CN112625292B - Preparation method of degradable shape memory polymer medical splint - Google Patents
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
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Abstract
The invention provides a degradable shape memory polymer medical splint and a preparation method thereof. The medical splint material provided by the invention is prepared by mixing an aliphatic polyester material with a main chain lateral group containing double bond functional groups and a photoinitiator according to a certain proportion, melting, blending, extruding into sheets, molding, perforating and irradiating by ultraviolet. Compared with the polycaprolactone type medical splint used at present, the medical splint provided by the invention has higher strength and deformation recovery rate and smaller retraction force, so that the medical splint has better fixing effect and stronger comfort.
Description
Technical Field
The invention relates to the field of high polymer materials and medical instruments, in particular to a preparation method of a degradable shape memory high polymer medical splint.
Background
The shape memory polymer material is a kind of intelligent material, and refers to a material capable of sensing the stimulus of environmental change (such as temperature, light, electric field, magnetic field, etc.) and responding to the change, so as to adjust the mechanical parameters (such as shape, position, strain, etc.) until the material returns to the initial state. Thermotropic shape memory polymer material is the most common shape memory polymer material in the earliest development. Thermotropic shape memory polymer generally contains two-phase structure, including stationary phase and reversible phase, wherein the stationary phase provides the permanent form of the material, generally composed of cross-linked structure in the polymer; the reversible phase provides a temporary form of the material, and the material can reversibly generate hardening and softening transformation along with temperature change, and the transformation can be glass transition or melting transformation.
In order to avoid secondary injury after fracture or orthopedic surgery, patients need to be externally fixed clinically. Although the plaster splint has low price, the plaster splint has high density, poor air permeability, long curing time, complex operation, no secondary forming and poor X-ray permeability, is not beneficial to observing the postoperative recovery condition of a patient in time and brings inconvenience to treatment. The medical splint material widely used clinically at present is a cross-linked polycaprolactone material with a shape memory function, and can be softened at a lower temperature (55-65 ℃) due to a lower melting point (57 ℃) of polycaprolactone, and can be recrystallized and hardened to form after being cooled. The medical splint has the advantages of simple and convenient operation, is particularly suitable for fixing complicated parts such as the head, the neck and the like, and also has the advantages of repeated use, natural degradation after being discarded and the like. However, there are no reactive groups on the main chain of polycaprolactone, and the crosslinking and curing are usually performed by irradiation with high-energy electron beam or gamma ray, and the crosslinking and curing effect is achieved by generating active free radicals on the main chain of polycaprolactone (CN109608842A, CN 10169874B). On one hand, the high-energy rays can cause the main chain of polycaprolactone to break and degrade while crosslinking the polycaprolactone, so that the mechanical property of the material is reduced, and the fixing effect of the splint is influenced. On the other hand, the crosslinking mode is to randomly generate crosslinking sites on the main chain structure, so that the product performance has poor controllability and the repeatability among batches is poor.
The glass transition temperature of the poly (4-hydroxybutyrate) is-45 ℃, the melting point is 60 ℃, the poly (4-hydroxybutyrate) is similar to that of polycaprolactone, the poly (caprolactone) has good shape memory function after crosslinking, can be softened at a lower temperature (55-65 ℃), and is an ideal material for preparing degradable medical splints. In addition, as the ester bond density in the poly (4-hydroxybutyrate) main chain is higher than that of polycaprolactone, the medical splint theoretically has higher mechanical strength than that of polycaprolactone, and the medical splint obtained after crosslinking has higher strength and better fixing effect. However, poly (4-hydroxybutyrate) also suffers from the lack of reactive groups in the backbone.
In order to solve the problems, the invention provides a preparation method of a degradable shape memory polymer material and application of the degradable shape memory polymer material in the aspect of medical splints. The invention introduces crosslinkable double bond functional groups in the main chain structure of polycaprolactone or poly (4-hydroxybutyrate) through copolymerization, realizes double bond crosslinking through ultraviolet irradiation, obtains a degradable shape memory polymer material, and is used for preparing medical splints. Compared with the methods reported in the prior art, the method provided by the invention has the following advantages: 1) the polymer structure main chain contains reactive double bond functional groups, so that the polymer structure main chain can generate crosslinking reaction under the irradiation of ultraviolet light with lower energy, and the breakage of the main chain structure caused by the irradiation of high-energy rays is avoided; 2) the density of double bond functional groups on the main chain of the polymer can be regulated, so that the subsequent crosslinking density can be conveniently controlled, and the regulation and control on the strength, the deformation recovery rate and the shrinkage force of the material can be realized; 3) by controlling the composition and content of the comonomer in the polymer main chain, the thermal transition temperature of the obtained material can be regulated, and the regulation of material softening and molding can be realized in a larger temperature range (40-60 ℃).
Disclosure of Invention
The invention aims to provide a preparation method of a degradable shape memory polymer medical splint.
A preparation method of a degradable shape memory polymer medical splint comprises the following steps:
(1) uniformly mixing a polyester material with a main chain side group containing double-bond functional groups and a photoinitiator according to a certain proportion, heating the mixture in a double-screw extruder to a molten state, and extruding the mixture to form a sheet;
(2) the obtained sheet is punched according to the requirement, and then ultraviolet irradiation treatment is carried out.
In the preparation method, the chemical structure of the polyester with the main chain side group containing double bond functional groups is shown as the formula (I):
(I)
the method is characterized in that n and m are natural numbers which are more than or equal to 1, x, y and z are natural numbers which are more than or equal to 5, x/(x + y + z) is 0.01-0.2, y/(x + y + z) is 0-0.99, and z/(x + y + z) is 0-0.99.
According to an embodiment of the present invention, the polyester having a pendant backbone group with a double bond functional group has a structure of one of:
(II)(III)
(IV)(V)
(VI)
(VII)
wherein x and y are natural numbers of 5 or more.
In the above production process, the polyester of the formula (II) may be obtained by random copolymerization of α -methylene- γ -butyrolactone and γ -butyrolactone, the polyester of the formula (III) may be obtained by random copolymerization of α -methylene- γ -butyrolactone and ε -caprolactone, the polyester of the formula (IV) may be obtained by random copolymerization of α -methylene- ε -caprolactone and γ -butyrolactone, the polyester of the formula (V) may be obtained by random copolymerization of α -methylene- ε -caprolactone and ε -caprolactone, the polyester of the formula (VI) may be obtained by ternary random copolymerization of α -methylene- γ -butyrolactone, γ -butyrolactone and ε -caprolactone, the polyester of the formula (VII) may be obtained by random copolymerization of α -methylene- ε -caprolactone, the gamma-butyrolactone and the epsilon-caprolactone are subjected to ternary random copolymerization.
In the preparation method, the molecular weight of the polyester is preferably 30-300 kDa; the photoinitiator is at least one of methyl vinyl ketone, benzoin, 2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
In the preparation method, the weight fraction of the polyester material is 95-99.9 parts, and the weight fraction of the photoinitiator is 0.1-5 parts.
The melt blending temperature is 50-80 ℃, and the melt blending extrusion speed is 30-120 rpm.
The wavelength of the ultraviolet light is 200-400 nm, and the intensity of the ultraviolet light is 10-200W/cm 2 The irradiation time is 0.5-10 h.
Detailed Description
The following embodiments specifically describe the present invention, but the present invention is not limited to these embodiments. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Wherein the polyester with the side group of the main chain containing double bond functional group is synthesized by the method reported in references (Macromolecules 2020,53, 3380-28089; Macromolecules 2006,39, 2804-2807).
Example 1
96 parts by weight of a random copolyester (M) of alpha-methylene-gamma-butyrolactone and gamma-butyrolactone n 100kDa, wherein alpha-methylene-gamma-The mol fraction of butyrolactone is 2 mol%), 4 weight parts of methyl vinyl ketone are stirred in a high-speed stirrer for 10min and uniformly mixed, the mixture is added into a double-screw extruder to be melted and extruded at 80 ℃, the rotating speed is 50rpm, a plate with the thickness of 2mm is obtained by extrusion, and the plate is perforated, and the aperture is 2 mm. Irradiating with 254nm ultraviolet lamp for 10min at 30W/cm intensity 2 And obtaining the medical splint. The modulus of elasticity, the deformation recovery rate and the contraction force are shown in Table 1.
Example 2
98 parts by weight of a random copolyester (M) of alpha-methylene-gamma-butyrolactone and epsilon-caprolactone n 150kDa, wherein the mole fraction of the alpha-methylene-gamma-butyrolactone is 4mol percent), 2 parts by weight of azobisisobutyronitrile are stirred in a high-speed stirrer for 15min and uniformly mixed, the mixture is added into a double-screw extruder to be melted and extruded at 80 ℃ and the rotating speed is 80rpm, a plate with the thickness of 2mm is obtained by extrusion, and the plate is perforated and has the aperture of 2 mm. Irradiating with 365nm ultraviolet lamp for 20min at 40W/cm intensity 2 And obtaining the medical splint. The modulus of elasticity, the deformation recovery rate and the contraction force are shown in Table 1.
Example 3
99 parts by weight of a random copolyester of alpha-methylene-epsilon-caprolactone and epsilon-caprolactone (M) n The alpha-methylene-epsilon-caprolactone comprises 300kDa, wherein the mole fraction of alpha-methylene-epsilon-caprolactone is 1mol percent), 1 part by weight of di-tert-butyl peroxide is stirred in a high-speed stirrer for 10min and uniformly mixed, added into a double-screw extruder and melt-extruded at 80 ℃ at the rotating speed of 100rpm to obtain a plate with the thickness of 2mm, and the plate is punched with the aperture of 2 mm. Irradiating with 254nm ultraviolet lamp at 100W/cm intensity for 30min 2 And obtaining the medical splint. The modulus of elasticity, the deformation recovery rate and the contraction force are shown in Table 1.
Example 4
98 parts by weight of a random copolyester (M) of alpha-methylene-epsilon-caprolactone and gamma-butyrolactone n 200kDa, wherein the mole fraction of the alpha-methylene-epsilon-caprolactone is 5mol percent), 2 parts by weight of dibenzoyl peroxide are stirred in a high-speed stirrer for 20min and uniformly mixed, and then the mixture is added into a double-screw extruder to be melted and extruded at 80 ℃, the rotating speed is 100rpm and the extrusion is carried outAnd (5) obtaining a plate with the thickness of 2mm, and punching the plate with the aperture of 2 mm. Irradiating with 365nm ultraviolet lamp for 30min at 150W/cm intensity 2 And obtaining the medical splint. The modulus of elasticity, the deformation recovery rate and the contraction force are shown in Table 1.
Example 5
97 parts by weight of ternary random copolyester (M) of alpha-methylene-gamma-butyrolactone, gamma-butyrolactone and epsilon-caprolactone n 300kDa, wherein the mole fraction of alpha-methylene-gamma-butyrolactone is 3mol percent, the mole fraction of gamma-butyrolactone is 10mol percent), 3 parts by weight of dicumyl peroxide are stirred in a high-speed stirrer for 15min and uniformly mixed, added into a double-screw extruder and melted and extruded at 80 ℃, the rotating speed is 110rpm, a plate with the thickness of 2mm is obtained by extrusion, and the hole diameter is 2 mm. Irradiating with 254nm ultraviolet lamp at 160W/cm intensity for 30min 2 And obtaining the medical splint. The modulus of elasticity, the deformation recovery rate and the contraction force are shown in Table 1.
Example 6
98 parts by weight of ternary random copolyester (M) of alpha-methylene-epsilon-caprolactone, gamma-butyrolactone and epsilon-caprolactone n The molecular weight of the alpha-methylene-epsilon-caprolactone is 300kDa, the mol fraction of the alpha-methylene-epsilon-caprolactone is 2mol percent, the mol fraction of the gamma-butyrolactone is 5mol percent, 2 parts of tert-butyl peroxybenzoate is stirred in a high-speed stirrer for 20min and uniformly mixed, the obtained mixture is added into a double-screw extruder to be melted and extruded at 80 ℃, the rotating speed is 110rpm, a plate with the thickness of 2mm is obtained through extrusion, and the plate is punched, and the aperture is 2 mm. Irradiating with 254nm ultraviolet lamp at intensity of 180W/cm for 30min 2 And obtaining the medical splint. The modulus of elasticity, the deformation recovery rate and the contraction force are shown in Table 1.
Comparative example 1
Mixing polycaprolactone (M) n 100kDa) was added to a twin-screw extruder and melt extruded at 80 c, 50rpm, to give a 2mm thick sheet, which was perforated to a 2mm pore size. The medical splint was obtained by electron beam irradiation at a dose of 50 kGy. The modulus of elasticity, the deformation recovery rate and the contraction force are shown in Table 1.
TABLE 1 modulus of elasticity, deformation restoring force and contraction force of medical splint material
| Modulus of elasticity (MPa) | Percent recovery from deformation (%) | Contractile force (N) | |
| Comparative example 1 | 256±10 | 90±0.5 | 56±0.8 |
| Example 1 | 430±15 | 98±0.3 | 33±1.2 |
| Example 2 | 470±12 | 97±0.4 | 34±0.8 |
| Example 3 | 490±16 | 99±0.5 | 28±0.7 |
| Example 4 | 480±14 | 98±0.5 | 32±1.4 |
| Example 5 | 520±12 | 99.5±0.5 | 20±0.8 |
| Example 6 | 500±16 | 99±0.3 | 19±0.7 |
As can be seen from the above table, compared with the polycaprolactone type medical splint obtained by irradiation crosslinking of high-energy electron beams, the medical splint provided by the invention has the advantages that the elastic modulus and the deformation recovery rate are obviously improved, so that the medical splint has better fixing strength, and the secondary damage caused by bone dislocation due to splint deformation is avoided. In addition, compared with a polycaprolactone type medical splint, the contraction force of the medical splint provided by the invention is obviously reduced, and the comfort of a patient is enhanced.
Claims (5)
1. A preparation method of a degradable shape memory polymer medical splint comprises the following steps:
(1) uniformly mixing polyester with a main chain side group containing double bond functional groups and a photoinitiator according to a certain proportion, heating the mixture in a double-screw extruder to a molten state, and extruding the mixture to form a sheet;
(2) punching the obtained sheet according to requirements, and then carrying out ultraviolet irradiation treatment;
the polyester is at least one of a random copolymer of alpha-methylene-gamma-butyrolactone and gamma-butyrolactone, a random copolymer of alpha-methylene-gamma-butyrolactone and epsilon-caprolactone, a random copolymer of alpha-methylene-epsilon-caprolactone and gamma-butyrolactone, a random copolymer of alpha-methylene-epsilon-caprolactone and epsilon-caprolactone, a ternary random copolymer of alpha-methylene-gamma-butyrolactone, gamma-butyrolactone and epsilon-caprolactone, and a ternary random copolymer of alpha-methylene-epsilon-caprolactone, gamma-butyrolactone and epsilon-caprolactone;
the photoinitiator is at least one of methyl vinyl ketone, benzoin, 2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
2. The method of claim 1, wherein the weight fraction of the polyester with the pendant main chain group containing double bond functional group is 95 to 99.9 parts, and the weight fraction of the photoinitiator is 0.1 to 5 parts.
3. The method of claim 1, wherein the melt blending temperature is 50 to 80 ℃ and the melt blending extrusion speed is 30 to 120 rpm.
4. The method of claim 1, wherein the ultraviolet light has a wavelength of 200-400 nm and an intensity of 10-200W/cm 2 The irradiation time is 0.5-10 h.
5. A medical splint produced by the method according to any one of claims 1 to 4.
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