WO2015043496A1 - Bone injury repair and fixation instrument and method of manufacturing same - Google Patents

Abstract

A bone injury repair fixation instrument and a method of manufacturing same. A crosslinked biodegradable polymer material is adopted for the instrument. The polymer material is a homopolymer of monomers, a copolymer of multiple monomers or a blend of 2 or 3 kinds of the homopolymer and copolymer, and has a three-dimensional crosslinked network structure. The instrument comprises a bone nail, a bone screw, a bone plate or a fixing support, and has great mechanical performance, structural stability, controllable degradation speed, and excellent biocompatibility.

Description

Bone damage repair and fixation device and preparation method thereof Technical field

The invention relates to the field of medical devices. More specifically, the present invention relates to a bone injury repair fixation device and a method of preparing the same.

Background technique

Bone trauma is a common disease in surgical surgery. With the aging of the population structure, the development of transportation and manufacturing, and the increasing environmental pollution, the number of patients requiring bone repair due to bone trauma is rising. The lesions and injuries of bone tissue directly affect people's quality of life, so the repair of bone tissue has always been a medical research topic of great concern. Implantation of artificial materials into the body to repair or replace lesions and damage bone tissue is the main clinical treatment.

In the repair of fractures, bone fractures or other types of bone repair, bone bones, spikes, bone screws, bone plates, etc. are often used to join together damaged bone tissue to promote bone tissue regeneration and recovery. These bone nails, spikes, bone screws and bone plates are generally made of a metallic material such as stainless steel, nickel titanium alloy, ceramic or polymeric material. Absorbable polymer materials have received extensive attention in recent years, such as the successful application of polylactic acid, polyglycolide and their copolymers in fracture fixation systems. These orthopedic fixation devices come in different shapes and sizes to provide special features. The bone screw fixation is usually inserted into a screw hole previously drilled in the bone to be repaired. Bone nails or spikes differ from bone screws in that they have no threads and nuts and are often used to increase the stiffness of the bone rather than providing compression. The role of the bone plate is to tightly bond the bone or other parts of the bone together. The bone plate is usually fixed using bone screws. An anchor is used as an attachment for stitching.

Metal, ceramic and polymeric bone fixation devices are not without problems. Medical metal materials mainly include stainless steel, cobalt, chromium, nickel-based alloys, titanium alloys, and precious metals such as gold and platinum. Its biggest advantages: high strength, mature technology, low cost, easy to change shape Adapts to the contours of the bone and is easy to store. However, it also has significant defects: the mechanical compatibility and the tissue compatibility of the metal material and the bone tissue are poor, and the mismatch of the mechanical properties will lead to uneven stress distribution, which will cause the relative movement of the implant and the bone to cause loosening and dislocation. It is easy to cause osteoporosis, bone resorption or bone atrophy and is prone to secondary fractures; poor histocompatibility, lack of sufficient mechanical stress stimulation may lead to delayed initial bone healing. Metal internal fixations such as metal nails and bone screws are usually removed after a second operation after use, again causing great pain to the patient. The second trauma to the patient also reduces the support of the repaired bone.

Inorganic non-metallic materials are mainly a series of calcium phosphate-based bioceramics (including α-tricalcium phosphate, β-tricalcium phosphate, tetracalcium phosphate, etc.), hydroxyapatite (HA), bioglass and wollastonite. Biomedical inorganic non-metallic materials have excellent biological activity, but have defects of large brittleness and poor wear resistance.

Medical polymer materials are divided into two kinds of natural polymer materials and synthetic polymer materials. Among them, natural polymer materials mainly include polysaccharides and proteins. Commonly used are: chitosan and collagen; synthetic polymer materials. According to the structural characteristics of the main chain, it is divided into polyesters, polyanhydrides, polyamides, polyphosphates, etc. Commonly used are polyglycolide (polyglycolic acid, PGA), polylactide (polylactic acid, polylactic acid). Acid, PLA), poly-β-hydroxybutyrate (PHB), copolymers and complexes thereof, and the like are generally linear polymers. Polymer materials have incomparable flexibility between metallic materials and inorganic non-metallic materials. Since 1965, attempts have been made to replace traditional metal materials with biodegradable polymer materials for fracture internal fixation. With the application of degradable internal fixation in the treatment of fractures, clinical advantages have been shown. The main features are: simple operation, bone grafting and osteogenic induction. When the material loses strength, the stress gradually shifts. To the healing of the bone tissue, stress shielding is avoided. No metal corrosion reaction, does not interfere with radiographic images. The internal fixation material degradable material is absorbed by the tissue, no need for a second operation, reducing the patient's pain, the overall cost is low; no obvious rejection and infection, and the healing is relatively fast. However, in the application process, some shortcomings have also appeared, such as low mechanical strength of the fixing member, poor biological activity, easy wear and tear, difficulty in storage, uncontrollable degradation rate, excessive absorption time, and fracture problem. Effective external fixation, such as plaster fixation, time Relatively long. It is not suitable for some parts, such as the part with large tension, which has limited fracture indications, including intra-articular fractures, cancellous bone fractures, tubular bone fractures, osteotomy, and arthrodesis.

U.S. Patent No. 4,539,981 is incorporated herein by reference. The apparatus is made of an L-lactide polymer having an intrinsic viscosity of 4.5 or more and a very high molecular weight. The polymer contains less than 2% unreacted monomer and is polymerized at selected monomer to catalyst ratios and temperature conditions. The device is absorbed by the body and does not need to be removed after the bone has healed.

European Patent Application No. 0,266,146 A2, which is incorporated herein incorporated by reference in its entirety in its entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire portion production.

US Patent No. 4,655,777 is directed to a method of making a biodegradable prosthesis, and its use in bone plates and orthopedic devices, wherein the prosthesis is made of a composite of biodegradable polymers reinforced with absorbable fibers. The fibers include ceramic powder, beta-TCP, CaAl, biodegradable glass, CMP, especially calcium phosphate fibers. The invention aims to combine the advantages of both ceramic and polymeric materials while eliminating the drawbacks (brittleness and strength) of both.

U.S. Patent No. 5,108,755 discloses biodegradable composites suitable for use as a building material for implantable medical devices. The composite is made of a biodegradable substrate (e.g., polyorthoester) and a biodegradable reinforcing material (e.g., calcium metaphosphate (CSM) fiber. This invention is intended to balance the strength and biodegradability of the composite.

U.S. Patent No. 7,378,144 B2 is directed to an oriented polymer implantable device and a method of making the same, the device comprising an implantable tissue or a bone fixation device. Since the degree of polymer orientation is related to physical properties (e.g., strength, elasticity, etc.), the invention achieves higher strength by providing a higher degree of polymer orientation.

The above patents or applications are based on linear degradable polymer materials, especially polylactic acid or its copolymers, or further processing these materials, such as orientation to enhance the mechanical properties of the materials, to prepare degradable bone nails, bone screws, Fixing parts such as bone plates. The main problem is that the bone nail plate prepared by these materials is not strong enough, is easy to break, and the degradation time is too long.

In order to make up for the above-mentioned deficiencies of the bone injury fixation system, it is imperative to develop a bone injury fixation system with excellent biocompatibility, high mechanical strength, and controllable degradation.

Summary of the invention

It is an object of the present invention to design a set of degradable medical devices for the fixation of fractures and bone injuries, including bone nails, bone screws, bone plates, fixation frames, and methods of making the same. The material used for preparing the bone repair system is a cross-linked degradable polymer (polymer) material having a three-dimensional crosslinked network structure, so that it has higher mechanical strength than a linear polymer material (for example, polylactic acid). And toughness, easy to store, and can avoid breakage, to ensure the stability of the bone wound site in the early stage of healing. In addition, due to the adjustable monomer composition and ratio of the polymer, the material has a controlled degradation rate, which can be matched with the rate of bone tissue repair, avoiding delayed occlusion caused by delayed stress in the late healing, which is beneficial to the repair of bone tissue. Reconstruction, speed up its clinical healing, and can control the degradation rate of orthopedic products according to the needs of different parts and different products.

The fracture and bone damage fixing member of the present invention can be designed as an orthopedic fixing member made of a standard metal or polymer material, and different structures are designed on the basis of the above, and the material for preparing the fixing member of the present invention is cross-linked type. Degradation of polymer materials.

Specifically, the present invention relates to a bone injury repair and fixation device, characterized in that the device uses a cross-linked biodegradable polymer material, the polymer material is a monomer homopolymer, and a plurality of single substances. The copolymer of the body, or a blend of 2 to 3 kinds of the homopolymers and copolymers, has a three-dimensional crosslinked network structure.

According to the present invention, the monomer for preparing the crosslinked degradable polymer material is a left-handed milk Acid, D-lactic acid, lactide, ε-caprolactone, salicylic acid, carbonate, amino acids and derivatives thereof.

According to the invention, the proportion of comonomer is between 95:5 and 50:50.

The invention also relates to a bone nail having the features of the bone injury repair fixation device described above.

The invention further relates to a bone screw comprising a nail cap, a screw, a thread and a tip having the features of the bone injury repair fixation device described above.

The present invention also relates to a bone plate or a holder comprising a body and a fixing hole provided in the body, which has the features of the above-described bone damage repairing and fixation device.

The present invention also relates to a method for preparing the above-described bone damage repair and fixation device, comprising performing a cross-linking treatment before, during, or after the molding process.

According to the invention, the forming process is injection molding, injection molding - laser cutting molding, hot pressing - laser cutting molding, extrusion molding or extrusion-laser cutting molding.

According to the present invention, the crosslinking treatment employs ultraviolet crosslinking, thermal reaction crosslinking, chemical reaction crosslinking, and/or physical crosslinking.

According to the present invention, a three-dimensional network crosslinked copolymer is formed by introducing a crosslinkable group at the terminal group of the polymer material, by ultraviolet crosslinking or thermal reaction crosslinking.

According to the invention, the crosslinkable group is a methacrylic acid containing a double bond, an acrylic acid containing a double bond, anthracene, cinnamic acid or coumarin.

According to the invention, a crosslinking agent is added to the polymer material, and the crosslinking agent chemically reacts with the terminal group of the polymer material to form a three-dimensional network crosslinked copolymer after heating.

According to the invention, the cross-linking agent is multi-armed, for example, by a 2-arm linear, 3-arm or 4-arm star prepolymer, preferably a 3-arm or 4-arm star prepolymer, which is cross-linked. The terminal group contains a reactive group such as an isocyanate, an epoxy group or the like.

According to the present invention, the crosslinking agent is multi-armed, and the terminal group contains a crosslinkable group of an unsaturated olefin, which can itself undergo a crosslinking reaction to form a three-dimensional network structure, which is irradiated by heating or ultraviolet light, and the high The molecular material forms a semi-interpenetrating network structure.

According to the present invention, the fixing device formed of a degradable polymer material is subjected to radiation crosslinking, and the radiation crosslinking is selected from electron beam crosslinking and gamma ray crosslinking.

According to the present invention, a small amount, for example, 0.5-5.0% of triallyl isocyanurate or trimethylallyl isocyanurate (TMAIC) is added to the degradable polymer material to promote crosslinking. reaction.

According to the present invention, at the time of the molding process, an orientation force is applied to the polymer melt to orient the molecular material, so that the crosslinked polymer has higher mechanical properties.

According to the present invention, the fixing means is heated and stretched after the forming to orient the molecular material, and the applied temperature is between the glass transition temperature and the melting point of the polymer.

According to the present invention, the degradable polymer material comprises L-polylactic acid, racemic polylactic acid, polyglycolic acid, poly-ε-caprolactone, polytrimethylene carbonate, polydioxanone, polyamino acid derivative. a carbonate or polyorthoester degradable polymer material, a blend of any two or three kinds of degradable polymer materials, a synthetic monomer of the above degradable polymer material and a small amount of a second monomer Copolymer. The copolymerization mode between the degradable materials includes, but is not limited to, graft copolymerization, block copolymerization, random copolymerization, and the like. The monomers of the three copolymerization methods include, but are not limited to, L-lactic acid, D-lactic acid, glycolic acid (glycolic acid), and ε-. Two or more of ester, salicylic acid, carbonate, amino acid and derivatives thereof. The polymer material has a molecular weight of 5,000 to 1.2 million and an intrinsic viscosity of 0.1 to 9.0 dl/g.

According to the present invention, an initiator and a catalyst are usually added in the synthesis of a linear or star-degradable polymer. The linear prepolymer is synthesized from an initiator containing two hydroxyl groups, and the star prepolymer is synthesized from an initiator containing three or four hydroxyl groups. The initiator includes, but is not limited to, an initiator containing two hydroxyl groups, such as ethylene glycol, 1,4-butanediol, n-decanediol, tripropylene glycol, triethylene glycol, triethylene glycol dimethyl Acrylate, triethylene glycol dimethyl ether, triethylene glycol mono-11-decyl undecyl ether, triethylene glycol monobutyl ether, triethylene glycol methyl ether methacrylate, molecular weight 100- 10,000 polyethylene glycol (PEG), polytetrahydrofuran diol (pTHF) having a molecular weight of 100-10,000, polycaprolactone diol (PCL) having a molecular weight of 100-10,000, etc.; an initiator containing three hydroxyl groups, such as Polycaprolactone triol (molecular weight 300,900), trihydroxy polyoxypropylene ether, 1,2,3-heptanetriol, 1,2,6-hexanetriol, trimethylolpropane, 3-methyl -1,3,5-pentanetriol; an initiator containing four hydroxyl groups, such as pentaerythritol, 1,2,7,8-octanetetraol, pentaerythritol propoxide, dipentaerythritol. The catalyst includes, but is not limited to, stannous octoate and dibutyltin dilaurate. The catalyst is present in an amount between one ten thousandth to five thousandths, preferably between one ten thousandth and one thousandth.

In the case where a crosslinkable group is introduced to the terminal group of the degradable polymer material, the number average molecular weight of the star (polylactic acid copolymer) prepolymer can be controlled by the relative content of the initiator and the second monomer, and the number The average molecular weight is controlled between 5,000 and 100,000, preferably between 5,000 and 50,000, and then a crosslinkable reactive group is introduced.

The degradation rate of the synthetic degradable polymeric material is determined by the relative ratio of the first monomer to the second monomer, and the second monomer is between 5-50%.

The synthetic methods of the degradable polymer material include, but are not limited to, a ring-opening polymerization method, a direct polycondensation method, and the like. The ring-opening polymerization is a ring-shaped monomer which is polymerized by ring-opening under the action of an initiator or a catalyst; the polycondensation method means that a bifunctional or polyfunctional monomer is formed by repeated condensation reaction. Molecular reactions include melt polycondensation, solution polycondensation, interfacial polycondensation, solid phase polycondensation, and the like.

For the preparation of cross-linking polymers and cross-linking agents, see Patent Application No. 201310064472.9, filed on February 28, 2013, entitled "Modified Polylactic Acid Degradable Stents and Preparation Methods", October 9, 2012 U.S. Patent Application No. 201210380863.7, entitled "Biodegradable Crosslinked Polymer and Process for Its Preparation", and Patent Application No. 201210380316.9, filed on Oct. 9, 2012, entitled "Degradable Vascular Stent and Preparation thereof" method". The above-identified applications are incorporated herein by reference.

As shown in Figure 1, the bone screw for fracture and bone injury repair fixation consists of a nail cap, a screw, a thread and a nail tip. The shape and size of the bone screw can be referred to the AISF standard for bone screws or moderately modified.

Table 1. Dimensions of bone screws

Thread diameter (mm)	Nut diameter (mm)	Nail diameter (mm)	Thread part minimum diameter (mm)	Pitch (mm)
					1.5 full thread	3.0		1.0	1.25
2.0 full thread	4.0		1.5	1.25
					2.7 full thread	5.0	2.5	1.9	1.25
3.5 full thread	6.0	2.5	2.4	1.25
					4.0 part thread	6.0	2.5	1.9	1.75
4.0 full thread	6.0	2.5	1.9	1.75
					4.5 part thread	8.0	3.0	3.0	1.75
4.5 full thread	8.0	3.0	3.0	1.75
					6.5 full thread	8.0	3.0	3.0	1.75

The diameter of the shank is between 2-6mm, the minimum diameter of the thread is between 1-6mm, the pitch is chosen to be between 1-3mm, preferably 1.25mm or 1.75mm, as shown in Figure 2. The shank portion can be designed as a partially threaded structure as shown in Figure 1 (middle). The length of the thread occupies 40-80% of the entire shank, wherein the shank or threaded portion can be selected with a microporous knot This is conducive to the growth of bone cells and is well integrated with the degradable bone screws.

The size of the nut is between 1 and 12 mm, preferably between 3 and 8 mm. The nut can be selected in various forms in Figure 3. The upper end of the nut can be provided with a cross recess structure, and the middle of the groove can be perforated for easy integration with the suture.

The present invention also includes bone nails which may be smooth or barbed to prevent displacement (as shown in Figure 4). The diameter of the bone nail is between 2 and 8 mm, preferably between 2 and 5 mm.

The present invention also includes a bone plate having a variety of shapes. As shown in FIG. 5, the bone plate has a corresponding hole for the bone nail and the bone screw.

In summary, the present invention provides a bone injury repair and fixation device and a preparation method thereof. The device comprises a bone nail, a bone screw, a bone plate or a fixing frame. Compared with the linear polymer material used in the current orthopedic products, the crosslinked polymer material has higher mechanical strength, is easy to store, and is not easily broken. Thereby ensuring the stability of the bone wound site in the early stage of healing; and because the monomer composition and ratio are adjustable, the material has a controllable degradation rate, which matches the rate of bone tissue repair, and solves the stress occlusion caused by the late healing period. Delayed fracture; due to its good degradability and biocompatibility, it avoids secondary surgery, reduces patient pain and inflammation, and accelerates clinical healing.

DRAWINGS

In order to more clearly describe the technical solution of the present invention, a brief description will be made below with reference to the accompanying drawings. It is obvious that these drawings are only some specific embodiments of the bone injury repair and fixation device described in the present application, but are not intended to be limiting.

Figure 1 shows a bone-fixing bone screw, full thread of the screw, partial thread of the screw, micro-hole of the screw;

Figure 2 is the thread size;

Figure 3 shows the shape of a bone screw cap;

Figure 4 is a barbed nail and a barb without a barb;

Figure 5 illustrates the design and shape of various bone plates;

Figure 6 is a schematic diagram of the synthesis of a degradable crosslinker.

detailed description

In order to further understand the present invention, the preferred embodiments of the present invention will be described below in conjunction with the embodiments. These descriptions are only illustrative of the features and advantages of the invention and are not intended to limit the scope of the invention.

Example 1: Synthesis of 3-arm star polylactic acid copolymer prepolymer and functionalization of prepolymer

Synthesis: 3 liter glass reactor was vacuum dried at 80 ° C for 1 hour before polymerization, 2000 g of L-lactide, 100 g of glycolide and 14 g of 1,2,6 under nitrogen protection. - Glycerol was added to the reactor and dried under vacuum at 60 ° C for 1 hour. Then, 2 g of stannous octoate was added, the temperature was raised to 140 ° C, and the reaction was maintained at 140 ° C for 3 hours to obtain a star polylactic acid prepolymer having a number average molecular weight of 20,000 (see Reaction Formula 1). The molecular weight of the star polylactic acid copolymer prepolymer is controlled by the relative amounts of the initiator and the monomer, and the number average molecular weight is controlled between 5,000 and 50,000. When the molecular weight of the star polylactic acid copolymer prepolymer reaches the experimental design requirements, 48 g (0.32 mol) of methacrylic anhydride and 0.6 g (300 ppm) of the free radical inhibitor p-hydroxyanisole are directly added dropwise. The reaction was carried out at ° C for 2 hours to form a crosslinkable star polymer (see Reaction Scheme 2). After the reaction was completed, the temperature was lowered to 60 ° C. 5 L of ethyl acetate was added to the reactor to dissolve the prepolymer, and then slowly poured. In a mixture of n-hexane and ethanol, precipitation and drying yield a prepolymer product.

Where x=3-300 and y=1-100.

For the sake of clarity, the above structure is simplified to:

That is, a degradable polymer having three hydroxyl groups (n = 3).

Reaction formula 1: Formation of a 3-arm star polymer prepolymer

Reaction Formula 2: Formation of a 3-arm star crosslinkable prepolymer with a crosslinkable reactive group

Crosslinking and molding of prepolymers:

(a) processing the obtained crosslinkable prepolymer having a reactive group into a fracture and bone injury fixation system such as a bone nail, a bone plate, a bone block, a bone rod, etc., as described above, in the 200-400 nm band Irradiation under ultraviolet light, the temperature is controlled between 35-65 ° C, and the crosslinking reaction is carried out for 5-30 min to obtain a product;

(b) or the obtained crosslinkable prepolymer with reactive groups and the linear degradable polymer material are mixed in a certain ratio to be processed into the fracture and bone damage fixation system such as bone nail and bone plate described above. Bone block, bone rod, etc., irradiated under ultraviolet light in the 200-400nm band, and the temperature is controlled between 35-65 ° C, and the cross-linking reaction is carried out for 5-30 min to obtain a product;

(c) or cross-linking the obtained crosslinkable prepolymer having a reactive group, and then pressurizing on a flat vulcanizer at 130-190 ° C, 10-20 MPa for 10-30 min to obtain a bone nail, The material of the bone plate and the bone block is cut into the bone nail, the bone plate, the bone block, the bone rod and the like.

Example 2: Synthesis of crosslinking agent

As shown in Fig. 6, first, a cyclic monomer or a cyclic comonomer such as L-lactide and ε-caprolactone (L-LA/ε-CL molar ratio of 95/5) is obtained by a ring-opening polymerization method. Synthetic star degradable polymer copolymer as a prepolymer (including 2, 3 or 4 arm linear or star polymers, preferably a star polymer with 3 or 4 arms to facilitate Cross-linking reaction), such as a tetrahydroxy polymer. The number average molecular weight of the tetrahydroxy polymer is controlled between 500 and 100,000. The isocyanate is then introduced at the end of the tetrahydroxy polymer by polycondensation, and the remaining isocyanate is removed by polymer precipitation washing to ensure that no isocyanate residue is present, thereby synthesizing the crosslinker.

Mix linear or multi-arm degradable polymers (number average molecular weight between 50,000 and 1.2 million, number of arms is 2, 3, 4) and the above-mentioned degradable crosslinker with isocyanate end groups in a certain ratio . The proportion of the crosslinking agent in the mixture is between 10% and 80%, and an appropriate amount can be added. The (for example, 0.1 mol%) catalyst, such as dibutyltin dilaurate, is then prepared by injection extrusion or injection molding to obtain bone nails, bone screws, bone plates and the like. The apparatus to be prepared may be subjected to a suitable heat treatment for completion of the crosslinking reaction, thereby obtaining a polymer article having a three-dimensional crosslinked network structure.

Example 3: Performance test

The prepolymer or the prepolymer and the blend of the above Example 1 are thoroughly mixed, heated and melted between two glasses, and a PTFE-cut frame film is placed between the glass to control the thickness of the sheet. The composite sheet was prepared by cross-linking polymerization by heating or UV light irradiation, and the mechanical properties and thermal properties of the polymer are shown in Table 1 below. The degradation rate experiment was carried out in a constant temperature oscillating degrader. A sample of a certain size and weight was placed in a pH 7 buffer solution, and the bath temperature was controlled at 37 °C. The samples were taken out at regular intervals and weighed, so that the weight loss (%) of the samples was measured.

Table 1: Mechanical and thermal behavior of crosslinked degradable polymers

Note:

PLGA: L-lactide and glycolide copolymer, PLGA (95/5) indicates that the ratio of polymerized L-lactic acid to glycolide is 95:5, and so on;

PLLA: poly-L-lactic acid;

PDLLA: poly- lactic acid;

P(L-LA70-DL-LA30)-TERA represents that the ratio of the polymerized L-lactide L-LA to the racemic lactide DL-LA is 70:30, and the initiator is pentaerythritol;

pTHF250: polytetrahydrofuran diol having a molecular weight of 250;

PCL: polycaprolactone diol, PCL500 and PCL540 represent polycaprolactone diols having molecular weights of 500 and 540, respectively;

PLGA(85/15)-tetra-20K-PLA32: wherein PLGA(85/15)-tetra-15K represents a molecular weight of 20kk of crosslinker with 4 arms of isocyanate, and a polymer which is cross-linked with it It is PLA polylactic acid and its intrinsic viscosity is 3.2dL/g.

PEG600 and PEG1000 represent polyethylene glycols having molecular weights of 600 and 1000, respectively;

PLGA(85/15)-PCL trio1900: indicates that the ratio of the polymerized L-lactide to glycolide is 85:15, the initiator is polycaprolactone triol, and the molecular weight is 900;

P(DL-LA/ε-CL 90/10)-PCL 540: indicates that the ratio of the polymerized racemic lactide DL-LA to caprolactone ε-CL is 90:10, and the initiator is polycaprolactone a triol having a molecular weight of 540;

PLGA(85/15)-PC500: wherein the ratio of polymerized L-lactide to glycolide is 85:15, the initiator is polycarbonate diol, and the molecular weight is 500;

ND: Not tested.

The above description of the embodiments is merely for helping to understand the core idea of the present invention. It should be noted that many modifications and variations of the present invention may be made without departing from the spirit and scope of the invention. .

Claims (19)

1. A bone damage repairing and fixing device, characterized in that the device adopts a cross-linked biodegradable polymer material, wherein the polymer material is a monomer homopolymer, a copolymer of a plurality of monomers, or 2 ~3 kinds of the homopolymer, a blend of copolymers, having a three-dimensional crosslinked network structure.
2. The fixing device according to claim 1, wherein the monomer material for preparing the crosslinked degradable polymer material is L-lactic acid, D-lactic acid, lactide, ε-caprolactone, salicylic acid, Carbonates, amino acids and their derivatives.
3. The fixation device of claim 1 wherein said comonomer ratio is between 95:5 and 50:50.
4. A bone nail characterized by having the features of any one of claims 1 to 3.
5. A bone screw comprising a nail cap, a screw, a thread and a tip, characterized by further having the features of any of claims 1-3.
6. A bone plate or holder comprising a body and a fixing hole provided in the body, characterized by further having the features of any one of claims 1 to 3.
7. A method of preparing a bone injury repair and fixation device according to claim 1, wherein the crosslinking treatment is performed before the molding process, during the molding process, or after the molding process.
8. The production method according to claim 7, wherein the molding process is injection molding, injection molding-laser cutting molding, hot press-laser cutting molding, extrusion molding or extrusion-laser cutting molding.
9. The preparation method according to claim 7, wherein said crosslinking treatment is carried out UV crosslinking, thermal reaction crosslinking, chemical reaction crosslinking, and/or physical crosslinking.
10. The preparation method according to claim 7, wherein a three-dimensional network crosslinked copolymer is formed by introducing a crosslinkable group at the terminal group of the polymer material by ultraviolet crosslinking or thermal reaction crosslinking.
11. The process according to claim 10, wherein the crosslinkable group is methacrylic acid containing a double bond, acrylic acid, hydrazine, cinnamic acid or coumarin containing a double bond.
12. The preparation method according to claim 7, wherein a crosslinking agent is added to the polymer material, and the crosslinking agent chemically reacts with the terminal group of the polymer material to form a three-dimensional network cross-linking copolymerization by heating. Things.
13. The process according to claim 12, wherein the crosslinking agent is multi-armed and the terminal group contains a reactive group.
14. The preparation method according to claim 12, wherein the crosslinking agent is multi-armed, and the terminal group contains a crosslinkable group of an unsaturated olefin, which can undergo cross-linking reaction to form a three-dimensional network structure, and is heated by heating. Or irradiated with a UV lamp to form a semi-interpenetrating network structure with the polymer material.
15. The preparation method according to claim 7, wherein the fixing device formed of the degradable polymer material is subjected to radiation crosslinking, and the radiation crosslinking is selected from electron beam crosslinking and gamma ray crosslinking.
16. The process according to claim 15, wherein triallyl isocyanurate or trimethylallyl isocyanurate is added to the degradable polymer material to promote a crosslinking reaction.
17. The production method according to claim 7, wherein said comonomer The ratio is between 95:5 and 50:50.
18. The production method according to any one of claims 7 to 16, wherein an orientation force is applied to the polymer melt during the molding process to orient the molecular material.
19. The preparation method according to any one of claims 7 to 16, characterized in that after the processing and molding, the fixing device is heated and stretched to orient the polymer material, and the temperature is applied to the glass of the polymer. Between the transition temperature and the melting point.

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