaped and then immersed in an ethyl acetate solvent, and the porous polycaprolactone is recovered to the initial shape within 0-1 s.
Compared with the prior art, the invention has the following advantages:
the invention provides a response method for quickly recovering solvent type porous shape memory polycaprolactone; the porous shape memory polycaprolactone generates a wrinkle effect under the action of a solvent, and the rapid shape recovery of the porous shape memory polycaprolactone (which can be as fast as 1 second) is realized;
the invention combines the pore structure, the biocompatibility, the biodegradability and the shape memory property of the polycaprolactone, and the prepared porous shape memory polycaprolactone still has higher mechanical strength, thereby expanding the application of the porous shape memory polycaprolactone in the field of biological tissue engineering.
Drawings
FIG. 1 is a scanning electron microscope image of a cross section of porous shape memory polycaprolactone frozen and quenched by liquid nitrogen;
FIG. 2 is an optical microscope photograph of the surface topography of porous shape memory polycaprolactone prepared in accordance with the present invention before and after dropping ethyl acetate on the surface thereof;
FIG. 3 is a photograph of the shape recovery of a solvent driven porous shape memory polycaprolactone made in accordance with the present invention;
FIG. 4 is a picture of the mechanical properties of porous shape memory polycaprolactone prepared according to the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A response method of fast recovery solvent type porous shape memory polycaprolactone is carried out according to the following steps:
s01, dissolving polycaprolactone in N, N-dimethylformamide, and magnetically stirring at 50 ℃ until the solution is transparent to obtain a polycaprolactone solution with the mass concentration of 20%;
s02, standing the polycaprolactone solution obtained in the step S01 for 2min, pouring the polycaprolactone solution into a polytetrafluoroethylene mold, putting the mold into an oven, and drying to obtain the porous polycaprolactone.
And (3) quick shape recovery:
at the temperature of 10-60 ℃, applying acting force to the porous polycaprolactone for shaping to obtain a temporary shape;
then the porous polycaprolactone with temporary shape is immersed in ethyl acetate solvent, and the original shape is recovered for 1s, and the recovery temperature is 10-60 ℃.
Example 2:
s01, dissolving polycaprolactone in N, N-dimethylformamide, and magnetically stirring at 45 ℃ until the solution is transparent to obtain a polycaprolactone solution with the mass concentration of 30%;
s02, standing the polycaprolactone solution obtained in the step S01 for 2min, pouring the polycaprolactone solution into a polytetrafluoroethylene mold, putting the mold into an oven, and drying to obtain the porous polycaprolactone.
And (3) quick shape recovery:
at the temperature of 10-60 ℃, applying acting force to the porous polycaprolactone for shaping to obtain temporary properties;
then the porous polycaprolactone with temporary shape is immersed in ethyl acetate solvent, and the original shape is recovered for 1s, and the recovery temperature is 10-60 ℃.
Example 3:
s01, dissolving polycaprolactone in N, N-dimethylformamide, and magnetically stirring at 35 ℃ until the solution is transparent to obtain a polycaprolactone solution with the mass concentration of 5%;
s02, standing the polycaprolactone solution obtained in the step S01 for 2min, pouring the polycaprolactone solution into a polytetrafluoroethylene mold, putting the mold into an oven, and drying to obtain the porous polycaprolactone. And (3) quick shape recovery:
at the temperature of 10-60 ℃, applying acting force to the porous polycaprolactone for shaping to obtain temporary properties;
then the porous polycaprolactone with temporary shape is immersed in ethyl acetate solvent, and the original shape is recovered for 1s, and the recovery temperature is 10-60 ℃.
Example 4
A response method of fast recovery solvent type porous shape memory polycaprolactone is a solution casting method and comprises the following steps:
s01, dissolving polycaprolactone in N, N-dimethylformamide, and stirring at 20 ℃ until the solution is transparent, namely completely dissolving to obtain a polycaprolactone solution with the mass concentration of 5%;
s02, pouring the polycaprolactone solution obtained in the step S01 into a polytetrafluoroethylene mold, then putting the mold into an oven, and drying to obtain the porous polycaprolactone.
And (3) quick shape recovery:
and (3) at the temperature of 10 ℃, applying an acting force on the porous polycaprolactone obtained in the S02 for shaping to obtain the porous polycaprolactone with a temporary shape.
When the temperature is 10 ℃, when the porous polycaprolactone in the temporary shape is immersed in the ethyl acetate solvent, the solvent and the polycaprolactone act to quickly generate wrinkles, and the porous polycaprolactone is restored to the initial shape within 0.9 s.
Example 5
A response method of fast recovery solvent type porous shape memory polycaprolactone is a solution casting method and comprises the following steps:
s01, dissolving polycaprolactone in N, N-dimethylformamide, and stirring at 50 ℃ until the solution is transparent, namely completely dissolving to obtain a polycaprolactone solution with the mass concentration of 20%;
s02, pouring the polycaprolactone solution obtained in the step S01 into a polytetrafluoroethylene mold, then putting the mold into an oven, and drying to obtain the porous polycaprolactone.
And (3) quick shape recovery:
and (3) at the temperature of 40 ℃, applying an acting force on the porous polycaprolactone obtained in the S02 for shaping to obtain the porous polycaprolactone with a temporary shape.
When the temperature is 50 ℃, when the porous polycaprolactone in the temporary shape is immersed in the ethyl acetate solvent, the solvent and the polycaprolactone act to quickly generate wrinkles, and the porous polycaprolactone is restored to the initial shape within 0.6 s.
Example 6
A response method of fast recovery solvent type porous shape memory polycaprolactone is a solution casting method and comprises the following steps:
s01, dissolving polycaprolactone in N, N-dimethylformamide, and stirring at 60 ℃ until the solution is transparent, namely completely dissolving to obtain a polycaprolactone solution with the mass concentration of 30%;
s02, pouring the polycaprolactone solution obtained in the step S01 into a polytetrafluoroethylene mold, then putting the mold into an oven, and drying to obtain the porous polycaprolactone.
And (3) quick shape recovery:
and (3) at the temperature of 60 ℃, applying an acting force on the porous polycaprolactone obtained in the step S02 to shape, so as to obtain the porous polycaprolactone with a temporary shape.
When the temperature is 60 ℃, when the porous polycaprolactone in the temporary shape is immersed in the ethyl acetate solvent, the solvent and the polycaprolactone act to quickly generate wrinkles, and the porous polycaprolactone is recovered to the initial shape within 1 s.
A fast recovery solvent pore-forming porous shape memory polycaprolactone, polycaprolactone molecular chains form a sheet structure in N, N-dimethylformamide solution, and the sheet structures are mutually connected to form a porous structure, so that porous polycaprolactone is obtained; after the porous polycaprolactone is shaped, the porous polycaprolactone is immersed in an ethyl acetate solvent, and the initial shape of the porous polycaprolactone is recovered within 0-1 s. The solvent driving the reversion is not limited to ethyl acetate and comprises other organic solvents with similar chemical structures.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (6)
1. A response method of fast recovery solvent type porous shape memory polycaprolactone is characterized by comprising the following steps:
s01, dissolving polycaprolactone in N, N-dimethylformamide, and stirring until the polycaprolactone is completely dissolved to obtain a polycaprolactone solution;
s02, pouring the polycaprolactone solution obtained in the step S01 into a mold, then putting the mold into an oven, and drying to obtain porous polycaprolactone;
s03, applying acting force to the porous polycaprolactone obtained in the S02 for shaping to obtain porous polycaprolactone in a temporary shape;
s04, when the porous polycaprolactone in the temporary shape is immersed in ethyl acetate, the solvent and the micro-nano polycaprolactone sheet structure act to quickly generate wrinkles, so that the porous polycaprolactone returns to the original shape.
2. The method of claim 1 wherein the rapid recovery solvent-borne porous shape memory polycaprolactone is prepared by a reaction of: in the S01, when the polycaprolactone is dissolved in the N, N-dimethylformamide, the polycaprolactone is stirred at the temperature of 20-60 ℃ until the solution is transparent.
3. The method of claim 1 wherein the rapid recovery solvent-borne porous shape memory polycaprolactone is prepared by a reaction of: in the S01, the mass concentration of the polycaprolactone solution is 5-30%.
4. The method of claim 1 wherein the rapid recovery solvent-borne porous shape memory polycaprolactone is prepared by a reaction of: the range of the shaping temperature is 10-60 ℃.
5. The method of claim 1 wherein the rapid recovery solvent-borne porous shape memory polycaprolactone is prepared by a reaction of: the recovery time is 0-1 s.
6. The method of claim 1 wherein the rapid recovery solvent-borne porous shape memory polycaprolactone is prepared by a reaction of: the recovery temperature is 10-60 ℃.
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