CN107286363A - A kind of Quick-return solvent-borne type porous shape memory polycaprolactone and preparation method thereof - Google Patents
A kind of Quick-return solvent-borne type porous shape memory polycaprolactone and preparation method thereof Download PDFInfo
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- CN107286363A CN107286363A CN201710618394.0A CN201710618394A CN107286363A CN 107286363 A CN107286363 A CN 107286363A CN 201710618394 A CN201710618394 A CN 201710618394A CN 107286363 A CN107286363 A CN 107286363A
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2207/00—Foams characterised by their intended use
- C08J2207/10—Medical applications, e.g. biocompatible scaffolds
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- 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
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Abstract
The invention discloses a kind of Quick-return solvent-borne type porous shape memory polycaprolactone and preparation method thereof, the porous polycaprolactone has the shape memory function of Quick-return in 1s；Preparation method uses solution casting method, the N of polycaprolactone, N dimethyl formamide solutions, with the slow volatilization of solvent, and polycaprolactone strand can form the micro/nano level laminated structure of interconnection, and then form porous polycaprolactone.The SME of the porous polycaprolactone material, can be to its figuration, and it is in the organic solvent of immersion room temperature（Ethyl acetate）When middle, can in 1s Quick-return.This is due to that organic solvent can quickly enter loose structure and the polycaprolactone laminated structure of micro/nano level is acted, and forms fold, and rapid release makes the residual stress that polycaprolactone is produced when deforming, sample is replied original shape rapidly.This method preparation technology is simple, with low cost, and does not introduce other impurities.
Description
Technical field
The invention belongs to novel high polymer material technical field, more particularly to a kind of Quick-return solvent-borne type porous shape note
Recall polycaprolactone and preparation method thereof.
Background technology
Shape-memory polymer is a kind of intellectual material of stimuli responsive type, the energy with " remembeing " itself original shape
Power.Shape-memory polymer is had become after the another hot research after marmem because of its unique shape memory function
Field.Compared with marmem, there is shape-memory polymer low light weight, production cost, easy processing, performance to be easy to adjust
Control, can recovery strain be big, reply the advantages of response temperature range is wide；Response is replied in addition, can be produced to a variety of stimulation modes（Such as
Heat, light, PH, solvent and electromagnetism etc.）Although the solvent response type shape memory high molecule studied at present works as shape memory high score
When son is in the yardstick of micro/nano level, it is possible to achieve reply deformation faster, but bulk material generally existing is replied when responding
Between it is long the problem of（Generally hour level）.
Polycaprolactone is widely used in biological doctor because it has good biocompatibility and biodegradability
Treatment field.General at present is using polycaprolactone and other materials such as chitosan, tricalcium phosphate, hydroxyapatite, keratin mostly
After mixing, many methods using freeze-drying, which prepare loose structure, is used for orthopaedics support.
The content of the invention
The invention provides a kind of Quick-return solvent-borne type porous shape memory polycaprolactone and preparation method thereof, to solve
Prior art（Such as it is freeze-dried）, drill process is complicated, cost is high, low production efficiency and it is whard to control the problem of.In addition,
Solvent response type shape memory high molecule material, migration rate of the solvent in material is depended on during shape is replied, is made
Response time into material is long, it usually needs a few houres, or even tens hours could reply, and this limit shape significantly remembers material
The application of material.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of Quick-return solvent-borne type porous shape remembers the preparation method of polycaprolactone, it is characterised in that the preparation method
For solution casting method, comprise the following steps：
S01, polycaprolactone is dissolved in DMF, stirs to being completely dissolved, obtain polycaprolactone solution；
S02, the polycaprolactone solution that S01 is obtained poured into mould, mould is then put into baking oven, drying obtains porous gathering oneself
Lactone.
Further, in the S01, when polycaprolactone is dissolved in DMF, stirred at 20-60 DEG C to molten
The transparent shape of liquid.
Further, in the S01, the mass concentration of polycaprolactone is 5-30%.
Further, the porous polycaprolactone obtained in the S02 applies active force and carries out figuration, obtains temporary shapes
Porous polycaprolactone.
Further, the figuration temperature range is 10-60 DEG C.
Further, when in temporary shapes porous polycaprolactone immersion ethyl acetate solvent in, solvent with it is micro-nano
Level polycaprolactone laminated structure is acted, and fold is produced rapidly, porous polycaprolactone is replied its original shape.
Further, the turnaround time is 0-1s（Do not include 1s）.
Further, the recovery temperature is 10-60 DEG C.
A kind of Quick-return solvent-borne type porous shape remembers polycaprolactone, and polycaprolactone strand is in N, N- dimethyl formyls
Micro/nano level laminated structure is formed in amine aqueous solution, and these micro/nano level laminated structures are interconnected to form loose structure, obtain
Porous polycaprolactone.
Further, immersed after the porous polycaprolactone figuration in ethyl acetate solvent, porous polycaprolactone is in 0-1s
Time in reply its original shape.
Compared with prior art, the present invention has advantages below：
The invention provides the preparation method that a kind of Quick-return solvent-borne type porous shape remembers polycaprolactone；The porous shape is remembered
Recall polycaprolactone and gauffer effect is produced under solvent action, realize that porous shape remembers the quick recovery of shape of polycaprolactone（Can
Soon to 1 second）；
The present invention combines pore structure, the biocompatibility of polycaprolactone, biodegradability and shape-memory properties, makes
Still there is higher mechanical strength for the porous shape memory polycaprolactone gone out, its answering in bioengineered tissue field has been expanded
With.
Brief description of the drawings
Fig. 1 is that porous shape memory polycaprolactone prepared by the present invention is micro- by liquid nitrogen frozen disconnected cross-sectional scanning electron of quenching
Mirror picture；
Fig. 2 is that the optics of the surface topography before and after porous shape memory polycaprolactone surface drop ethyl acetate prepared by the present invention shows
Micro mirror picture；
Fig. 3 is the recovery of shape photo that porous shape prepared by the solvent driving present invention remembers polycaprolactone；
Fig. 4 is the mechanical property picture that porous shape prepared by the present invention remembers polycaprolactone.
Embodiment
The present invention is further described with reference to embodiment.
Embodiment 1
A kind of Quick-return solvent-borne type porous shape remembers the preparation method of polycaprolactone, follows the steps below：
S01, polycaprolactone is dissolved in DMF, magnetic agitation is obtained to the transparent shape of solution at 50 DEG C
Mass concentration is 20% polycaprolactone solution；
After S02, the polycaprolactone solution left standstill 2min for obtaining S01, pour into Teflon mould, be then put into mould
Baking oven, after drying, you can obtain porous polycaprolactone.
Shape Quick-return：
Temperature applies active force at 10-60 DEG C, to porous polycaprolactone and carries out figuration, obtains temporary shapes；
The porous polycaprolactone with temporary shapes is immersed in ethyl acetate solvent afterwards, 1s is returned to original shape, returned
Rewarming degree is 10-60 DEG C.
Embodiment 2：
S01, polycaprolactone is dissolved in at DMF, 45 DEG C magnetic agitation is to the transparent shape of solution, obtained matter
Measure the polycaprolactone solution that concentration is 30%；
Pour into Teflon mould, be then put into mould after S02, the polycaprolactone solution left standstill 2min for obtaining S01
Baking oven, after drying, you can obtain porous polycaprolactone.
Shape Quick-return：
Temperature applies active force at 10-60 DEG C, to porous polycaprolactone and carries out figuration, obtains interim character；
The porous polycaprolactone with temporary shapes is immersed in ethyl acetate solvent afterwards, 1s is returned to original shape, returned
Rewarming degree is 10-60 DEG C.
Embodiment 3：
S01, polycaprolactone is dissolved in DMF, magnetic agitation is obtained to the transparent shape of solution at 35 DEG C
Mass concentration is 5% polycaprolactone solution；
Pour into Teflon mould, be then put into mould after S02, the polycaprolactone solution left standstill 2min for obtaining S01
Baking oven, after drying, you can obtain porous polycaprolactone.
Shape Quick-return：
Temperature applies active force at 10-60 DEG C, to porous polycaprolactone and carries out figuration, obtains interim character；
The porous polycaprolactone with temporary shapes is immersed in ethyl acetate solvent afterwards, 1s is returned to original shape, returned
Rewarming degree is 10-60 DEG C.
Embodiment 4
A kind of Quick-return solvent pore porous shape remembers the preparation method of polycaprolactone, and the preparation method is that solution is poured
Casting, comprises the following steps：
S01, polycaprolactone is dissolved in DMF, stirred at 20 DEG C to the transparent shape of solution, i.e., it is completely molten
Solution, obtains mass concentration for 5% polycaprolactone solution；
S02, the polycaprolactone solution that S01 is obtained poured into Teflon mould, mould is then put into baking oven, dried
To porous polycaprolactone.
Shape Quick-return：
Temperature is at 10 DEG C, and the porous polycaprolactone obtained in the S02 applies active force and carries out figuration, obtains temporary shapes
Porous polycaprolactone.
Temperature be 10 DEG C when, when in temporary shapes porous polycaprolactone immersion ethyl acetate solvent in, solvent with
Polycaprolactone is acted on, and fold is produced rapidly, 0.9s makes porous polycaprolactone reply its original shape.
Embodiment 5
A kind of Quick-return solvent pore porous shape remembers the preparation method of polycaprolactone, and the preparation method is that solution is poured
Casting, comprises the following steps：
S01, polycaprolactone is dissolved in DMF, stirred at 50 DEG C to the transparent shape of solution, i.e., it is completely molten
Solution, obtains mass concentration for 20% polycaprolactone solution；
S02, the polycaprolactone solution that S01 is obtained poured into Teflon mould, mould is then put into baking oven, dried
To porous polycaprolactone.
Shape Quick-return：
Temperature is at 40 DEG C, and the porous polycaprolactone obtained in the S02 applies active force and carries out figuration, obtains temporary shapes
Porous polycaprolactone.
Temperature be 50 DEG C when, when in temporary shapes porous polycaprolactone immersion ethyl acetate solvent in, solvent with
Polycaprolactone is acted on, and fold is produced rapidly, 0.6s makes porous polycaprolactone reply its original shape.
Embodiment 6
A kind of Quick-return solvent pore porous shape remembers the preparation method of polycaprolactone, and the preparation method is that solution is poured
Casting, comprises the following steps：
S01, polycaprolactone is dissolved in DMF, stirred at 60 DEG C to the transparent shape of solution, i.e., it is completely molten
Solution, obtains mass concentration for 30% polycaprolactone solution；
S02, the polycaprolactone solution that S01 is obtained poured into Teflon mould, mould is then put into baking oven, dried
To porous polycaprolactone.
Shape Quick-return：
Temperature is at 60 DEG C, and the porous polycaprolactone obtained in the S02 applies active force and carries out figuration, obtains temporary shapes
Porous polycaprolactone.
Temperature be 60 DEG C when, when in temporary shapes porous polycaprolactone immersion ethyl acetate solvent in, solvent with
Polycaprolactone is acted on, and produce makes porous polycaprolactone reply its original shape rapidly within fold, 1s.
A kind of Quick-return solvent pore porous shape remembers polycaprolactone, and polycaprolactone strand is in N, N- dimethyl methyls
Laminated structure is formed in amide solution, laminated structure is interconnected to form loose structure, obtain porous polycaprolactone；It is described porous
Immersed after polycaprolactone figuration in ethyl acetate solvent, porous polycaprolactone replys its original shape within 0-1s time.Drive
The dynamic solvent replied is not limited to ethyl acetate, the organic solvent comprising other with similar chemical constitution.
Described above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of Quick-return solvent-borne type porous shape remembers the preparation method of polycaprolactone, it is characterised in that the preparation side
Method is solution casting method, is comprised the following steps：
S01, polycaprolactone is dissolved in DMF, stirs to being completely dissolved, obtain polycaprolactone solution；
S02, the polycaprolactone solution that S01 is obtained poured into mould, mould is then put into baking oven, drying obtains porous gathering oneself
Lactone.
2. Quick-return solvent-borne type porous shape according to claim 1 remembers the preparation method of polycaprolactone, its feature
It is：In the S01, when polycaprolactone is dissolved in DMF, stirred at 20-60 DEG C to the transparent shape of solution.
3. Quick-return solvent-borne type porous shape according to claim 1 remembers the preparation method of polycaprolactone, its feature
It is：In the S01, the mass concentration of polycaprolactone is 5-30%.
4. Quick-return solvent-borne type porous shape according to claim 1 remembers the preparation method of polycaprolactone, its feature
It is：The porous polycaprolactone obtained in the S02 applies active force and carries out figuration, obtains the porous of temporary shapes and gathers in oneself
Ester.
5. Quick-return solvent-borne type porous shape according to claim 4 remembers the preparation method of polycaprolactone, its feature
It is：The figuration temperature range is 10-60 DEG C.
6. Quick-return solvent-borne type porous shape according to claim 4 remembers the preparation method of polycaprolactone, its feature
It is：When in the porous polycaprolactone immersion solvent in temporary shapes, solvent is produced with micro/nano level polycaprolactone laminated structure
Raw effect, produces rapidly fold, porous polycaprolactone is replied its original shape.
7. Quick-return solvent-borne type porous shape according to claim 6 remembers the preparation method of polycaprolactone, its feature
It is：The turnaround time is 0-1s.
8. Quick-return solvent-borne type porous shape according to claim 6 remembers the preparation method of polycaprolactone, its feature
It is：The recovery temperature is 10-60 DEG C.
9. a kind of Quick-return solvent-borne type porous shape remembers polycaprolactone, it is characterised in that：Polycaprolactone strand is in N, N-
In dimethyl formamide solution formed micro/nano level laminated structure, and these micro/nano level laminated structures be interconnected to form it is porous
Structure, obtains porous polycaprolactone.
10. Quick-return solvent-borne type porous shape according to claim 9 remembers polycaprolactone, it is characterised in that：It is described
Immersed after porous polycaprolactone figuration in solvent, porous polycaprolactone replys its original shape within 0-1s time.
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| CN201710618394.0A CN107286363B (en) | 2017-07-26 | 2017-07-26 | Response method for rapidly recovering solvent type porous shape memory polycaprolactone |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921038A (en) * | 2012-08-06 | 2013-02-13 | 西南交通大学 | Method for preparing porous scaffold with shape memory function |
| US9603970B2 (en) * | 2014-07-11 | 2017-03-28 | Bronislava G. Belenkaya | Biodegradable shape-memory material and method |
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2017
- 2017-07-26 CN CN201710618394.0A patent/CN107286363B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921038A (en) * | 2012-08-06 | 2013-02-13 | 西南交通大学 | Method for preparing porous scaffold with shape memory function |
| US9603970B2 (en) * | 2014-07-11 | 2017-03-28 | Bronislava G. Belenkaya | Biodegradable shape-memory material and method |
Non-Patent Citations (3)
| Title |
|---|
| JORGE MA´S ESTELLE´S ET AL.: ""Physical characterization of polycaprolactone scaffolds"", 《J MATER SCI: MATER MED》 * |
| TONGFEI WU ET AL.,: ""Preparation and characterization of poly(ε-caprolactone)/Na+-MMT nanocomposites"", 《APPLIED CLAY SCIENCE》 * |
| 吕海宝: ""电驱动与溶液驱动形状记忆聚合物混合体系及其本构方程"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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