CN101240116B - Biodegradable macromolecule composite material with shape memory function and its preparation method and use - Google Patents
Biodegradable macromolecule composite material with shape memory function and its preparation method and use Download PDFInfo
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- CN101240116B CN101240116B CN2008100453754A CN200810045375A CN101240116B CN 101240116 B CN101240116 B CN 101240116B CN 2008100453754 A CN2008100453754 A CN 2008100453754A CN 200810045375 A CN200810045375 A CN 200810045375A CN 101240116 B CN101240116 B CN 101240116B
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Abstract
The invention relates to a biodegradable polymer composite material having shape memory function, comprising a biodegradable polymer material, which is characterized in that the molecular weight of the biodegradable polymer material is 20000 to 1500000, 1 to 20 parts of nano-scopic or micron-sized organic conductive particles and /or inorganic magnetic particles are added in the 100 parts by weight of the polymer, wherein, the organic conductive particles is one of polypyrrole, polyaniline, poly3,4-dioxane ethyl thiophene or the mixture of them, the inorganic magnetic particles is one of ferroferric oxide and ferric oxide magnetic particles or the mixture of them. The mechanical property and mechanical property of the materials, with good elasticity modulus, well elasticity, high shape recovery rate, easy shape memory and changing operation and fast shape recovery speed.
Description
Technical field
The present invention relates to a kind of polymer composite and its production and use with shape memory function.
Background technology
Shape-memory material is a kind of intelligent material, its shape memory characteristic shows as energy perception external stimulus (as temperature, power, electromagnetism, pH value, solvent etc.), and respond this variation, to its state parameter (as shape, position, strain etc.) adjust, preestablish state thereby be returned to it.
Divide from material category, shape-memory material can be divided into shape memory alloy, shape memory ceramics, shape-memory polymer and composite material of shape memory.In recent years, along with developing rapidly of life science and medical science, human health to self is growing interest also, in early days the shape memory alloy as body implant shows some human body non-safeties gradually, except that biocompatibility, influence and the restriction human pathology of alloy material detects and can not adapt to as the deformation temperature of shape-memory material the problem such as clinical adjustment; Prior problem is the tissue necrosis that metal does not match and causes owing to biomechanical property in human body; Because the metal inertia requires implantation instrument to retrieve, and certainly will increase medical treatment cost and patient suffering.Therefore, medical circle has proposed new requirement to for example this class shape-memory material of implantation instrument, and Here it is: good biocompatibility, biomechanical property and human body coupling does not need many-sided requirements such as second operation and deformation temperature be adjustable.Not ccontaining doubting, in the existing shape-memory material, biodegradable shape memory macromolecule material and mixture thereof are optimal selections.
Because biodegradable shape memory macromolecule Character of Shape Memorizing, it can implant with the form that tightens, volume is little, by heating, makes it be returned to the shape of the comparatively large vol that needs voluntarily in human body, can reduce wound like this, alleviate patient's misery.And Biodegradable polymer material with shape memory, behind the implant into body, need not perform the operation once more in operation, it can be decomposed into small molecules voluntarily, get rid of externally with normal metabolic, better biocompatibility and biological safety are arranged than biostable polymers; This Character of Shape Memorizing can be shaped to required shape arbitrarily in surgical procedure, can play the effect that simplifies the operation, but also the operation that makes some ordinary methods be difficult to finish can be carried out easily.Its application has alleviated patient's the misery and the expense of operative treatment greatly, also can reduce loaded down with trivial details surgical procedure and doctor's operating pressure simultaneously.
Existing research with Biodegradable polymer material of shape memory, a kind of biodegradable polymkeric substance with shape memory function such as US Patent6281262.2001 report is used for purposes such as bondage blood vessel, sutures.Chinese patent 200410043386.0,200410010734.4,200610017025.8,200410013749.6,200610020481.8 also reported some researchs of relevant degradable macromolecule as shape-memory material, but they have the following disadvantages:
1, the polymer materials that has the physical crosslinking structure, externally under the stress, the easy relatively sliding of its inner molecule segment causes the mechanical properties decrease of material.
2, can only carry out operation inconvenience in shape memory and the recovery operation by heat conducting direct heating mode.
3, especially shape resume speed and restorer and mechanical mechanics are not high for shape-memory properties, and are difficult to guarantee simultaneously.
Summary of the invention
First purpose of the present invention provides a kind of Biodegradable macromolecule composite material with shape memory function, and the machinery of this kind material and mechanical property are good, the Young's modulus height, good springiness, the shape recovery ratio height, shape memory and change are easy and simple to handle, and the shape resume speed is fast.
The present invention realizes its goal of the invention, and the technical scheme that is adopted is: a kind of Biodegradable macromolecule composite material with shape memory function comprises the inorganic particulate of degradable macromolecular material and biologically active.Wherein the molecular weight of degradable macromolecular material is 20000-1500000; The nanometer or micron-sized organic conductive particle and/or the inorganic magnetic conduction particle that also comprise 1%-20% in the matrix material; Organic conductive particle wherein is: polypyrrole, polyaniline, poly-3, and the mixture of one or more of 4-dioxoethyl thiophene, inorganic magnetic conduction particle is: the mixture of one or more of Z 250, ferric oxide magnetic particle.
Compared with prior art, the invention has the beneficial effects as follows:
In degradable macromolecular material, form composite high-molecular material by adding micron order or nano level organic conductive particle or inorganic particulate, micron order or nano level organic filler and inorganic particulate have strengthened the intensity of polymer composite, its machinery and mechanical property have been improved, its Young's modulus height, good springiness, the shape recovery ratio height.The Young's modulus that experiment showed, matrix material of the present invention is not add more than the twice of macromolecular material Young's modulus of the same race of particle.Polypyrrole, polyaniline, poly-3,4-dioxoethyl thiophene organic conductive particle has excellent electric susceptibility; Z 250, the inorganic magnetic conduction particle of ferric oxide have good magnetic responsiveness, therefore can make conduction, the heating of magnetic conduction particle by the method that adds electromagnetic field, thereby make macromolecular material be warming up to deformation temperature, implement change of shape, than the direct heat conduction heating, operation control is convenient, and it is more even to be heated, the thermal conversion efficiency height, change of shape and resume speed are fast.And, can also improve the biocompatibility of matrix material owing to magnetic conduction particle Z 250, ferric oxide are the very strong inorganicss of biological activity.Can also regulate the degradation rate and the pattern of matrix material by the addition of controlling organic and inorganic particle.
Second purpose of the present invention provides a kind of method for preparing above biodegradable polymer composite, and the concrete practice of this kind method is:
A, dispersion are dissolved in its organic solvent with degradable macromolecular material; Nanometer or micron-sized conduction organic filler and/or magnetic conduction inorganic particulate join in its dispersion agent ultrasonic wave or dispersed with stirring; Macromolecule material solution and dispersion system are mixed, and ultrasonic once more or dispersed with stirring after the sealing gets mixing solutions.
B, stirring and the air-dry mixing solutions that a is gone on foot open wide, and magnetic agitation 10-300 minute, natural air drying obtained the emulsus settling.
C, drying are carried out vacuum-drying to not conforming to organic solvent, promptly to the emulsus settling.
Compared with prior art, the beneficial effect of the inventive method is: the micron, nano level organic and inorganic particle under liquid phase state by ultrasonic dispersing and magnetic agitation, organic filler can twine with polymeric matrix equably well and combine on the one hand, organic and inorganic on the other hand particle can be filled in the hole of polymeric matrix equably, and produces good combination.Thereby the mechanical mechanics property that makes thing is good, good springiness.Shape memory and resume speed are fast.Preparation process only has dissolving, dispersion of particles and dry three steps of macromolecular material, and preparation method's adaptability is strong, and technology is simple, safety, and required equipment is few, and expense is low.Do not add nondegradable material in the preparation process, biological safety is good.
The organic solvent in above-mentioned a step is the organic solvent behind the drying and dehydrating, and adds 1～5 part of peroxide cross-linking agent or azo compound linking agent in mixing solutions; After the drying treatment in c step, will make thing again and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, be incubated 1-120 minute, make macromolecular material carry out crosslinking reaction.
Make the shape-memory material of composite inner produce crosslinked more like this, extent of polymerization is higher, further improve polymer shape memory performance, raising and improve chemical stability, thermostability, the mechanical property of thermoplasticity shape-memory polymer, widen the range of application of shape-memory material.
Above-mentioned peroxide cross-linking agent is specially: benzoyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, peroxidation 3,3, the 5-tri-methyl hexanoic acid tert-butyl ester, 3, a kind of in two (t-butyl peroxy) ethyl butyrates of 3-, the peroxidation acetic acid tert-pentyl ester; The azo compound linking agent is specially: Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).They are the small molecules linking agent of sophisticated degradable high polymer material, dependable performance, and consumption is few, and metabolism is fallen in vivo, has good security.
The 3rd purpose of the present invention provides a kind of above-mentioned purposes with Biodegradable macromolecule composite material of shape memory function, and its purposes is to go up the immobilising device that uses as medical treatment, and its detailed directions is:
The formation of A, original shape is put into the mould of the original shape of design in advance with the matrix material grind into powder that makes; Compression molding is medical immobilising device in extrusion press.
The fixing medical immobilising device with original shape of B, deformation and deformation places magnetic field or applies alternating-current, make the heating of magnetic particle or conducting particles, the medical treatment immobilising device is warming up to and exceeds its second-order transition temperature, but exceeds value≤30 ℃, makes it soften and apply and be deformed into the secondary shape; Immediately it is moved to and be lower than frozen material stress in 4 ℃ of environment, fix its shape.
When C, shape are recovered to recover, with the medical immobilising device of secondary shape, add electromagnetic field once more and make the heating of magnetic particle or conducting particles, be warming up to and exceed its second-order transition temperature, be lower than 30 ℃ but exceed value, medical immobilising device recovers and the maintenance original shape.
Like this, when matrix material of the present invention in use needs to heat, for the matrix material that has added inorganic magnetic conduction particle, can be placed in the magnetic field, the heating that utilizes magnetic particle magnetic domain in alternating magnetic field to change and cause, thus make macromolecule compound material heating produce first deformation or deformation recovery; And for the matrix material that has added organic conductive particles such as polypyrrole, polyaniline, then can make the conducting particles heating, promptly utilize polypyrrole, polyaniline, poly-3 by applying alternating-current, the heating that the conduction of 4-dioxoethyl thiophene causes reaches and heats up and the purpose of enforcement deformation or recovery.Certainly, material of the present invention in use also can adopt existing thermal conduction type of heating to heat, and is about to physiological saline, deionized water, hot gas flow, nontoxic oil bath enforcement heating that material places heating.
This electricity, magnetic heating means are than the direct heat conduction heating, and the doctor operates that control is convenient, accurate, and it is more even to be heated, the thermal conversion efficiency height, and change of shape and resume speed are fast, can alleviate patient's misery.Matrix material of the present invention can be widely used as the various fixed device of medical field, as: shrink memory nail, the outer shape retaining plate of bone, vessel support frame, cancer treatment heat release pin, cell conductive pin etc. in the bone.
The present invention is further detailed explanation below in conjunction with embodiment.
Embodiment
Embodiment one
The preparation of poly(lactic acid)/polyaniline composite material:
With 100 parts of heavy molecular weight is that 140000 poly(lactic acid) adds in the organic solvent-acetone, sealing, magnetic agitation dissolving; With the nano level layer/polyaniline conductive particulate material of 4 parts of weights, join the dispersion agent of polyaniline: in the N-Methyl pyrrolidone simultaneously.After treating that polyaniline dissolves fully, ultra-sonic dispersion 30 minutes.Above two kinds of solution are under agitation mixed, sealing, ultrasonic dispersing 30 minutes are opened wide solution at last again, magnetic agitation 200 minutes, and natural air drying is to obtaining the emulsus settling; Again the emulsus settling is carried out vacuum-drying and remove residual organic solvent, obtain poly(lactic acid)/polyaniline composite material.
Purposes with Biodegradable macromolecule composite material of shape memory function.
The formation of original shape: with poly(lactic acid)/polyaniline composite material grind into powder that above step makes, put into the mould of the specific original shape of design in advance, in extrusion press, be warmed up to 105 ℃, keep mold pressing 10～15MPa, time 5 minutes again; Take out at last, obtain the poly(lactic acid)/polyaniline composite material of original shape.
Fixing of deformation and deformation: the poly(lactic acid)/polyaniline composite material device that processes is added the alternating-current of 12-36V, the layer/polyaniline conductive heating, be raised to 65 ℃-70 ℃ until device temperature, (value that exceeds 56 ℃ of its second-order transition temperatures is 9 ℃-14 ℃) kept 3 minutes, the matrix material device of original shape softened and implements to be deformed into the secondary shape of a more convenient operation.At once it is moved to frozen material stress in 0 ℃ of environment, fixed deformation shape then.
Shape is recovered: when needing to recover, the matrix material device taking-up with the secondary shape applies same alternating-current, is heated to 65 ℃-70 ℃, and material is returned to original shape again rapidly.
Embodiment two
This example and embodiment one are basic identical, different only be: the conducting particles of adding is the micron order polypyrrole thing of 1 part of weight.
Embodiment three
This example is basic identical with embodiment one, and different is: the conducting particles of adding is that 20 parts of heavy micron orders gather 3,4-dioxoethyl thiophene thing.
Embodiment four
This example is basic identical with embodiment one, and different is: the conducting particles of adding is nano level 7 parts and meets again 3,4-dioxoethyl thiophene and 7 parts of reunion pyrroles' mixture.
Embodiment five
This example and embodiment one are basic identical, and different is: the conducting particles of adding is nano level 5 parts heavy poly-3, the mixture of the polyaniline of 4-dioxoethyl thiophene, 5 parts of heavy polypyrroles, 5 parts of weights.
Embodiment six
The preparation of poly(lactic acid)/ferriferrous oxide composite material.
With 100 parts of heavy molecular weight is that 20000 poly(lactic acid) adds in the organic solvent-acetone, sealing, magnetic agitation dissolving; Simultaneously the micron-sized Z 250 magnetic conduction particle of 20 parts of weights is joined and carry out ultra-sonic dispersion in its dispersion agent-dehydrated alcohol.Again above two kinds of solution are under agitation mixed, sealing, ultrasonic dispersing 30 minutes, at last solution is opened wide, magnetic agitation 300 minutes, natural air drying is to forming the emulsus settling, again the emulsus settling is carried out vacuum-drying and remove residual organic solvent, obtain poly(lactic acid)/ferriferrous oxide composite material.
The purposes of poly(lactic acid)/ferriferrous oxide composite material.
Poly(lactic acid)/ferriferrous oxide composite material the grind into powder of the formation of A, original shape after with complete drying put into the mould of design shape in advance; In extrusion press, be warmed up to 105 ℃, keep mold pressing 10-15MPa, time 5 minutes again; Take out at last, obtain poly(lactic acid)/ferriferrous oxide composite material medical treatment immobilising device.
The fixing of B, deformation and deformation put into the alternating magnetic field environment with the poly(lactic acid)/polyaniline composite material medical treatment immobilising device that processes, the heating of Z 250 particle, thereby make medical immobilising device be warmed up to 65-70 ℃ (value that exceeds 56 ℃ of its second-order transition temperatures is 9 ℃-14 ℃), kept 3 minutes, remollescent medical treatment immobilising device is deformed into the secondary shape of a more convenient implementation and operation, at once it is moved to 4 ℃ of environment frozen material stress, fixedly the secondary shape of medical device then.
When C, shape recover to need to recover, with the medical device of secondary shape, insert in the identical alternating magnetic field environment of B step and be heated to 65-70 ℃, medical immobilising device is replied rapidly again and is kept original shape.
Embodiment seven
This example is basic identical with embodiment six, and different is: the magnetic conduction particle of adding is the nano level ferric oxide material of 2 parts of weights.
Embodiment eight
This example and embodiment six are basic identical, and different is: the magnetic conduction particle of adding is the mixture of the nano level Z 250 of 5 parts heavy nano level ferric oxide and 5 parts of weights.
Embodiment nine
The preparation of crosslinked polycaprolactone/hydroxyapatite/ferriferrous oxide composite material.
100 parts heavy degradable polycaprolactones, 2.5 parts heavy benzoyl peroxide linking agent and the nano-grade hydroxy apatite particle (hydroxyapatite is the material of biologically active) of 5 parts of weights are dissolved with the trichloromethane that anhydrates respectively, disperse, stir.Benzoyl peroxide solution is as the dispersion agent of ferriferrous oxide nano powder, with the Z 250 adding wherein formation Z 250 dispersion system of 1 part of weight simultaneously.With Z 250 dispersion system and polycaprolactone solution and three kinds of solution mixing of hydroxyapatite solution, sealing, ultrasonic dispersing 10 minutes, even again to system, make mixing solutions.At last mixing solutions is opened wide, magnetic agitation 10 minutes, natural air drying is to producing the emulsus settling; Again the emulsus settling is carried out vacuum-drying and remove residual organic solvent, obtain containing the polycaprolactone/hydroxyapatite/ferriferrous oxide composite material of linking agent benzoyl peroxide.Dried matrix material is carried out the radical crosslinking reaction in warm-up mill, temperature of reaction is 130 ℃, and the reaction times is 10 minutes, obtains crosslinked polycaprolactone/hydroxyapatite/ferriferrous oxide composite material.
The purposes of crosslinked polycaprolactone/hydroxyapatite/ferriferrous oxide composite material is as medical device, and its detailed directions is:
The formation of original shape:, put into the mould of the original shape of design in advance with the matrix material grind into powder that makes; Compression molding is medical immobilising device in extrusion press.The processing parameter of its compression molding is: 70 ℃ of temperature, mold pressing 10～15MPa, time 5 minutes.
Fixing of deformation and deformation: it is 1-40KA.m that the medical immobilising device that will process is put into magneticstrength
-1, alternative frequency 100-3000Hz alternating magnetic field in, be warmed up to 23 ℃ (exceeding its second-order transition temperature is 30 ℃ for-6 ℃ value), kept 2 minutes, remollescent medical treatment immobilising device is deformed into the secondary shape of a more convenient operation, at once it is moved to-18 ℃ of environment then, frozen material stress, fixedly secondary shape.
Shape is recovered: when needing to recover, the device of this secondary shape taken out put into alternating magnetic field, be heated in 25 ℃ the environment, material is returned to initial shape again rapidly.
Embodiment ten:
This example is basic identical with embodiment nine, and different is: change hydroxyapatite into conduction organic filler polyaniline, making thing is crosslinked polycaprolactone/polyaniline/ferriferrous oxide composite material
This example makes the usage of the purposes of thing can be identical with embodiment nine.Also can adopt following usage: the crosslinked polycaprolactone that will process/polyaniline composite material medical treatment immobilising device applies the 12-36V alternating-current, by because layer/polyaniline conductive heating, thereby heat medical immobilising device to 25 ℃ more than the second-order transition temperature, kept 2 minutes, remollescent medical treatment immobilising device is deformed into the shape of a more convenient operation, at once it is moved to-18 ℃ of environment frozen material stress then, the fixed deformation shape, at last same conduction environment is put in this deformed shape taking-up and be heated to 25 ℃, material is returned to initial shape again rapidly.
Embodiment 11
This example is basic identical with embodiment nine, and different is: macromolecular material is the polyglycolic acid of 100 parts of weights, and molecular weight is 80000, and the weight of hydroxyapatite is 10 parts.The linking agent that adds is the dicumyl peroxide of 0.5 part of weight, and in the C drying treatment in step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 1 minute, makes macromolecular material carry out crosslinking reaction.
Embodiment 12
This example is basic identical with embodiment nine, and different is: macromolecular material is 100 parts of weights, and molecular weight is 1500000 poly(lactic acid).The linking agent that adds is the peroxidized t-butyl perbenzoate of 5 parts of weights, and in the C drying treatment in step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 120 minutes, makes macromolecular material carry out crosslinking reaction.
Embodiment 13
This example is basic identical with embodiment nine, and different is: macromolecular material is the poly(lactic acid) of 100 parts of weights and the multipolymer of polyglycolic acid, and molecular weight is 120000.The linking agent that adds is 1.5 parts of heavy peroxidation 3,3, the 5-tri-methyl hexanoic acid tert-butyl ester.And in the drying treatment in C step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 110 minutes, makes macromolecular material carry out crosslinking reaction.
Embodiment 14
This example is basic identical with embodiment nine, and different is: macromolecular material is the polylactic acid-polyglycol multipolymer of 100 parts of weights, and molecular weight is 200000.The linking agent that adds be 3.5 parts heavy 3, two (t-butyl peroxy) ethyl butyrates of 3-.And in the drying treatment in C step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 60 minutes, makes macromolecular material carry out crosslinking reaction.
Embodiment 15
This example is basic identical with embodiment nine, and different is: macromolecular material is 100 parts heavy poly-ε one caprolactone and the multipolymer of poly(lactic acid), and molecular weight is 600000.The linking agent that adds is the peroxidation acetic acid tert-pentyl ester of 4 parts of weights.And in the drying treatment in C step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 5 minutes, makes macromolecular material carry out crosslinking reaction.
Embodiment 16
This example is basic identical with embodiment nine, and different is: macromolecular material is 100 parts heavy poly-ε one caprolactone and the multipolymer of polyoxyethylene glycol, and molecular weight is 1200000.The linking agent that adds be 2 parts heavy 3, two (t-butyl peroxy) ethyl butyrates of 3-.And in the drying treatment in C step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 3 minutes, makes macromolecular material carry out crosslinking reaction.
Embodiment 17
This example is basic identical with embodiment nine, and different is: macromolecular material is the polydioxanone of 100 parts of weights, and molecular weight is 1000000.The linking agent that adds is 1 part of heavy peroxidation 3,3, the 5-tri-methyl hexanoic acid tert-butyl ester.And in the drying treatment in C step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 10 minutes, makes macromolecular material carry out crosslinking reaction.
Embodiment 18
This example is basic identical with embodiment nine, and different is: macromolecular material is 100 parts heavy, poly-ε one caprolactone, and molecular weight is 50000.The linking agent that adds is the azo compound linking agent Diisopropyl azodicarboxylate of 4 parts of weights.And in the drying treatment in C step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 115 minutes, makes macromolecular material carry out crosslinking reaction.
Embodiment 19
This example is basic identical with embodiment nine, and different is: macromolecular material is the polycarbonate of 100 parts of weights, and molecular weight is 90000.The linking agent that adds is the azo compound linking agent 2,2'-Azobis(2,4-dimethylvaleronitrile) of 0.1 part of weight.And in the drying treatment in C step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 90 minutes, makes macromolecular material carry out crosslinking reaction.
Embodiment 20
This example is basic identical with embodiment nine, and different is: macromolecular material is the poly-acid anhydrides of 100 parts of weights, and molecular weight is 110000.The linking agent that adds be 2 parts heavy 3, two (t-butyl peroxy) ethyl butyrates of 3-.And in the drying treatment in C step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 50 minutes, makes macromolecular material carry out crosslinking reaction.
Embodiment 21
This example and embodiment nine are basic identical, and different is: macromolecular material is the mixture of the polymeric amide of 50 parts heavy poly-acid anhydrides and 50 parts of weights, and molecular-weight average is 110000.The linking agent that adds is the dicumyl peroxide of 1 part of weight.And in the drying treatment in C step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 15 minutes, makes macromolecular material carry out crosslinking reaction.
Embodiment 22
This example is basic identical with embodiment nine, and different is: macromolecular material is the multipolymer of the polylactic acid-polyglycolic acid of 40 parts of heavy poly(lactic acid), 30 parts of heavy polyglycolic acids, 30 parts of weights, and molecular-weight average is 140000.The linking agent that adds is the benzoyl peroxide of 3 parts of weights.And in the drying treatment in C step, will make thing and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, soaking time is 25 minutes, makes macromolecular material carry out crosslinking reaction.
The matrix material that obvious the present invention makes when using as medical immobilising device, also can adopt existing thermal conduction type of heating to heat, and is about to physiological saline, deionized water, hot gas flow, nontoxic oil bath enforcement heating that material places heating.
Multipolymer, polydioxanone, poly-ε one caprolactone, the polycarbonate of the multipolymer of poly(lactic acid), polyglycolic acid, poly(lactic acid) and the polyglycolic acid of biodegradable polymer in can be above embodiment that the present invention uses, polylactic acid-polyglycol multipolymer, poly-ε one caprolactone and poly(lactic acid) or polyoxyethylene glycol, gathering the mixture on a kind of or a kind of in acid anhydrides, the polymeric amide, can also be other biodegradable polymer.
Matrix material of the present invention when using as medical immobilising device, in the fixation procedure of deformation and deformation, the alternating-current that is applied except that the alternating-current that can be 12-36V, can also be higher than 36V as 220, the alternating-current of 380V.And in shape recovery process, heat, owing to be to heat on human body, the voltage that then applies can not surpass 36V.In deformation fixedly the time, its solid shape of matrix material that various macromolecular materials are formed, the temperature of frozen strss only otherwise be higher than 4 ℃ all can, temperature is low more, its set time is short more.And also can be higher than 4 ℃ to its solid shape of matrix material of some macromolecular material composition, the temperature of frozen strss.
Claims (5)
1. the Biodegradable macromolecule composite material with shape memory function comprises degradable macromolecular material, it is characterized in that: the molecular weight of described degradable macromolecular material is 2000-1500000; And in the macromolecular material of 100 parts of weight, be added with nanometer or the micron-sized organic conductive particle and/or the inorganic magnetic conduction particle of 1-20 part, also be added with the nano-grade hydroxy apatite particle; Organic conductive particle wherein is: polypyrrole, polyaniline, poly-3, and the mixture of one or more of 4-dioxoethyl thiophene, inorganic magnetic conduction particle is: the mixture of one or more of Z 250, ferric oxide magnetic particle.
2. one kind prepares the described method with Biodegradable macromolecule composite material of shape memory function of claim 1, and its concrete practice is:
A, dispersion are dissolved in its organic solvent with degradable macromolecular material; Nanometer or micron-sized conduction organic filler and/or magnetic conduction inorganic particulate and nano-grade hydroxy apatite particle join in its dispersion agent ultrasonic wave or dispersed with stirring; Macromolecule material solution and dispersion system are mixed, and ultrasonic once more or dispersed with stirring after the sealing gets mixing solutions;
B, stirring and the air-dry mixing solutions that a is gone on foot open wide, and magnetic agitation 10-300 minute, natural air drying obtained the emulsus settling;
C, drying are carried out vacuum-drying to not containing organic solvent, promptly to the emulsus settling.
3. a kind of preparation according to claim 2 has the method for the Biodegradable macromolecule composite material of shape memory function, it is characterized in that:
The organic solvent in described a step is the organic solvent behind the drying and dehydrating, and adds 0.5～5 part of peroxide cross-linking agent or azo compound linking agent in mixing solutions; After the drying treatment in c step, will make thing again and place vacuum drying oven or warm-up mill, be warmed up to make the thing fusing after, be incubated 1-120 minute, make macromolecular material carry out crosslinking reaction.
4. a kind of preparation according to claim 3 has the method for the Biodegradable macromolecule composite material of shape memory function, it is characterized in that:
Described peroxide cross-linking agent is specially: benzoyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, peroxidation 3,3, the 5-tri-methyl hexanoic acid tert-butyl ester, 3, a kind of in two (t-butyl peroxy) ethyl butyrates of 3-, the peroxidation acetic acid tert-pentyl ester; The azo compound linking agent is specially: Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
5. the purposes with Biodegradable macromolecule composite material of shape memory function as claimed in claim 1 is as medical immobilising device, and its detailed directions is:
The formation of A, original shape is put into the mould of the original shape of design in advance with the matrix material grind into powder that makes; Compression molding is medical immobilising device in extrusion press;
The fixing medical immobilising device with original shape of B, deformation and deformation places magnetic field or applies alternating-current, make the heating of magnetic particle or conducting particles, the medical treatment immobilising device is warming up to and exceeds its second-order transition temperature, but exceeds value≤30 ℃, makes it soften and apply and be deformed into the secondary shape; Immediately it is moved to and be lower than frozen material stress in 4 ℃ of environment, fix its shape;
When C, shape are recovered to recover, with the medical immobilising device of secondary shape, add electromagnetic field once more and make the heating of magnetic particle or conducting particles, be warming up to and exceed its second-order transition temperature, be lower than 30 ℃ but exceed value, medical immobilising device recovers and the maintenance original shape.
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| CN101402737B (en) * | 2008-11-19 | 2011-01-12 | 武汉理工大学 | Degradable conductive biological medical polymer material |
| CN102371006B (en) * | 2010-08-17 | 2014-08-20 | 上海微创医疗器械（集团）有限公司 | Biodegradable scaffold |
| CN102764168A (en) * | 2011-05-03 | 2012-11-07 | 上海理工大学 | Elastic shape memory recyclable bracket and manufacturing method and using method thereof |
| EP2832381B1 (en) | 2012-03-28 | 2019-08-28 | Toray Industries, Inc. | Biodegradable material and method for producing biodegradable material |
| CN104185480B (en) * | 2012-03-28 | 2016-04-20 | 东丽株式会社 | The manufacture method of Biodegradable material and Biodegradable material |
| CN105944144A (en) * | 2016-04-29 | 2016-09-21 | 哈尔滨工业大学 | Bone tissue repair material based on shape memory composite material as well as preparation method and application method of bone tissue repair structure |
| CN106633721A (en) * | 2016-11-18 | 2017-05-10 | 中国科学院深圳先进技术研究院 | Self-repair material and article with shape memory effect and preparation method thereof |
| CN106601338B (en) * | 2016-11-18 | 2018-11-23 | 深圳先进技术研究院 | A kind of flexible electrode and preparation method thereof with functionalization |
| CN108066826A (en) * | 2017-12-22 | 2018-05-25 | 西南交通大学 | A kind of wireless electric current self-powered moves composite fibre and its application in implantable neural electrical stimulator |
| CN110194834B (en) * | 2019-05-07 | 2020-07-10 | 西南交通大学 | Visual photoinduced shape memory polymer and preparation method thereof |
| CN114618014A (en) * | 2020-12-11 | 2022-06-14 | 深圳先进技术研究院 | Bone repair scaffold and preparation method thereof |
| CN113072723B (en) * | 2021-03-31 | 2022-11-18 | 上海大学 | Shape memory material film and preparation method thereof |
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