WO2015043496A1 - Instrument de réparation et de fixation de lésion osseuse et son procédé de fabrication - Google Patents

Instrument de réparation et de fixation de lésion osseuse et son procédé de fabrication Download PDF

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WO2015043496A1
WO2015043496A1 PCT/CN2014/087498 CN2014087498W WO2015043496A1 WO 2015043496 A1 WO2015043496 A1 WO 2015043496A1 CN 2014087498 W CN2014087498 W CN 2014087498W WO 2015043496 A1 WO2015043496 A1 WO 2015043496A1
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bone
crosslinking
polymer material
molding
polymer
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PCT/CN2014/087498
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Chinese (zh)
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姜洪焱
康亚红
侯娟
汪璟
罗七一
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上海微创医疗器械（集团）有限公司
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • 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.
  • 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.
  • 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.
  • Inorganic non-metallic materials are mainly a series of calcium phosphate-based bioceramics (including ⁇ -tricalcium phosphate, ⁇ -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.
  • 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- ⁇ -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.
  • 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.
  • 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.
  • CSM calcium metaphosphate
  • 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.
  • 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.
  • 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.
  • 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.
  • the monomer for preparing the crosslinked degradable polymer material is a left-handed milk Acid, D-lactic acid, lactide, ⁇ -caprolactone, salicylic acid, carbonate, amino acids and derivatives thereof.
  • 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.
  • the forming process is injection molding, injection molding - laser cutting molding, hot pressing - laser cutting molding, extrusion molding or extrusion-laser cutting molding.
  • the crosslinking treatment employs ultraviolet crosslinking, thermal reaction crosslinking, chemical reaction crosslinking, and/or physical crosslinking.
  • 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.
  • the crosslinkable group is a methacrylic acid containing a double bond, an acrylic acid containing a double bond, anthracene, cinnamic acid or coumarin.
  • 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.
  • 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.
  • 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.
  • 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.
  • TMAIC trimethylallyl isocyanurate
  • an orientation force is applied to the polymer melt to orient the molecular material, so that the crosslinked polymer has higher mechanical properties.
  • 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.
  • the degradable polymer material comprises L-polylactic acid, racemic polylactic acid, polyglycolic acid, poly- ⁇ -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 ⁇ -. 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.
  • 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
  • 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, tri
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • (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;
  • a cyclic monomer or a cyclic comonomer such as L-lactide and ⁇ -caprolactone (L-LA/ ⁇ -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.
  • 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.
  • 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.
  • 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/ ⁇ -CL 90/10)-PCL 540 indicates that the ratio of the polymerized racemic lactide DL-LA to caprolactone ⁇ -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;

Abstract

La présente invention concerne un instrument de fixation et de réparation de lésion osseuse et son procédé de fabrication. Un matériau polymère biodégradable réticulé a été adopté pour l'instrument. Le matériau polymère est un homopolymère de monomères, un copolymère de monomères multiples ou un mélange de deux ou trois sortes de l'homopolymère et du copolymère, et a une structure de réseau réticulé tridimensionnelle. L'instrument comprend un clou à os, une vis à os, une plaque à os ou un support de fixation, et a une grande performance mécanique, stabilité structurelle, une vitesse de dégradation grandement maîtrisable et une excellente biocompatibilité.
PCT/CN2014/087498 2013-09-26 2014-09-26 Instrument de réparation et de fixation de lésion osseuse et son procédé de fabrication WO2015043496A1 (fr)

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CN106730043B (zh) * 2016-12-19 2022-09-20 苏州西脉新诚生物科技有限公司 一种高强度可吸收骨折内固定骨螺钉
CN109648770A (zh) * 2018-11-27 2019-04-19 广东省医疗器械研究所 一种可降解接骨钉的制作模具及该接骨钉
CN111420274A (zh) * 2020-04-03 2020-07-17 复旦大学附属中山医院 一种固定装置及其起搏电极导线
CN114176698A (zh) * 2021-12-20 2022-03-15 神遁医疗科技(上海)有限公司 一种栓塞物

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