CN113402758A - Degradable shape memory medical splint and processing technology thereof - Google Patents
Degradable shape memory medical splint and processing technology thereof Download PDFInfo
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- CN113402758A CN113402758A CN202110672458.1A CN202110672458A CN113402758A CN 113402758 A CN113402758 A CN 113402758A CN 202110672458 A CN202110672458 A CN 202110672458A CN 113402758 A CN113402758 A CN 113402758A
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices; Anti-rape devices
- A61F5/01—Orthopaedic devices, e.g. splints, casts or braces
- A61F5/04—Devices for stretching or reducing fractured limbs; Devices for distractions; Splints
- A61F5/05—Devices for stretching or reducing fractured limbs; Devices for distractions; Splints for immobilising
- A61F5/058—Splints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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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- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses a degradable shape memory medical splint and a processing technology thereof, wherein the splint comprises a substrate and chitosan-curcumin loaded on the surface of the substrate, comb-shaped polycaprolactone is creatively adopted as a main material, the number of arms of the polycaprolactone is 20, and the shape stability and the shape recovery rate of the material are more excellent; according to the method, dihydroxyl diperoxydiiodate nickel potassium is used as an initiator, chitosan nanoparticles with hydrophobic cores and hydrophilic surfaces are synthesized by a free radical polymerization method, curcumin is loaded on the chitosan nanoparticles, a chitosan-curcumin suspension is prepared and deposited on the surface of a substrate, and a drug-loaded layer is formed; the splint prepared by the method has excellent shape stability and shape recovery rate, has excellent antibacterial performance, can effectively inhibit inflammation, bacterial infection and other conditions in actual use, and has high practicability.
Description
Technical Field
The invention relates to the technical field of medical splints, in particular to a degradable shape memory medical splint and a processing technology thereof.
Background
The shape memory polymer material is an intelligent material which can accept the change of peripheral conditions and respond to peripheral stimulation so as to automatically return to the pre-designed form, because the shape memory polymer material has unique characteristics and shows potential in application, the attention degree is gradually improved while the shape memory polymer material goes into the sight of researchers, and the most common polycaprolactone is widely applied as the shape memory polymer.
Before the research on shape memory polymer materials is started, the medical treatment outer part 3 is generally fixed externally by gypsum and other materials, but the materials have the defects of high density, air impermeability, high moisture tendency, high possibility of breakage, poor antibacterial property, incapability of secondary forming and the like, and are gradually replaced by the shape memory polymer materials, and the orthopedic external fixation polycaprolactone plate becomes the traditional medical fixation splint, but the situations of poor antibacterial property, low splint recovery rate, poor shape memory stability and the like still exist, so that the practical application is inconvenient.
Aiming at the situation, a degradable shape memory medical splint and a processing technology thereof are disclosed to solve the technical problem.
Disclosure of Invention
The invention aims to provide a degradable shape memory medical splint and a processing technology thereof, which aim to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a processing technology of a degradable shape memory medical splint comprises the following steps:
(1) mixing graphene oxide and tetrahydrofuran, stirring, performing ultrasonic oscillation, adding dehydrated L-lactic acid and stannous octoate, vacuumizing, heating to 150-;
(2) adding vinyl acetate and an initiator into chitosan and deionized water in a nitrogen environment, stirring and reacting in a water bath at 38-45 ℃, cooling, dialyzing to remove impurities, and freeze-drying to obtain chitosan nanoparticles;
mixing curcumin and ethanol, and stirring to obtain a material A; uniformly mixing chitosan nanoparticles and deionized water, adding the material A, and performing ultrasonic oscillation to obtain a chitosan-curcumin suspension;
(3) mixing and stirring polylactic acid, polycaprolactone and modified graphene oxide, adding a silane coupling agent and a filler, performing melt extrusion, performing calendaring molding to obtain a plate, uniformly punching holes on the plate, washing with deionized water, and performing vacuum drying to obtain a substrate;
(4) taking a substrate, placing the substrate in a DBD plasma reactor, carrying out surface plasma treatment on the upper surface of the substrate, taking out the substrate after plasma treatment, placing the substrate in chitosan-curcumin suspension, carrying out heat preservation treatment for 1-1.5h under the condition of water bath at 45-50 ℃, washing with deionized water, drying, and cutting into required size and shape to obtain the medical splint.
The optimized scheme comprises the following steps:
(1) mixing graphene oxide and tetrahydrofuran, stirring for 10-20min, ultrasonically oscillating for 1-1.2h, adding dehydrated L-lactic acid and stannous octoate, vacuumizing, heating to 150-;
(2) adding vinyl acetate and an initiator into chitosan and deionized water in a nitrogen environment, stirring and reacting in a water bath at 38-45 ℃ for 3-4h, cooling, dialyzing to remove impurities, and freeze-drying to obtain chitosan nanoparticles;
mixing curcumin and ethanol, and stirring for 20-30min to obtain material A; uniformly mixing chitosan nanoparticles and deionized water, adding the material A, and ultrasonically oscillating for 30-40min to obtain chitosan-curcumin suspension;
(3) mixing and stirring polylactic acid, polycaprolactone and modified graphene oxide for 10-20min, adding a silane coupling agent and a filler, performing melt extrusion, performing calendaring molding to obtain a plate, uniformly punching holes on the plate, washing with deionized water, and performing vacuum drying to obtain a substrate;
(4) taking a substrate, placing the substrate in a DBD plasma reactor, carrying out surface plasma treatment on the upper surface of the substrate, taking out the substrate after plasma treatment, placing the substrate in chitosan-curcumin suspension, carrying out heat preservation treatment for 1-1.5h under the condition of water bath at 45-50 ℃, washing with deionized water, drying, and cutting into required size and shape to obtain the medical splint.
In the optimized scheme, in the step (3), the aperture is 2-3 mm.
According to the optimized scheme, in the step (4), during plasma treatment, the treatment atmosphere is argon and oxygen mixed gas, the treatment time is 2-3min, and the treatment power is 3-4 KW.
In a more preferable embodiment, in the step (2), the initiator is dihydroxy dipersodic acid nickel potassium.
In the optimized scheme, in the step (3), the polycaprolactone is comb-shaped polycaprolactone, and the number of arms of the polycaprolactone is 20.
According to an optimized scheme, in the step (3), by mass, the components comprise 40-60 parts of polylactic acid, 50-80 parts of polycaprolactone, 10-12 parts of modified graphene oxide, 2-3 parts of a silane coupling agent and 10-15 parts of a filler.
In an optimized scheme, the filler is one or more of tourmaline, opal, rare earth salt and rare earth oxide.
According to an optimized scheme, the medical splint is prepared by the processing technology of the degradable shape memory medical splint.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a degradable shape memory medical splint and a processing technology thereof, wherein the medical splint comprises a substrate and chitosan-curcumin loaded on the surface of the substrate, the conventional medical splint adopts polycaprolactone as a main material, but the polycaprolactone is found to have the characteristics of high deformation degree, low transition temperature and the like in the using process, but the polycaprolactone still has low recovery speed, low recovery rate and poor shape memory stability, aiming at the problem, the comb-shaped polycaprolactone is creatively adopted as the main material, the number of arms of the polycaprolactone is 20, and the shape stability and the shape recovery rate of the material are more excellent.
On the basis, modified graphene oxide is prepared, polylactic acid grafted graphene oxide is prepared through reaction of graphene oxide, dehydrated L-lactic acid and stannous octoate, and polylactic acid is added into components of the splint to improve the plasticity and the degradability of the splint, so that the polylactic acid is grafted on the surface of the graphene, the compatibility between the components and other components of the splint can be improved, and the excellent mechanical property and the antibacterial property of the graphene can be utilized to improve the mechanical property and the antibacterial property of the splint, so that the actual using effect of the splint is improved;
and then, mixing and stirring polylactic acid, polycaprolactone and modified graphene oxide, adding a silane coupling agent and a filler, performing melt extrusion, calendering and molding to obtain a plate, uniformly punching holes on the plate to prepare a substrate, performing surface plasma treatment on the upper surface of the substrate, introducing active groups containing oxygen, nitrogen and the like on the surface of the substrate, improving the surface activity and roughness of the substrate, facilitating subsequent loading of chitosan-curcumin, and enabling the chitosan-curcumin to be uniformly deposited on the surface of the substrate.
According to the application, dihydroxyl diperoxydiiodate nickel potassium is used as an initiator, chitosan nanoparticles with a hydrophobic core and a hydrophilic surface are synthesized by a free radical polymerization method, curcumin is loaded on the chitosan nanoparticles, a chitosan-curcumin suspension is prepared and deposited on the surface of a substrate to form a drug-loaded layer, one side of the drug-loaded layer is in contact with a fracture part when the splint is actually used, and due to the existence of the chitosan and the curcumin, the curcumin has pharmacological activities of anti-inflammation, antibiosis and anti-infection, is low in toxicity and small in adverse reaction, can be used for performing anti-inflammation and antibacterial treatment on the fracture part, inhibiting the generation of inflammation, reducing the condition of bacterial infection, and is more excellent in actual use effect.
The application discloses medical splint of degradable shape memory and processing technology thereof, process design is reasonable, the component proportion adaptation, splint that the preparation obtained not only have excellent shape stability, shape recovery rate, and it has more excellent antibacterial property moreover, can effectively restrain the condition such as inflammation, bacterial infection when in actual use, have higher practicality.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a processing technology of a degradable shape memory medical splint comprises the following steps:
(1) mixing graphene oxide and tetrahydrofuran, stirring for 10min, ultrasonically oscillating for 1h, adding dehydrated L-lactic acid and stannous octoate, vacuumizing, heating to 150 ℃ for 5h, collecting reaction products, cleaning, and vacuum drying to obtain modified graphene oxide;
(2) adding vinyl acetate and an initiator into chitosan and deionized water in a nitrogen environment, stirring and reacting in a water bath at 38 ℃ for 4 hours, cooling, dialyzing to remove impurities, and freeze-drying to obtain chitosan nanoparticles; the initiator is dihydroxy diperoxodic acid nickel potassium;
mixing curcumin and ethanol, and stirring for 20min to obtain material A; uniformly mixing chitosan nanoparticles and deionized water, adding the material A, and performing ultrasonic oscillation for 30min to obtain a chitosan-curcumin suspension;
(3) mixing and stirring polylactic acid, polycaprolactone and modified graphene oxide for 10min, adding a silane coupling agent and a filler, performing melt extrusion, performing calendaring molding to obtain a plate, uniformly punching holes with the aperture of 2mm on the plate, washing with deionized water, and performing vacuum drying to obtain a substrate; the polycaprolactone is comb-shaped polycaprolactone, and the number of arms of the polycaprolactone is 20;
(4) placing a substrate in a DBD plasma reactor, performing surface plasma treatment on the upper surface of the substrate, wherein in the plasma treatment, the treatment atmosphere is argon and oxygen mixed gas, the treatment time is 2min, the treatment power is 3KW, taking out the substrate after the plasma treatment, placing the substrate in chitosan-curcumin suspension, performing heat preservation treatment for 1.5h under the condition of water bath at 45 ℃, washing with deionized water, drying, and cutting into required size and shape to obtain the medical splint.
In the embodiment, the raw materials of the components comprise, by mass, 40 parts of polylactic acid, 50 parts of polycaprolactone, 10 parts of modified graphene oxide, 2 parts of a silane coupling agent and 10 parts of a filler.
The filler is tourmaline.
Example 2:
a processing technology of a degradable shape memory medical splint comprises the following steps:
(1) mixing graphene oxide and tetrahydrofuran, stirring for 15min, ultrasonically oscillating for 1.1h, adding dehydrated L-lactic acid and stannous octoate, vacuumizing, heating to 152 ℃ for reacting for 4.8h, collecting reaction products, cleaning, and vacuum drying to obtain modified graphene oxide;
(2) adding vinyl acetate and an initiator into chitosan and deionized water in a nitrogen environment, stirring and reacting in a water bath at 40 ℃ for 3.5h, cooling, dialyzing to remove impurities, and freeze-drying to obtain chitosan nanoparticles; the initiator is dihydroxy diperoxodic acid nickel potassium;
mixing curcumin and ethanol, and stirring for 25min to obtain material A; uniformly mixing chitosan nanoparticles and deionized water, adding the material A, and performing ultrasonic oscillation for 35min to obtain a chitosan-curcumin suspension;
(3) mixing and stirring polylactic acid, polycaprolactone and modified graphene oxide for 15min, adding a silane coupling agent and a filler, performing melt extrusion, performing calendaring molding to obtain a plate, uniformly punching holes with the aperture of 2mm on the plate, washing with deionized water, and performing vacuum drying to obtain a substrate; the polycaprolactone is comb-shaped polycaprolactone, and the number of arms of the polycaprolactone is 20;
(4) placing a substrate in a DBD plasma reactor, performing surface plasma treatment on the upper surface of the substrate, wherein in the plasma treatment, the treatment atmosphere is argon and oxygen mixed gas, the treatment time is 2min, the treatment power is 3KW, taking out the substrate after the plasma treatment, placing the substrate in chitosan-curcumin suspension, performing heat preservation treatment for 1.1h under the condition of water bath at 48 ℃, washing with deionized water, drying, and cutting into required size and shape to obtain the medical splint.
In the embodiment, the raw materials of the components comprise, by mass, 45 parts of polylactic acid, 60 parts of polycaprolactone, 11 parts of modified graphene oxide, 2.5 parts of a silane coupling agent and 12 parts of a filler.
The filler is opal.
Example 3:
a processing technology of a degradable shape memory medical splint comprises the following steps:
(1) mixing graphene oxide and tetrahydrofuran, stirring for 18min, ultrasonically oscillating for 1.1h, adding dehydrated L-lactic acid and stannous octoate, vacuumizing, heating to 153 ℃ for reacting for 4.8h, collecting reaction products, cleaning, and vacuum drying to obtain modified graphene oxide;
(2) adding vinyl acetate and an initiator into chitosan and deionized water in a nitrogen environment, stirring and reacting in a water bath at 42 ℃ for 3.5h, cooling, dialyzing to remove impurities, and freeze-drying to obtain chitosan nanoparticles; the initiator is dihydroxy diperoxodic acid nickel potassium;
mixing curcumin and ethanol, and stirring for 28min to obtain material A; uniformly mixing chitosan nanoparticles and deionized water, adding the material A, and performing ultrasonic oscillation for 36min to obtain a chitosan-curcumin suspension;
(3) mixing and stirring polylactic acid, polycaprolactone and modified graphene oxide for 18min, adding a silane coupling agent and a filler, performing melt extrusion, performing calendaring molding to obtain a plate, uniformly punching holes in the plate, wherein the hole diameter is 3mm, washing with deionized water, and performing vacuum drying to obtain a substrate; the polycaprolactone is comb-shaped polycaprolactone, and the number of arms of the polycaprolactone is 20;
(4) placing a substrate in a DBD plasma reactor, performing surface plasma treatment on the upper surface of the substrate, wherein in the plasma treatment, the treatment atmosphere is argon and oxygen mixed gas, the treatment time is 3min, the treatment power is 4KW, taking out the substrate after the plasma treatment, placing the substrate in chitosan-curcumin suspension, performing heat preservation treatment for 1.4h under the water bath condition of 49 ℃, washing with deionized water, drying, and cutting into required size and shape to obtain the medical splint.
In the embodiment, the raw materials of the components comprise, by mass, 55 parts of polylactic acid, 70 parts of polycaprolactone, 11 parts of modified graphene oxide, 2.8 parts of a silane coupling agent and 14 parts of a filler.
The filler is opal.
Example 4:
a processing technology of a degradable shape memory medical splint comprises the following steps:
(1) mixing graphene oxide and tetrahydrofuran, stirring for 20min, ultrasonically oscillating for 1.2h, adding dehydrated L-lactic acid and stannous octoate, vacuumizing, heating to 155 ℃ for reacting for 4.5h, collecting reaction products, cleaning, and vacuum drying to obtain modified graphene oxide;
(2) adding vinyl acetate and an initiator into chitosan and deionized water in a nitrogen environment, stirring and reacting in a water bath at 45 ℃ for 3 hours, cooling, dialyzing to remove impurities, and freeze-drying to obtain chitosan nanoparticles; the initiator is dihydroxy diperoxodic acid nickel potassium;
mixing curcumin and ethanol, and stirring for 30min to obtain material A; uniformly mixing chitosan nanoparticles and deionized water, adding the material A, and performing ultrasonic oscillation for 40min to obtain a chitosan-curcumin suspension;
(3) mixing and stirring polylactic acid, polycaprolactone and modified graphene oxide for 20min, adding a silane coupling agent and a filler, performing melt extrusion, performing calendaring molding to obtain a plate, uniformly punching holes in the plate, wherein the hole diameter is 3mm, washing with deionized water, and performing vacuum drying to obtain a substrate; the polycaprolactone is comb-shaped polycaprolactone, and the number of arms of the polycaprolactone is 20;
(4) placing a substrate in a DBD plasma reactor, performing surface plasma treatment on the upper surface of the substrate, wherein in the plasma treatment, the treatment atmosphere is argon and oxygen mixed gas, the treatment time is 3min, the treatment power is 4KW, taking out the substrate after the plasma treatment, placing the substrate in chitosan-curcumin suspension, performing heat preservation treatment for 1h under the condition of water bath at 50 ℃, washing with deionized water, drying, and cutting into required size and shape to obtain the medical splint.
In the embodiment, the raw materials of the components comprise, by mass, 60 parts of polylactic acid, 80 parts of polycaprolactone, 12 parts of modified graphene oxide, 3 parts of a silane coupling agent and 15 parts of a filler.
The filler is tourmaline.
Comparative example 1:
a processing technology of a degradable shape memory medical splint comprises the following steps:
(1) mixing graphene oxide and tetrahydrofuran, stirring for 15min, ultrasonically oscillating for 1.1h, adding dehydrated L-lactic acid and stannous octoate, vacuumizing, heating to 152 ℃ for reacting for 4.8h, collecting reaction products, cleaning, and vacuum drying to obtain modified graphene oxide;
(2) adding vinyl acetate and an initiator into chitosan and deionized water in a nitrogen environment, stirring and reacting in a water bath at 40 ℃ for 3.5h, cooling, dialyzing to remove impurities, and freeze-drying to obtain chitosan nanoparticles; the initiator is dihydroxy diperoxodic acid nickel potassium;
mixing curcumin and ethanol, and stirring for 25min to obtain material A; uniformly mixing chitosan nanoparticles and deionized water, adding the material A, and performing ultrasonic oscillation for 35min to obtain a chitosan-curcumin suspension;
(3) mixing and stirring polylactic acid, common polycaprolactone and modified graphene oxide for 15min, adding a silane coupling agent and a filler, performing melt extrusion, performing calendaring molding to obtain a plate, uniformly punching holes in the plate, wherein the hole diameter is 2mm, washing with deionized water, and performing vacuum drying to obtain a substrate;
(4) placing a substrate in a DBD plasma reactor, performing surface plasma treatment on the upper surface of the substrate, wherein in the plasma treatment, the treatment atmosphere is argon and oxygen mixed gas, the treatment time is 2min, the treatment power is 3KW, taking out the substrate after the plasma treatment, placing the substrate in chitosan-curcumin suspension, performing heat preservation treatment for 1.1h under the condition of water bath at 48 ℃, washing with deionized water, drying, and cutting into required size and shape to obtain the medical splint.
In the embodiment, the raw materials of the components comprise, by mass, 45 parts of polylactic acid, 60 parts of common polycaprolactone, 11 parts of modified graphene oxide, 2.5 parts of a silane coupling agent and 12 parts of a filler.
The filler is opal.
The comparative example 1 is improved on the basis of the example 2, the conventional polycaprolactone is selected in the comparative example 1, the comb-shaped polycaprolactone is not adopted, and other process parameters and component contents are consistent with those of the example 2.
Comparative example 2:
a processing technology of a degradable shape memory medical splint comprises the following steps:
(1) mixing graphene oxide and tetrahydrofuran, stirring for 15min, ultrasonically oscillating for 1.1h, adding dehydrated L-lactic acid and stannous octoate, vacuumizing, heating to 152 ℃ for reacting for 4.8h, collecting reaction products, cleaning, and vacuum drying to obtain modified graphene oxide;
(3) mixing and stirring polylactic acid, polycaprolactone and modified graphene oxide for 15min, adding a silane coupling agent and a filler, performing melt extrusion, performing calendaring molding to obtain a plate, uniformly punching holes with the aperture of 2mm on the plate, washing with deionized water, and performing vacuum drying to obtain a substrate; the polycaprolactone is comb-shaped polycaprolactone, and the number of arms of the polycaprolactone is 20;
(4) taking a substrate, placing the substrate in a DBD plasma reactor, carrying out surface plasma treatment on the upper surface of the substrate, wherein in the plasma treatment, the treatment atmosphere is argon and oxygen mixed gas, the treatment time is 2min, the treatment power is 3KW, taking out the substrate after the plasma treatment, washing with deionized water, drying, cutting into required size and shape after drying, and obtaining the medical splint.
In the embodiment, the raw materials of the components comprise, by mass, 45 parts of polylactic acid, 60 parts of polycaprolactone, 11 parts of modified graphene oxide, 2.5 parts of a silane coupling agent and 12 parts of a filler.
The filler is opal.
Comparative example 2 was modified based on example 2, in comparative example 2 no chitosan-curcumin was loaded, and the remaining process parameters and component content were consistent with example 2.
Detection experiment:
1. taking the splint samples prepared in the examples 1-4 and the comparative examples 1-2, and cutting the splint samples into strips with the sizes of 50mm multiplied by 10mm multiplied by 5 mm; the sample is arranged on a die, is placed in hot water for softening, is bent to the deformation position of 180 ℃, is bent into a U shape from a strip shape, is kept at a constant temperature for 8 minutes, is cooled to room temperature after being formed, rebounds, tests the rebounding angle A (the final deformation angle of the sample), and calculates the shape fixing rate; the shape fixation rate is A/180 multiplied by 100%;
then, the sample was again put into hot water, the shape of the sample was recovered, the recovery angle B (the final deformation angle of the sample) was measured, and the shape recovery rate was calculated. The shape recovery rate is (180-B)/180X 100%;
the above operation was repeated 6 times, and the shape recovery after 6 times was again tested to characterize the shape memory stability.
2. The antibacterial rate of the medical splints prepared in examples 1-4 and comparative examples 1-2 was tested by colony counting, and the test strain was Escherichia coli.
| Item | Shape fixation ratio% | Shape recovery Rate% | Shape recovery after 6 times% | The antibacterial rate% |
| Example 1 | 93.9％ | 97.4％ | 95.1％ | 99.6％ |
| Example 2 | 94.3％ | 97.8％ | 95.4％ | 99.8％ |
| Example 3 | 94.5 | 97.8％ | 95.5％ | 99.8％ |
| Example 4 | 94.1％ | 97.6％ | 95.3％ | 99.7％ |
| Comparative example 1 | 91.2％ | 94.3％ | / | 99.8％ |
| Comparative example 2 | 94.3％ | 97.7％ | / | 85.4％ |
And (4) conclusion: the application discloses medical splint of degradable shape memory and processing technology thereof, process design is reasonable, the component proportion adaptation, splint that the preparation obtained not only have excellent shape stability, shape recovery rate, and it has more excellent antibacterial property moreover, can effectively restrain the condition such as inflammation, bacterial infection when in actual use, have higher practicality.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A processing technology of a degradable shape memory medical splint is characterized in that: the method comprises the following steps:
(1) mixing graphene oxide and tetrahydrofuran, stirring, performing ultrasonic oscillation, adding dehydrated L-lactic acid and stannous octoate, vacuumizing, heating to 150-;
(2) adding vinyl acetate and an initiator into chitosan and deionized water in a nitrogen environment, stirring and reacting in a water bath at 38-45 ℃, cooling, dialyzing to remove impurities, and freeze-drying to obtain chitosan nanoparticles;
mixing curcumin and ethanol, and stirring to obtain a material A; uniformly mixing chitosan nanoparticles and deionized water, adding the material A, and performing ultrasonic oscillation to obtain a chitosan-curcumin suspension;
(3) mixing and stirring polylactic acid, polycaprolactone and modified graphene oxide, adding a silane coupling agent and a filler, performing melt extrusion, performing calendaring molding to obtain a plate, uniformly punching holes on the plate, washing with deionized water, and performing vacuum drying to obtain a substrate;
(4) taking a substrate, placing the substrate in a DBD plasma reactor, carrying out surface plasma treatment on the upper surface of the substrate, taking out the substrate after plasma treatment, placing the substrate in chitosan-curcumin suspension, carrying out heat preservation treatment for 1-1.5h under the condition of water bath at 45-50 ℃, washing with deionized water, drying, and cutting into required size and shape to obtain the medical splint.
2. The processing technology of the degradable medical shape memory splint according to claim 1, characterized in that: the method comprises the following steps:
(1) mixing graphene oxide and tetrahydrofuran, stirring for 10-20min, ultrasonically oscillating for 1-1.2h, adding dehydrated L-lactic acid and stannous octoate, vacuumizing, heating to 150-;
(2) adding vinyl acetate and an initiator into chitosan and deionized water in a nitrogen environment, stirring and reacting in a water bath at 38-45 ℃ for 3-4h, cooling, dialyzing to remove impurities, and freeze-drying to obtain chitosan nanoparticles;
mixing curcumin and ethanol, and stirring for 20-30min to obtain material A; uniformly mixing chitosan nanoparticles and deionized water, adding the material A, and ultrasonically oscillating for 30-40min to obtain chitosan-curcumin suspension;
(3) mixing and stirring polylactic acid, polycaprolactone and modified graphene oxide for 10-20min, adding a silane coupling agent and a filler, performing melt extrusion, performing calendaring molding to obtain a plate, uniformly punching holes on the plate, washing with deionized water, and performing vacuum drying to obtain a substrate;
(4) taking a substrate, placing the substrate in a DBD plasma reactor, carrying out surface plasma treatment on the upper surface of the substrate, taking out the substrate after plasma treatment, placing the substrate in chitosan-curcumin suspension, carrying out heat preservation treatment for 1-1.5h under the condition of water bath at 45-50 ℃, washing with deionized water, drying, and cutting into required size and shape to obtain the medical splint.
3. The processing technology of the degradable medical shape memory splint according to claim 2, characterized in that: in the step (3), the aperture is 2-3 mm.
4. The processing technology of the degradable medical shape memory splint according to claim 2, characterized in that: in the step (4), during plasma treatment, the treatment atmosphere is argon and oxygen mixed gas, the treatment time is 2-3min, and the treatment power is 3-4 KW.
5. The processing technology of the degradable medical shape memory splint according to claim 2, characterized in that: in the step (2), the initiator is dihydroxy dipersodic acid nickel potassium.
6. The processing technology of the degradable medical shape memory splint according to claim 2, characterized in that: in the step (3), the polycaprolactone is comb-shaped polycaprolactone, and the number of arms of the polycaprolactone is 20.
7. The processing technology of the degradable medical shape memory splint according to claim 2, characterized in that: in the step (3), the components comprise, by mass, 40-60 parts of polylactic acid, 50-80 parts of polycaprolactone, 10-12 parts of modified graphene oxide, 2-3 parts of a silane coupling agent and 10-15 parts of a filler.
8. The processing technology of the degradable medical shape memory splint according to claim 2, characterized in that: the filler is one or more of tourmaline, opal, rare earth salt and rare earth oxide.
9. The medical splint prepared by the processing technology of the degradable medical splint with shape memory according to any one of claims 1-8.
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