CN111671981A - Absorbable composite material for interface screw sheath and preparation method thereof - Google Patents

Absorbable composite material for interface screw sheath and preparation method thereof Download PDF

Info

Publication number
CN111671981A
CN111671981A CN202010590650.1A CN202010590650A CN111671981A CN 111671981 A CN111671981 A CN 111671981A CN 202010590650 A CN202010590650 A CN 202010590650A CN 111671981 A CN111671981 A CN 111671981A
Authority
CN
China
Prior art keywords
composite material
polylactic acid
screw sheath
absorbable composite
peg
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.)
Pending
Application number
CN202010590650.1A
Other languages
Chinese (zh)
Inventor
李若云
李凌晨
吴侃
胡程程
蒋冠森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hangzhou Ruijian Masiding Medical Equipment Co ltd
Original Assignee
Hangzhou Ruijian Masiding Medical Equipment Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hangzhou Ruijian Masiding Medical Equipment Co ltd filed Critical Hangzhou Ruijian Masiding Medical Equipment Co ltd
Priority to CN202010590650.1A priority Critical patent/CN111671981A/en
Publication of CN111671981A publication Critical patent/CN111671981A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • A61L31/02—Inorganic materials
    • A61L31/028—Other inorganic materials not covered by A61L31/022 - A61L31/026
    • 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
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • 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
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148—Materials at least partially resorbable by the body

Abstract

The invention relates to an absorbable composite material for an interface screw sheath and a preparation method thereof, wherein the preparation method comprises the following steps: the absorbable composite material for the interface screw sheath is prepared by melt blending of hydroxyapatite, maleic anhydride, PEG and polylactic acid, wherein the polylactic acid is polylactic acid and/or a copolymer thereof, the elongation at break of the absorbable composite material for the interface screw sheath is not less than 110%, and the impact strength of the absorbable composite material is not less than 12kJ/m2The breaking strength is not lower than 34 MPa; the finally prepared absorbable composite material for the interface screw sheath contains a crosslinked network structure with hydroxyapatite as a crosslinking point, polylactic acid material as a hard segment and PEG as a soft segment, wherein the hydroxyapatite, the polylactic acid material and the PEG are connected with each other through a residual chain segment of maleic anhydride after ring opening. The preparation method is simple, and the final product isThe absorbable composite material for the interface screw sheath has excellent mechanical strength and better toughness, and the interface screw sheath prepared from the material is not easy to crack in the using process.

Description

Absorbable composite material for interface screw sheath and preparation method thereof
Technical Field
The invention belongs to the technical field of biomedical materials, and relates to an absorbable composite material for an interface screw sheath and a preparation method thereof.
Background
The present absorbable interfacial screw sheath is made of a material mainly comprising polylactic acid (PLLA) or a blend of a poly (lactide-co-glycolide) (PLGA) and β -TCP or Hydroxyapatite (HA), which HAs good osteoinductive properties and promotes bone ingrowth, and the degradation products thereof are weakly alkaline and neutralize lactic acid or glycolic acid generated by the degradation of the poly (lactic acid) or poly (lactide-co-glycolide) (PLGA), thereby reducing the occurrence of inflammation in the surrounding tissue of the implant<5kJ/m2Elongation at break<5 percent, the prepared interface screw sheath is easy to crack in the using process and seriously influences the treatment effect, so the interface screw sheath also needs to be improved.
In order to increase the interfacial bonding force between HA and organic polymer, document 1 (Hydroxyacrylate-Polyethylene Composites: Effect of Grafting and Surface Treatment of Hydroxyacrylate [ J ]. Journal of Materials in Medicine,1996,7(4):191-193.) acrylic acid was grafted onto the molecular chain of HDPE, and the graft-modified HDPE was melt-blended with HA treated with A174 silane coupling agent, the hydrophilic terminal methylsiloxane of A174 formed P-O-SI bonds on the Surface of HA, while the nonpolar hydrophobic terminal propylmethacrylate covered the Surface of HA, which could entangle with the acrylic acid grafted on HDPE, thereby increasing the interfacial interaction force between HA and HDPE, and the experimental results showed that blending the untreated HA with HDPE, the tensile strength of the material was 17MPa, the elongation at break was 34%, and the silane-treated HA with the graft-treated HA, the tensile strength of the material is increased by 2MPa, and the elongation at break is increased by only 6%; document 2(surface modification of aqueous to internal interface bonding with reactive (TM)70/30in a biodegradable composite [ J ] Journal of Materials Science Materials in Medicine,1996,7(9):551 557.) and document 3 (acids as bonding agents in a hydrophilic polyester-ether (reactive TM 30/70) composites [ J ] Journal of Materials Science,1998,9(1):23-30.) HA was first surface-modified with polyacrylic acid (PAA) and ethylene maleic anhydride copolymer (EMA), respectively, then melt-blending with Polactivet 70/30 (containing PEG chain segment), utilizing the strong adsorption effect of HA on PAA and EMA to make PAA and EMA firmly adhere to HA surface, because the carboxyl on PAA and EMA and PEG can form hydrogen bonds, the interfacial adhesion between HA and the polymer is increased, the final mechanical strength is improved by 2MPa, and the elongation at break result shows that the elongation at break is only improved by 5%; document 4(Composite biomaterials with chemical bonding between hydrophilic Materials fillers and PEG/PBTcopolymer matrix [ J ]. Journal of biological Materials Research,1998,40(3):490-497.) use HMDI as a coupling agent to utilize the characteristic of reaction between isocyanate and HA hydroxyl groups to achieve chemical bonding between polymers such as PEG, PMMA and the like and HA and increase the interfacial force between the polymers and HA, and the experimental results show that the use of HMDI increases the fracture strength of the blend material by 1MPa, but the elongation at break is not changed and is not mentioned in terms of impact strength; document 5(Improvement of β -TCP/PLLA biodegradable surface modification with stearic acid [ J ]. Materials Science and engineering C,2016,62: 407-. Therefore, only the interfacial force between the inorganic material and the polymer is increased, the tensile strength of the blended material can be improved to a certain extent, the effect is not optimistic for the increase of the elongation at break, and for the blended material of the HA and the polymer, the existing research mainly focuses on only improving the interfacial bonding force between the inorganic material HA and the polymer so as to improve the tensile strength of the material, and further research on improving the elongation at break and the impact strength is not carried out on the basis.
Therefore, there is a need to develop a method for effectively improving the toughness of the material (i.e. effectively improving the elongation at break and impact strength of the material) and maintaining sufficient mechanical strength, so as to solve the problem that the existing absorbable interface screw sheath is not strong enough and has high brittleness, which leads to easy cracking.
Disclosure of Invention
The invention provides an absorbable composite material for an interface screw sheath and a preparation method thereof, and aims to solve the problem that the absorbable interface screw sheath is not high in strength and high in brittleness and is prone to cracking in the prior art. The invention utilizes the reaction characteristic of P-OH groups on the surface of Hydroxyapatite (HA), and adds maleic anhydride, PEG (polyethylene glycol) and polylactic acid materials for melt blending to prepare the absorbable composite material for the interface screw sheath with sufficient strength and excellent flexibility.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the absorbable composite material for the interface screw sheath comprises the steps of carrying out melt blending on hydroxyapatite, maleic anhydride, PEG and polylactic acid materials to prepare the absorbable composite material for the interface screw sheath, wherein the polylactic acid materials are polylactic acid and/or copolymers thereof, the breaking elongation of the absorbable composite material for the interface screw sheath is not lower than 110%, and the impact strength of the absorbable composite material is not lower than 12kJ/m2The breaking strength is not lower than 34MPa, the materials used by the interface screw sheath on the current market are mainly the blend materials of polylactic acid materials and β -TCP or hydroxyapatite, the elongation at break of the materials is less than 5 percent, and the impact strength is strongThe degree is less than 2kJ/m2The fracture strength is 30-55 MPa, the interface nail sheath is frequently broken in the using process of a doctor, and the material can effectively solve the problem of frequent breakage of the interface nail sheath.
As a preferred technical scheme:
according to the preparation method of the absorbable composite material for the interface screw sheath, the mass adding amount ratio of the hydroxyapatite to the PEG to the polylactic acid material is 5-20: 5-10: 70-90, and the mass adding amount of the maleic anhydride is 1-3% of the sum of the mass adding amounts of the hydroxyapatite to the PEG to the polylactic acid material. The mixture of the materials can generate in-situ reaction in the process of melt blending, and the adding amount of the hydroxyapatite can provide enough crosslinking reaction points and bone inductivity for the in-situ reaction of the blended material, and simultaneously can keep the strength of the blended material at a higher value; the addition amount of PEG can provide enough ductility and in-situ reaction points for the blended material; the polylactic acid-based material is used as the base material, and thus the addition amount is set thereto; the addition amount of the maleic anhydride is set to realize the connection of HA, PEG and polylactic acid materials.
According to the preparation method of the absorbable composite material for the interface screw sheath, the average particle size of hydroxyapatite is 200-750 nm. The average particle size of the hydroxyapatite should not be too large or too small, otherwise the strength of the polylactic acid material is greatly reduced.
According to the preparation method of the absorbable composite material for the interface screw sheath, the number average molecular weight of PEG is 400-6000 g/mol; the weight average molecular weight of the polylactic acid material is 200000-600000 g/mol.
In the preparation method of the absorbable composite material for the interface screw sheath, the polylactic acid material is a levorotatory lactide polymer, a copolymer of levorotatory lactide and dextrorotatory lactide (PDLLA) or a copolymer of levorotatory/dextrorotatory lactide and glycolide, and the polymers have excellent biocompatibility and in-vivo degradability and can provide basic strength for the interface screw sheath.
The preparation method of the absorbable composite material for the interface screw sheath has the advantage that the melt blending temperature is 170-250 ℃.
According to the preparation method of the absorbable composite material for the interface screw sheath, a double-screw extruder is adopted for melt blending, and the rotating speed of the screws is 100-300 rpm.
The invention also provides the absorbable composite material for the interface screw sheath, which is prepared by the preparation method of the absorbable composite material for the interface screw sheath, and comprises a cross-linked reticular structure with hydroxyapatite as a cross-linking point, polylactic acid material as a hard segment and PEG as a soft segment, wherein the hydroxyapatite, the polylactic acid material and the PEG are connected with each other through a maleic anhydride residual segment after ring opening.
The invention mechanism is as follows:
the polylactic acid material and the inorganic material HA which are organic high molecular materials are main materials used for preparing the absorbable interface screw sheath, but the compatibility between the polylactic acid material and the inorganic material HA is poor, the mechanical strength is reduced after blending, and the brittleness is higher, so that the absorbable interface screw sheath prepared from the polylactic acid material and the inorganic material HA is easy to crack in the using process.
The HA surface is rich in P-OH groups, and the reaction capability of the active groups and other substances is utilized, so that the interfacial bonding force between the HA and the polymer can be increased, and a plurality of hydroxyl groups on the HA surface can be utilized to enable the HA to be used as a crosslinking point. According to the invention, by utilizing the reaction characteristic of P-OH groups on the surface of HA, maleic anhydride, PEG and polylactic acid materials are added for melt blending, and extrusion granulation is carried out to obtain the absorbable composite material for the interface screw sheath with sufficient strength and excellent flexibility. Wherein, maleic anhydride can be esterified with hydroxyl to generate a substance with a carboxyl end group, the end group of PEG is alcoholic hydroxyl, the end group of polylactic acid material is alcoholic hydroxyl or carboxyl, and the hydroxyl and the carboxyl can react to generate an ester bond, so the following reaction can occur in the blending process (taking polylactic acid PLLA as an example):
Figure BDA0002555378050000041
due to the large number of hydroxyl groups on the surface of HA, a crosslinked network product (shown in figure 1) taking HHA as crosslinking points is generated during blending, the interfacial force between HA and the polylactic acid material is improved due to the formation of chemical bonds, PEG is an excellent plasticizer of the polylactic acid material, the brittleness of the polylactic acid material can be effectively reduced, and in the crosslinked network, the polylactic acid material chain segments existing between the HA crosslinking points enable the network to be rich in rigidity and strength, and the existence of the PEG chain segments enables the network to be rich in flexibility and elasticity. The overall blended product has sufficient strength, flexibility and elasticity.
Has the advantages that:
(1) the preparation method of the absorbable composite material for the interface screw sheath is simple and feasible, HAs low cost, greatly increases the interface acting force between HA and polylactic acid materials due to the existence of P-OH on the HA and the addition of maleic anhydride, and improves the tensile strength of the blended material by at least 5 MPa;
(2) according to the preparation method of the absorbable composite material for the interface screw sheath, the crosslinking points are made of a plurality of hydroxyl groups of HA, PEG with a good plasticizing effect is used, the connecting chain segment of PEG and polylactic acid materials is formed between the HA crosslinking points, the breaking elongation of the blended material can be improved to more than 110%, and the impact strength is improved to 12kJ/m2The above;
(3) the absorbable composite material for the interface screw sheath is excellent in mechanical strength and good in toughness, and the prepared absorbable interface screw sheath is not easy to crack and good in use experience.
Drawings
FIG. 1 is a schematic diagram of a crosslinked network product with HA as crosslinking points formed when the reaction materials of the present invention are blended.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of an absorbable composite material for an interface screw sheath comprises the steps of adding hydroxyapatite with the average particle size of 200nm, maleic anhydride, PEG with the number average molecular weight of 400g/mol and a polylactic acid material (polylactic acid PLLA with the weight average molecular weight of 200000 g/mol) into a double-screw extruder to be subjected to melt blending, and thus obtaining the absorbable composite material for the interface screw sheath, wherein the mass adding amount ratio of the hydroxyapatite, the PEG and the polylactic acid material is 20:10:70, the mass adding amount of the maleic anhydride is 3% of the sum of the mass adding amounts of the hydroxyapatite, the PEG and the polylactic acid material, the melt blending temperature is 185 ℃, and the screw rotating speed is 150 rpm.
The finally prepared absorbable composite material for the interface screw sheath contains a crosslinked reticular structure with hydroxyapatite as a crosslinking point, polylactic acid material as a hard segment and PEG as a soft segment, the hydroxyapatite, the polylactic acid material and the PEG are connected with each other through a residual chain segment of maleic anhydride after ring opening, the breaking elongation of the absorbable composite material is 205 percent, and the impact strength of the absorbable composite material is 17kJ/m2The breaking strength was 34 MPa.
Comparative example 1
A preparation method of an absorbable composite material for an interface screw sheath is basically the same as that of example 1, except that the reaction raw materials do not contain maleic anhydride, the proportional relationship among other raw materials is kept unchanged, and the finally prepared absorbable composite material for the interface screw sheath has the breaking elongation of 110 percent and the impact strength of 5kJ/m2The breaking strength was 29 MPa.
Comparing example 1 with comparative example 1, it can be seen that, after maleic anhydride is added into the blend, the elongation at break, impact strength and breaking strength of the blended material are all increased, because maleic anhydride HAs higher reactivity, generates carboxyl groups by ring opening during melt blending, and can react with hydroxyl groups on HA, PEG and polylactic acid to realize the connection of HA, PEG and polylactic acid. As HA is rich in hydroxyl, a cross-linked network structure taking HA as a cross-linking point is formed, so that the toughness of the blended material is improved, and the high strength is maintained.
Comparative example 2
A preparation method of an absorbable composite material for an interface screw sheath is basically the same as that of example 1, except that reaction raw materials do not include PEG, the proportional relationship among other raw materials is kept unchanged, and the finally prepared absorbable composite material for the interface screw sheath has the breaking elongation of 3% and the impact strength of 1.2kJ/m2The breaking strength was 54 MPa.
Comparing example 1 with comparative example 2, it can be seen that when PEG is absent in the blend, the elongation at break and impact strength of the blended material are significantly reduced, and the strength at break is increased, because PEG has a plasticizing effect on polylactic acid, the elongation at break and impact strength of polylactic acid can be increased, the brittleness of the material is reduced, PEG can promote the formation of a cross-linked network structure on one hand, and PEG can also be used as an elastic chain segment in the cross-linked network structure on the other hand, so that the elongation at break and impact strength of the material are improved.
Comparative example 3
A preparation method of an absorbable composite material for an interface screw sheath is basically the same as that of example 1, except that reaction raw materials do not include maleic anhydride and PEG, meanwhile, the proportional relationship among other raw materials is kept unchanged, and the finally prepared absorbable composite material for the interface screw sheath has the breaking elongation of 2 percent and the impact strength of 1.5kJ/m2The breaking strength was 50 MPa.
Comparing example 1 with comparative example 3, it can be seen that the elongation at break and impact strength of the blended material are decreased and the strength at break is increased in the absence of maleic anhydride and PEG in the blend because only HA in the blend at this time, the blend cannot form a cross-linked network structure having soft segments due to the absence of maleic anhydride and PEG, and toughness and ductility are insufficient.
Comparative example 4
A preparation method of an absorbable composite material for an interface screw sheath is the same as that in example 1, except that a blend is obtained by adopting a solution pouring method, during experiments, PLLA, HA, PEG and maleic anhydride are dissolved in chloroform according to the proportion in example 1, the solution is poured out after stirring for 1 hour at room temperature, and the blend material is obtained after the solvent is completely volatilized.
The finally prepared absorbable composite material for the interface screw sheath has the elongation at break of 113 percent and the impact strength of 2.1kJ/m2The breaking strength was 28 MPa.
As can be seen from a comparison between example 1 and comparative example 4, the blend obtained by the solution casting method does not achieve excellent ductility and toughness because maleic anhydride cannot undergo a ring-opening reaction, PLA, PEG, and HA cannot undergo an in-situ reaction due to a low temperature during solution casting, a cross-linked network structure having a hard segment and a soft segment is difficult to form, and the interfacial bonding force between HA and PLA cannot be improved.
Example 2
A preparation method of an absorbable composite material for an interface screw sheath comprises the steps of adding hydroxyapatite with the average particle size of 350nm, maleic anhydride, PEG with the number average molecular weight of 1000g/mol and a polylactic acid material (polylactic acid PLLA with the weight average molecular weight of 400000 g/mol) into a double-screw extruder to be subjected to melt blending, and thus obtaining the absorbable composite material for the interface screw sheath, wherein the mass adding amount ratio of the hydroxyapatite to the PEG to the polylactic acid material is 20:10:70, the mass adding amount of the maleic anhydride is 3% of the sum of the mass adding amounts of the hydroxyapatite to the PEG to the polylactic acid material, the melt blending temperature is 190 ℃, and the screw rotating speed is 150 rpm.
The finally prepared absorbable composite material for the interface screw sheath contains a crosslinked reticular structure with hydroxyapatite as a crosslinking point, polylactic acid material as a hard segment and PEG as a soft segment, the hydroxyapatite, the polylactic acid material and the PEG are connected with each other through a residual chain segment of maleic anhydride after ring opening, the breaking elongation of the absorbable composite material is 197 percent, and the impact strength of the absorbable composite material is 16kJ/m2The breaking strength was 37 MPa.
Example 3
A preparation method of an absorbable composite material for an interface screw sheath comprises the steps of adding hydroxyapatite with the average particle size of 750nm, maleic anhydride, PEG with the number average molecular weight of 6000g/mol and a polylactic acid material (polylactic acid PLLA with the weight average molecular weight of 600000 g/mol) into a double-screw extruder to be subjected to melt blending to prepare the absorbable composite material for the interface screw sheath, wherein the mass adding amount ratio of the hydroxyapatite to the PEG to the polylactic acid material is 5:5:90, the mass adding amount of the maleic anhydride is 1% of the sum of the mass adding amounts of the hydroxyapatite to the PEG to the polylactic acid material, the melt blending temperature is 200 ℃, and the screw rotating speed is 180 rpm.
The finally prepared absorbable composite material for the interface screw sheath contains a crosslinked reticular structure with hydroxyapatite as a crosslinking point, polylactic acid material as a hard segment and PEG as a soft segment, the hydroxyapatite, the polylactic acid material and the PEG are connected with each other through a residual chain segment of maleic anhydride after ring opening, the breaking elongation of the absorbable composite material is 110%, and the impact strength of the absorbable composite material is 12kJ/m2The breaking strength was 46 MPa.
Example 4
A preparation method of an absorbable composite material for an interface screw sheath comprises the steps of adding hydroxyapatite with the average particle size of 250nm, maleic anhydride, PEG with the number average molecular weight of 3200g/mol and a polylactic acid material (PLGA (85LA/15GA) with the weight average molecular weight of 300000 g/mol) into a double-screw extruder to be subjected to melt blending to obtain the absorbable composite material for the interface screw sheath, wherein the mass adding amount ratio of the hydroxyapatite, the PEG and the polylactic acid material is 18:7:75, the mass adding amount of the maleic anhydride is 2% of the sum of the mass adding amounts of the hydroxyapatite, the PEG and the polylactic acid material, the melt blending temperature is 178 ℃, and the rotating speed of a screw is 100 rpm.
The finally prepared absorbable composite material for the interface screw sheath contains a crosslinked reticular structure with hydroxyapatite as a crosslinking point, polylactic acid material as a hard segment and PEG as a soft segment, the hydroxyapatite, the polylactic acid material and the PEG are connected with each other through a residual chain segment of maleic anhydride after ring opening, the breaking elongation of the absorbable composite material is 152%, and the impact strength of the absorbable composite material is 15.5kJ/m2The breaking strength was 38.5 MPa.
Example 5
A method for preparing absorbable composite material for an interface screw sheath comprises the steps of adding hydroxyapatite with the average particle size of 440nm, maleic anhydride, PEG with the number average molecular weight of 4200g/mol and polylactic acid material (PDLLA (50/50) with the weight average molecular weight of 500000 g/mol) into a double-screw extruder to be subjected to melt blending, and obtaining the absorbable composite material for the interface screw sheath, wherein the mass adding amount ratio of the hydroxyapatite, the PEG and the polylactic acid material is 13:8:79, the mass adding amount of the maleic anhydride is 1.5% of the sum of the mass adding amounts of the hydroxyapatite, the PEG and the polylactic acid material, the melt blending temperature is 170 ℃, and the screw rotating speed is 200 rpm.
The finally prepared absorbable composite material for the interface screw sheath contains a crosslinked reticular structure with hydroxyapatite as a crosslinking point, polylactic acid material as a hard segment and PEG as a soft segment, the hydroxyapatite, the polylactic acid material and the PEG are connected with each other through a residual chain segment of maleic anhydride after ring opening, the breaking elongation of the absorbable composite material is 168%, and the impact strength of the absorbable composite material is 14.8kJ/m2The breaking strength was 41.3 MPa.

Claims (8)

1. A preparation method of an absorbable composite material for an interface screw sheath is characterized by comprising the following steps: the absorbable composite material for the interface screw sheath is prepared by melt blending of hydroxyapatite, maleic anhydride, PEG and polylactic acid, wherein the polylactic acid is polylactic acid and/or a copolymer thereof, the elongation at break of the absorbable composite material for the interface screw sheath is not less than 110%, and the impact strength of the absorbable composite material is not less than 12kJ/m2And the breaking strength is not lower than 34 MPa.
2. The preparation method of the absorbable composite material for the interfacial screw sheath, according to claim 1, is characterized in that the mass addition ratio of the hydroxyapatite, the PEG and the polylactic acid material is 5-20: 5-10: 70-90, and the mass addition amount of the maleic anhydride is 1-3% of the sum of the mass addition amounts of the hydroxyapatite, the PEG and the polylactic acid material.
3. The method for preparing the absorbable composite material for the interfacial screw sheath of claim 1, wherein the hydroxyapatite has an average particle size of 200-750 nm.
4. The method for preparing the absorbable composite material for the interfacial screw sheath as claimed in claim 1, wherein the number average molecular weight of PEG is 400-6000 g/mol; the weight average molecular weight of the polylactic acid material is 200000-600000 g/mol.
5. The method for preparing the absorbable composite material for the interface screw sheath as claimed in claim 1, wherein the polylactic acid material is a levolactide polymer, a copolymer of levolactide and dextrolactide or a copolymer of levolactide/dextrolactide and glycolide.
6. The preparation method of the absorbable composite material for the interfacial screw sheath as claimed in claim 5, wherein the temperature of melt blending is 170-250 ℃.
7. The preparation method of the absorbable composite material for the interface screw sheath, which is characterized in that a double-screw extruder is adopted for melt blending, and the screw rotating speed is 100-300 rpm.
8. The absorbable composite material for the interface screw sheath prepared by the preparation method of the absorbable composite material for the interface screw sheath as claimed in any one of claims 1 to 7, which is characterized in that: contains a cross-linked network structure which takes hydroxyapatite as a cross-linking point, a polylactic acid material as a hard segment and PEG as a soft segment, and the hydroxyapatite, the polylactic acid material and the PEG are connected with each other through a residual chain segment of maleic anhydride after ring opening.
CN202010590650.1A 2020-06-24 2020-06-24 Absorbable composite material for interface screw sheath and preparation method thereof Pending CN111671981A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010590650.1A CN111671981A (en) 2020-06-24 2020-06-24 Absorbable composite material for interface screw sheath and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010590650.1A CN111671981A (en) 2020-06-24 2020-06-24 Absorbable composite material for interface screw sheath and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111671981A true CN111671981A (en) 2020-09-18

Family

ID=72437125

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010590650.1A Pending CN111671981A (en) 2020-06-24 2020-06-24 Absorbable composite material for interface screw sheath and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111671981A (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1544524A (en) * 2003-11-17 2004-11-10 中国科学院长春应用化学研究所 Method for preparing hydroxyapatite biodegradable aliphatic polyester composite material
AU2004263721A1 (en) * 2003-07-19 2005-02-17 Smith & Nephew Plc High strength bioreabsorbable co-polymers
CN1810305A (en) * 2005-12-19 2006-08-02 四川大学 Reinforced compound nanometer apatite material and its prepn process
US20080305144A1 (en) * 2005-08-18 2008-12-11 Brown Malcolm Nmi High Strength Devices and Composites
CN104984414A (en) * 2015-07-29 2015-10-21 陕西博与再生医学有限公司 Composite absorbable interface screw and preparation method thereof
CN105268033A (en) * 2015-11-06 2016-01-27 杭州锐健马斯汀医疗器材有限公司 Absorbable reticular reinforced interface screw and preparation method thereof
CN105688272A (en) * 2016-02-02 2016-06-22 武汉理工大学 Polymer PRGD/polylactic acid/HAP-PEG composite directional macroporous stent and preparation method thereof
CN107376027A (en) * 2017-06-15 2017-11-24 昆明理工大学 A kind of macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket for cartilaginous tissue reparation and preparation method thereof
CN109337312A (en) * 2018-09-10 2019-02-15 武汉金发科技有限公司 A kind of lactic acid composite material and preparation method thereof
CN110051888A (en) * 2019-04-12 2019-07-26 杭州锐健马斯汀医疗器材有限公司 One kind absorbable compound interface screw sheath flexible and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2004263721A1 (en) * 2003-07-19 2005-02-17 Smith & Nephew Plc High strength bioreabsorbable co-polymers
CN1544524A (en) * 2003-11-17 2004-11-10 中国科学院长春应用化学研究所 Method for preparing hydroxyapatite biodegradable aliphatic polyester composite material
US20080305144A1 (en) * 2005-08-18 2008-12-11 Brown Malcolm Nmi High Strength Devices and Composites
CN1810305A (en) * 2005-12-19 2006-08-02 四川大学 Reinforced compound nanometer apatite material and its prepn process
CN104984414A (en) * 2015-07-29 2015-10-21 陕西博与再生医学有限公司 Composite absorbable interface screw and preparation method thereof
CN105268033A (en) * 2015-11-06 2016-01-27 杭州锐健马斯汀医疗器材有限公司 Absorbable reticular reinforced interface screw and preparation method thereof
CN105688272A (en) * 2016-02-02 2016-06-22 武汉理工大学 Polymer PRGD/polylactic acid/HAP-PEG composite directional macroporous stent and preparation method thereof
CN107376027A (en) * 2017-06-15 2017-11-24 昆明理工大学 A kind of macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket for cartilaginous tissue reparation and preparation method thereof
CN109337312A (en) * 2018-09-10 2019-02-15 武汉金发科技有限公司 A kind of lactic acid composite material and preparation method thereof
CN110051888A (en) * 2019-04-12 2019-07-26 杭州锐健马斯汀医疗器材有限公司 One kind absorbable compound interface screw sheath flexible and preparation method thereof

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
DHONG WON LEE: "Comparison of poly-L-Lactic acid and poly-L-Lactic acid/hydroxyapatite bioabsorbable screws for tibial fixation in ACL reconstruction: clinical and magnetic resonance imaging results", 《CLINICS IN ORTHOPEDIC SURGERY》 *
FATEMEH NEDAIPOUR: "Polylactic acid-polyethylene glycol-hydroxyapatite composite an efficient composition for interference screws", 《NANOCOMPOSITES》 *
HAN-SEUNG KO: "Mechanical Properties and Bioactivity of poly(Lactic Acid) Composites Containing Poly(Glycolic acid) fiber and hydroxyapatite particles", 《NANOMATERIALS》 *
LIU, ZHUO: "Preparation, dynamic rheological behavior, crystallization, and mechanical properties of inorganic whiskers reinforced polylactic acid/hydroxyapatite nanocomposites", 《JOURNAL OF APPLIED POLYMER SCIENCE》 *
NAINAR SM: "influence of maleic anhydride on mechanical properties and morphology of hydroxyapatite/poly-(lactic acid) composites", 《REGENERATIVE RESEARCH》 *
SHEIK MOHIDEEN MOHAMED NAINAR: "Effect of compatibilizers on in vitro biocompatibility of PLA–HA bioscaffold", 《BIOINSPIRED, BIOMIMETIC AND NANOBIOMATERIALS》 *
傅荣: "羟基磷灰石复合聚乳酸可吸收螺钉的力学及生物降解性", 《中国组织工程研究》 *
吴盾: "不同相对分子质量聚乙二醇增塑聚乳酸共混物的制备与性能", 《高分子材料科学与工程》 *
周尧等: "聚乳酸/羟基磷灰石复合材料研究进展", 《应用化工》 *
强涛等: "聚乳酸增韧研究进展", 《高分子材料科学与工程》 *
李玉宝: "《纳米材料技术研发与应用》", 28 February 2012 *
赵西坡等: "弹性体共混改性聚乳酸(PLA)高韧性共混物研究进展", 《材料导报》 *

Similar Documents

Publication Publication Date Title
Zhou et al. Recent progress on chemical modification of cellulose for high mechanical-performance Poly (lactic acid)/Cellulose composite: A review
Ebrahimi et al. Poly lactic acid (PLA) polymers: from properties to biomedical applications
WO2022037349A1 (en) Toughening degradable polyglycolic acid composition, and toughening degradable polyglycolic acid material and preparation method therefor and use thereof
Suwantong Biomedical applications of electrospun polycaprolactone fiber mats
Jayanth et al. A review on biodegradable polymeric materials striving towards the attainment of green environment
EP0108912B1 (en) Poly(glycolic acid)/poly(alkylene glycol)block copolymers and method of manufacturing the same
Dong et al. Degradation behaviors of electrospun resorbable polyester nanofibers
Gunn et al. Polyblend nanofibers for biomedical applications: perspectives and challenges
Zhao et al. Recent progress of preparation of branched poly (lactic acid) and its application in the modification of polylactic acid materials
EP2231913B1 (en) Medical devices containing melt-blown non-wovens of poly-r-hydroxybutyrate and copolymers
US20090274742A1 (en) Multimodal high strength devices and composites
EP1216132A2 (en) A method of making biodegradable polymeric implants
Xiang et al. Toughening modification of PLLA with PCL in the presence of PCL‐b‐PLLA diblock copolymers as compatibilizer
CN107376026B (en) Absorbable bio-medical composition and preparation method thereof
CN110051888A (en) One kind absorbable compound interface screw sheath flexible and preparation method thereof
Bednarek et al. New polylactide-based materials by chemical crosslinking of PLA
Li et al. Poly (L-lactic acid) bio-composites reinforced by oligo (D-lactic acid) grafted chitosan for simultaneously improved ductility, strength and modulus
JP2011506641A (en) Use of coupling agents to improve the interface in absorbent polymer composites
CN104558504A (en) Preparation method of polylactic acid and polyethylene glycol copolymer
Cipurković et al. Biodegradable Polymers: Production, properties and application in medicine
Mtibe et al. Recent insight into the biomedical applications of polybutylene succinate and polybutylene succinate-based materials
CN107320782A (en) Absorbable bio-medical lactic acid composite material and preparation method thereof
Kim et al. Structure–property relationships of 3D-printable chain-extended block copolymers with tunable elasticity and biodegradability
CN101085375A (en) Nanometer biological glass particles, composite material of the same and polyester, and preparation method
Asrar et al. Biosynthetic processes for linear polymers

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200918