CN112608586B - Degradable shape memory medical splint and preparation method thereof - Google Patents
Degradable shape memory medical splint and preparation method thereof Download PDFInfo
- Publication number
- CN112608586B CN112608586B CN202011494416.5A CN202011494416A CN112608586B CN 112608586 B CN112608586 B CN 112608586B CN 202011494416 A CN202011494416 A CN 202011494416A CN 112608586 B CN112608586 B CN 112608586B
- Authority
- CN
- China
- Prior art keywords
- medical splint
- parts
- weight
- shape memory
- hydroxybutyrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
Abstract
The invention provides a degradable shape memory medical splint and a preparation method thereof. The medical splint material provided by the invention is prepared by melting, blending and extruding 95-99.9 parts by weight of poly (4-hydroxybutyrate) and 0.1-5 parts by weight of crosslinking aid into a sheet, and then punching and irradiating by ultraviolet. Compared with the polycaprolactone medical splint used at present, the medical splint provided by the invention has higher strength and deformation recovery rate and smaller retraction force, thereby having better fixing effect and stronger comfort.
Description
Technical Field
The invention relates to the field of medical apparatus and instruments, in particular to a degradable shape memory poly (4-hydroxybutyrate) medical splint and a preparation method thereof.
Background
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. Some shape memory polymer medical splinting materials developed in recent years based on trans-polyisoprene rubber and polyurethane have advanced greatly compared with gypsum splints, but they are not degradable after being discarded and are liable to cause environmental pollution (CN105771002A, CN107415374B, CN 108084394B). The main body of the medical high-molecular splint which is widely used clinically at present is a polycaprolactone material, has a low melting point (57 ℃), has a shape memory function after cross-linking, can be softened at a low temperature (55-65 ℃), can be re-hardened and shaped after being cooled to room temperature, is simple and convenient to operate, is particularly suitable for fixing complicated parts such as the head, the neck and the like, and has the advantages of repeated use, natural degradation after being discarded and the like. However, polycaprolactone has poor strength and large retraction deformation after crosslinking, so that it needs to be reinforced by blending with high-strength polymer materials such as polylactic acid, and usually needs to be added with components such as coupling agents and inorganic fillers to improve compatibility and mechanical properties (CN109608842A, CN102430156A, CN108659483A, CN10169874B, and CN 102387818B). However, the addition of high melting point polymers such as polylactic acid may affect the softening performance of the material at low temperature, and may complicate the preparation process of the material. In addition, high-energy electron beams or gamma rays are generally adopted for crosslinking and curing of the polycaprolactone medical splint, and the high-energy rays can cause the main chain of polycaprolactone to break and degrade, reduce the mechanical property of the material and influence the fixation effect of the splint.
In order to solve the problems, the invention provides a degradable shape memory poly (4-hydroxybutyrate) medical splint material and a preparation method thereof. Poly (4-hydroxybutyrate) is a latest generation medical polyhydroxyalkanoate material, has good biocompatibility and biodegradability, is approved by the Food and Drug Administration (FDA) at present, and can be used as a surgical suture and a hernia patch clinically. Poly (4-hydroxybutyrate) can be obtained by the ring-opening polymerization of gamma-butyrolactone. The gamma-butyrolactone is a bio-based monomer with wide source and low price, can be obtained from biomass raw materials, such as corn, wheat and other crops, and is a renewable raw material. The glass transition temperature of the poly (4-hydroxybutyrate) is-45 ℃, the melting point is 60 ℃, the poly (4-hydroxybutyrate) also has the shape memory function after crosslinking, can be softened at a lower temperature (55-65 ℃), and is an ideal material for preparing the degradable medical splint. In addition, the density of ester bonds in the main chain of the poly (4-hydroxybutyrate) is higher than that of polycaprolactone, so that the poly (4-hydroxybutyrate) has better mechanical strength than that of polycaprolactone theoretically, can be directly used as a medical splint after being crosslinked, and does not need to be reinforced and modified by other polymer materials.
Disclosure of Invention
The invention aims to provide a degradable shape memory poly (4-hydroxybutyrate) medical splint. The invention also aims to provide a preparation method of the medical splint. The medical splint provided by the invention has the advantages of excellent mechanical property, good biocompatibility, air permeability, comfortableness, good X-ray permeability, low price and the like, and the prepared medical splint can be used for medical purposes such as orthopedic operation fixation, auxiliary positioning during radiotherapy of tumor patients and the like.
In order to solve the defects of the prior art, the invention provides a degradable shape memory poly (4-hydroxybutyrate) medical splint material and a preparation method thereof. The technical scheme adopted by the invention is as follows:
a degradable shape memory poly (4-hydroxybutyrate) medical splint material comprises the following components in parts by weight:
95-99.9 parts of poly (4-hydroxybutyrate);
crosslinking assistant agent: 0.1-5 parts.
The invention also provides a preparation method of the medical splint material, which comprises the following steps:
(1) uniformly mixing 95-99.9 parts by weight of poly (4-hydroxybutyrate) and 0.1-5 parts by weight of crosslinking aid, heating in a double-screw extruder to a molten state, and extruding a sheet to form;
(2) the obtained sheet is punched according to the requirement, and then ultraviolet irradiation treatment is carried out.
The molecular weight of the poly (4-hydroxybutyrate) is preferably 50-300 kDa; the crosslinking assistant is a photoinitiator, preferably methyl vinyl ketone, 2-dimethoxy-2-phenylacetophenone, benzoin, azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
The melt blending temperature is 50-80 ℃, and the melt blending extrusion speed is 30-100 rpm.
The wavelength of the ultraviolet light is 200-400 nm, and the ultraviolet illumination intensity is 30-400W/cm2The 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 materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
95 parts by weight of poly (4-hydroxybutyrate) (M)n100kDa), stirring 5 parts by weight of methyl vinyl ketone in a high-speed stirrer for 10min, uniformly mixing, adding the mixture into a double-screw extruder, performing melt extrusion at the temperature of 80 ℃, wherein the rotating speed is 50rpm, extruding to obtain a plate with the thickness of 2mm, and performing perforation treatment on the plate with the aperture of 2 mm. Irradiating with 254nm ultraviolet lamp at 120W/cm intensity for 30min2And 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 poly (4-hydroxybutyrate) (M)n200kDa), stirring 2 parts by weight of azodiisobutyronitrile in a high-speed stirrer for 10min, uniformly mixing, adding into a double-screw extruder, carrying out melt extrusion at 80 ℃ at the rotating speed of 80rpm to obtain a plate with the thickness of 2mm, and punching the plate with the aperture of 2 mm. Irradiating with 365nm ultraviolet lamp for 1 hr at the irradiation intensity of 180W/cm2And 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 poly (4-hydroxybutyrate) (M)n300kDa), stirring 1 part by weight of di-tert-butyl peroxide in a high-speed stirrer for 15min, uniformly mixing, adding into a double-screw extruder, carrying out melt extrusion at 80 ℃ at the rotating speed of 100rpm to obtain a plate with the thickness of 2mm, and punching the plate with the aperture of 2 mm. Irradiating with 254nm ultraviolet lamp at 200W/cm intensity for 1 hr2And 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)n100kDa) 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 | 420±15 | 98±0.3 | 33±1.2 |
| Example 2 | 480±12 | 98±0.4 | 34±0.8 |
| Example 3 | 540±16 | 99±0.5 | 28±0.7 |
As can be seen from the above table, compared with the polycaprolactone type medical splint obtained by irradiation crosslinking with 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, 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 medical splint provided by the invention has obviously reduced contractility, and the comfort of a patient is enhanced.
Claims (4)
1. A degradable medical splint with shape memory is characterized in that the preparation method comprises the following steps: (1) uniformly mixing 95-99.9 parts by weight of poly (4-hydroxybutyrate) and 0.1-5 parts by weight of crosslinking aid, heating in a double-screw extruder to a molten state, and extruding a sheet to form; (2) punching the obtained sheet according to requirements, and then carrying out ultraviolet irradiation treatment; the crosslinking assistant is a photoinitiator and is selected from methyl vinyl ketone, 2-dimethoxy-2-phenylacetophenone, azodiisobutyronitrile, azodiisoheptanonitrile, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
2. The method for preparing the degradable medical splint with shape memory according to claim 1, comprising the following steps:
(1) uniformly mixing 95-99.9 parts by weight of poly (4-hydroxybutyrate) and 0.1-5 parts by weight of crosslinking aid, heating in a double-screw extruder to a molten state, and extruding a sheet for forming;
(2) the sheet thus obtained was punched as required, and then subjected to ultraviolet irradiation treatment.
3. The method for manufacturing a medical splint according to claim 2, wherein the melt blending temperature is 50 to 80 ℃ and the melt blending extrusion speed is 30 to 100 rpm.
4. The method for preparing a medical splint according to claim 2, wherein the wavelength of the ultraviolet light is 200 to 400nm, and the intensity of the ultraviolet light is 30 to 400W/cm2The irradiation time is 0.5-10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011494416.5A CN112608586B (en) | 2020-12-17 | 2020-12-17 | Degradable shape memory medical splint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011494416.5A CN112608586B (en) | 2020-12-17 | 2020-12-17 | Degradable shape memory medical splint and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112608586A CN112608586A (en) | 2021-04-06 |
| CN112608586B true CN112608586B (en) | 2022-05-03 |
Family
ID=75241079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011494416.5A Active CN112608586B (en) | 2020-12-17 | 2020-12-17 | Degradable shape memory medical splint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112608586B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102430156A (en) * | 2011-12-05 | 2012-05-02 | 泰山医学院 | Medical external fixation material with shape memory function, and preparation method thereof |
| WO2014149024A1 (en) * | 2013-03-18 | 2014-09-25 | Washington State University Research Foundation | Biodegradable polyester-based blends |
| CN108084676A (en) * | 2016-11-22 | 2018-05-29 | 广州天泓医疗科技有限公司 | A kind of low-temp thermoplastic material |
| CN111961322B (en) * | 2020-08-21 | 2022-02-22 | 青岛科技大学 | Poly (4-hydroxybutyrate) biodegradable packaging film and preparation method thereof |
-
2020
- 2020-12-17 CN CN202011494416.5A patent/CN112608586B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112608586A (en) | 2021-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109608842B (en) | Low-temperature thermoplastic sheet and preparation method thereof | |
| CN102085397A (en) | Absorbable implant material in bone and preparation method thereof | |
| JPS6012068A (en) | Modification of structural surgical element of polyglycolic acid for achieving variable physical property in living body | |
| CN112625292B (en) | Preparation method of degradable shape memory polymer medical splint | |
| CN1887364A (en) | Biodegradable medical extracorporeal fixing material possessing shape memory function | |
| CN108084676A (en) | A kind of low-temp thermoplastic material | |
| WO2015043496A1 (en) | Bone injury repair and fixation instrument and method of manufacturing same | |
| Li et al. | Fast gelling and non-swellable photopolymerized poly (vinyl alcohol) hydrogels with high strength | |
| CN112608586B (en) | Degradable shape memory medical splint and preparation method thereof | |
| Liu et al. | Biodegradable cross-linked poly (L-lactide-co-ε-caprolactone) networks for ureteral stent formed by gamma irradiation under vacuum | |
| EP2492316B1 (en) | Low temperature thermoplastic material and preparing method thereof | |
| JP2004059926A (en) | Starch hydrogel | |
| US20210269638A1 (en) | Adhesion prevention film with excellent adhesive property | |
| Liu et al. | Development prospect and research value of biodegradable poly (lactic acid) for bone repair | |
| Hossain et al. | Poly (trimethylene carbonate-co-caprolactone): An emerging drug delivery nanosystem in pharmaceutics | |
| CN112625413B (en) | Modified poly (4-hydroxybutyrate) low-temperature thermoplastic medical splint material | |
| CN111698972B (en) | Fixing device | |
| KR20200083108A (en) | Polyglycolic acid based block copolymer with high stiffness and bioresorbability and method of producing thereof | |
| CN112625412A (en) | Preparation method of poly (4-hydroxybutyrate) low-temperature thermoplastic medical splint | |
| KR101692986B1 (en) | Enhanced physical properties of bioasorbable polymer materials by stereocomplex organic filler and manufacturing method | |
| EP3656406B1 (en) | Absorbable biomedical composite material and preparation method therefor | |
| CN1357388A (en) | New-type medical bandage | |
| CN102488931A (en) | Spiral urethral stent and production method thereof | |
| CN112972762A (en) | Degradable resin and preparation method and application thereof | |
| CN110452511A (en) | A kind of low temperature shape memory high molecule material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220531 Address after: 264006 building 6, No. 302, Changjiang Road, Yantai City, Shandong Province Patentee after: Shandong Zhirui Biotechnology Co.,Ltd. Address before: 266000 Room 608, Jufeng venture building, No.52, Miaoling Road, Laoshan District, Qingdao City, Shandong Province Patentee before: Qingdao Boyuan Polymer Materials Research Institute Co.,Ltd. |