CN116036386A - Absorbable glass fiber reinforced polylactic acid composite material and craniomaxillofacial nail plate system - Google Patents
Absorbable glass fiber reinforced polylactic acid composite material and craniomaxillofacial nail plate system Download PDFInfo
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- CN116036386A CN116036386A CN202310159367.7A CN202310159367A CN116036386A CN 116036386 A CN116036386 A CN 116036386A CN 202310159367 A CN202310159367 A CN 202310159367A CN 116036386 A CN116036386 A CN 116036386A
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- polylactic acid
- glass fiber
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 218
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 217
- 239000003365 glass fiber Substances 0.000 title claims abstract description 200
- 239000002131 composite material Substances 0.000 title claims abstract description 137
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims abstract description 59
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims abstract description 34
- -1 16-26% of D Chemical compound 0.000 claims abstract description 8
- 238000001746 injection moulding Methods 0.000 claims description 34
- 239000008187 granular material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 8
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012567 medical material Substances 0.000 abstract description 2
- 210000000988 bone and bone Anatomy 0.000 description 68
- 239000000463 material Substances 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 20
- 238000002347 injection Methods 0.000 description 15
- 239000007924 injection Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000005452 bending Methods 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- 239000011246 composite particle Substances 0.000 description 7
- 239000007943 implant Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- 206010061218 Inflammation Diseases 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000035876 healing Effects 0.000 description 4
- 230000004054 inflammatory process Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 210000004373 mandible Anatomy 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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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
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L31/127—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing fillers of phosphorus-containing inorganic 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
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L31/128—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing other specific inorganic fillers not covered by A61L31/126 or A61L31/127
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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
- A61L31/14—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
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Surgery (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Heart & Thoracic Surgery (AREA)
- Chemical & Material Sciences (AREA)
- Vascular Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention provides an absorbable glass fiber reinforced polylactic acid composite material and a craniomaxillofacial nail plate system, and belongs to the technical field of absorbable medical materials. The absorbable glass fiber reinforced polylactic acid composite material comprises 60-85% of polylactic acid copolymer and 15-40% of degradable glass fiber, wherein the total mass of the composite material is 100%, and the polylactic acid copolymer comprises 70-80% of L-lactide, 16-26% of D, L-lactide and 3-11% of trimethylene carbonate. The absorbable glass fiber reinforced polylactic acid composite material is suitable for preparing a craniomaxillofacial nail plate system, and the obtained craniomaxillofacial nail plate system has excellent mechanical properties and smaller size.
Description
Technical Field
The invention belongs to the technical field of absorbable medical materials, and particularly relates to an absorbable glass fiber reinforced polylactic acid composite material and a craniomaxillofacial nail plate system.
Background
For craniomaxillofacial fracture, a miniature bone plate and screw system is basically adopted for fixation in clinic. The miniature bone plates and screws used are mostly made of titanium alloy, and some of polyetheretherketone. The craniomaxillofacial nail plate system made of two materials of titanium alloy or polyether-ether-ketone has high mechanical strength and good biocompatibility, can meet the requirement of fracture fixation, but has other problems, such as high strength of titanium alloy metal implants, stress shielding, and poor bone healing; for example, titanium alloys and polyetheretherketone are inert implants that are not resorbable and require a secondary surgical removal after bone healing. Therefore, the research on the craniomaxillofacial nail plate system becomes a hot spot, the craniomaxillofacial nail plate system has good biocompatibility, can be degraded and absorbed after in-vivo bone healing, does not need to be taken out by an operation, and is the product most suitable for fracture internal fixation and bone repair at present.
Currently, most of the absorbable pegboard systems clinically used for craniomaxillofacial are products imported from the united states, japan and finland, and the materials used are basically polylactic acid (PLA) or polylactic-co-glycolic acid (PLGA). However, acidic monomers are generated in the degradation process of PLA or PLGA, so that local tissues are in an acidic environment, and thus non-bacterial inflammation can be caused; and the simple PLA or PLGA material has poor mechanical property, and can only increase the size of the product under the condition of meeting the clinical use requirement, thereby being inconvenient to use.
In recent years, composite materials using degradable polymers such as PLA or PLGA as a matrix are used for craniomaxillofacial nail plate systems to make up for the defects of pure PLA or PLGA. For example, patent application CN 108066822A discloses a glass fiber reinforced polylactic acid composite material orthopedic implant and a preparation method thereof, wherein glass fibers are connected with a polylactic acid molecular chain structure through pretreatment, and are compounded with a polylactic acid melt to prepare a prepreg tape, and finally, the prepreg tape is formed through lamination. However, the glass fiber reinforced polylactic acid composite material disclosed in the related art has poor mechanical properties, and the prepared craniomaxillofacial nail plate system has larger size.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems: the glass fiber reinforced polylactic acid composite material disclosed by the related art is not good enough in mechanical property, the prepared craniomaxillofacial nail plate system is large in size, the absorbable glass fiber reinforced polylactic acid composite material is required to be further researched, and the absorbable glass fiber reinforced polylactic acid composite material and the craniomaxillofacial nail plate system are designed, so that the craniomaxillofacial nail plate system has better mechanical property and smaller size.
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides an absorbable glass fiber reinforced polylactic acid composite material and a craniomaxillofacial nail plate system, and the embodiment of the invention combines the two materials according to the characteristics of the polylactic acid copolymer and the degradable glass fiber to prepare the absorbable glass fiber reinforced polylactic acid composite material and the craniomaxillofacial nail plate system. Compared with a craniomaxillofacial nail plate system made of a pure polylactic acid material, the craniomaxillofacial nail plate system made of the absorbable glass fiber reinforced polylactic acid composite material has better mechanical properties, so that the craniomaxillofacial nail plate system can have smaller size.
The absorbable glass fiber reinforced polylactic acid composite material comprises, by taking the total mass of the composite material as 100%, 60-85% of polylactic acid copolymer and 15-40% of degradable glass fiber, and by taking the total mass of the polylactic acid copolymer as 100%, 70-80% of L-lactide, 16-26% of D, L-lactide and 3-11% of trimethylene carbonate.
The absorbable glass fiber reinforced polylactic acid composite material provided by the embodiment of the invention has the following advantages and technical effects:
(1) The degradable glass fiber reinforced polylactic acid composite material provided by the embodiment of the invention contains the degradable glass fiber, and the glass fiber has higher modulus and strength, so that the degradable glass fiber and the polylactic acid copolymer are mixed and then conduct force through an interface, the degradable glass fiber plays a role in reinforcing the polylactic acid copolymer, and the strength of the absorbable glass fiber reinforced polylactic acid composite material obtained after the degradable glass fiber reinforced polylactic acid composite material and the polylactic acid copolymer are combined is higher, so that the mechanical property of the absorbable glass fiber reinforced polylactic acid composite material is obviously better than that of a pure polylactic acid material;
(2) The polylactic acid copolymer is adopted in the absorbable glass fiber reinforced polylactic acid composite material, but not the mixture of poly-L-lactide, poly-D, L-lactide and trimethylene carbonate, so that the mechanical property of the absorbable glass fiber reinforced polylactic acid composite material is improved;
(3) The polylactic acid copolymer is adopted in the absorbable glass fiber reinforced polylactic acid composite material, and the mechanical property of the absorbable glass fiber reinforced polylactic acid composite material can be remarkably improved by adjusting the proportion of three monomer units of L-lactide, D, L-lactide and trimethylene carbonate in the polylactic acid copolymer;
(4) Because the mechanical strength of the absorbable glass fiber reinforced polylactic acid composite material is higher than that of the pure polylactic acid material or the glass fiber reinforced polylactic acid composite material in the related technology, the craniomaxillofacial nail plate system prepared from the absorbable glass fiber reinforced polylactic acid composite material of the embodiment of the invention can have smaller size and is more convenient to use under the condition of reaching the same mechanical strength than that of the pure polylactic acid material or the glass fiber reinforced polylactic acid composite material in the related technology;
(5) The absorbable glass fiber reinforced polylactic acid composite material provided by the embodiment of the invention adopts degradable glass fibers and polylactic acid copolymers, so that the absorbable glass fiber reinforced polylactic acid composite material and the craniomaxillofacial nail plate system provided by the embodiment of the invention can be completely degraded;
(6) The degradation rate of the absorbable glass fiber reinforced polylactic acid composite material and the craniomaxillofacial nail plate system is controllable, degradation products are mutually neutralized, accumulation of acidic products is avoided, and the problem of aseptic inflammation caused by implant degradation is solved.
In some embodiments, the polylactic acid copolymer comprises 70-73% L-lactide, 21-25.5% D, L-lactide, and 4.5-6% trimethylene carbonate, based on 100% total mass of the polylactic acid copolymer.
In some embodiments, the polylactic acid copolymer has a number average molecular weight of 60000-200000g/mol.
In some embodiments, the degradable glass fibers comprise 67-69% silica, 8-9% calcium oxide, 13-14% sodium oxide, 5-6% magnesium oxide, 1-2% phosphorus pentoxide, 0-0.2% aluminum oxide, 0-5.4% boron oxide, 0-0.1% titanium oxide, 0-0.1% strontium oxide, 0-0.1% iron oxide, 0-0.1% barium oxide, based on 100% total mass of the degradable glass fibers.
In some embodiments, the degradable glass fibers have a glass fiber length of 50-1000 μm.
In some embodiments, the degradable glass fiber has a glass fiber length of 100-500 μm.
In some embodiments, the polylactic acid copolymer comprises 70-80% and the degradable glass fiber comprises 20-30% based on 100% of the total mass of the composite.
The embodiment of the invention also provides a preparation method of the absorbable glass fiber reinforced polylactic acid composite material, which comprises the following steps: and extruding the granules of the polylactic acid copolymer and the degradable glass fiber together in an extruder to obtain the absorbable glass fiber reinforced polylactic acid composite material.
The preparation method of the absorbable glass fiber reinforced polylactic acid composite material provided by the embodiment of the invention has the advantages and technical effects that: the absorbable glass fiber reinforced polylactic acid composite material is prepared by adopting an extruder extrusion process, and the method has the advantages of simple steps, convenient operation and convenient industrialized popularization.
The embodiment of the invention also provides a craniomaxillofacial nail plate system which is made of the absorbable glass fiber reinforced polylactic acid composite material.
The craniomaxillofacial nail plate system provided by the embodiment of the invention has the following advantages and technical effects: the craniomaxillofacial nail plate system is made of the absorbable glass fiber reinforced polylactic acid composite material, so that the craniomaxillofacial nail plate system has higher mechanical property; the size is smaller, and the use is more convenient; can be completely degraded; in addition, the problem of aseptic inflammation caused by implant degradation can be solved.
The embodiment of the invention also provides a preparation method of the craniomaxillofacial nail plate system, which comprises the following steps:
(1) Extruding the granules of the polylactic acid copolymer and the degradable glass fiber together in an extruder to obtain the absorbable glass fiber reinforced polylactic acid composite material, or directly mixing the granules of the polylactic acid copolymer and the degradable glass fiber to obtain mixed granules;
(2) Adding the absorbable glass fiber reinforced polylactic acid composite material or the mixed granules obtained in the step (1) into a charging barrel of an injection molding machine, and performing injection molding through a mold to obtain the craniomaxillofacial nail plate system.
The preparation method of the craniomaxillofacial nail plate system provided by the embodiment of the invention has the following advantages and technical effects: the preparation method of the craniomaxillofacial nail plate system provided by the embodiment of the invention can be used for obtaining the craniomaxillofacial nail plate system through the combination of an extrusion process and an injection molding process, can also be independently completed through the injection molding process, is flexible, has simple steps and is suitable for industrial popularization.
Drawings
FIG. 1 is a schematic illustration of the different glass fiber feed locations of examples 1-9 of the present invention;
FIG. 2 is a photograph of a craniomaxillofacial bone plate according to example 1 of the present invention;
FIG. 3 is a photograph of a craniomaxillofacial bone plate according to example 6 of the present invention;
FIG. 4 is a photograph of a craniomaxillofacial bone plate according to example 7 of the present invention taken with a 2.5-dimensional image measuring instrument;
FIG. 5 is a graph showing the length distribution of fibreglass in a craniomaxillofacial bone plate according to example 7 of the present invention;
FIG. 6 is an SEM image of a craniomaxillofacial bone plate of example 7 of the invention;
FIG. 7 is a photograph of a craniomaxillofacial bone plate according to example 8 of the present invention taken with a 2.5-dimensional image measuring instrument;
FIG. 8 is a graph showing the length distribution of fibreglass in a craniomaxillofacial bone plate according to example 8 of the present invention;
FIG. 9 is a photograph of a craniomaxillofacial screw of example 9 of the present invention;
fig. 10 is a photograph of the craniomaxillofacial screw of example 9 and the craniomaxillofacial bone plate of example 1 of the present invention fixed to the mandible after molding at 60 ℃.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The embodiment of the invention provides an absorbable glass fiber reinforced polylactic acid composite material, which comprises 60-85% of polylactic acid copolymer and 15-40% of degradable glass fiber based on 100% of the total mass of the composite material, wherein the polylactic acid copolymer comprises 70-80% of L-lactide (LLA), 16-26% of D, L-lactide (DLLA) and 3-11% of trimethylene carbonate (TMC) based on 100% of the total mass of the polylactic acid copolymer.
Working principle: the absorbable glass fiber reinforced polylactic acid composite material provided by the embodiment of the invention contains the degradable glass fiber and the polylactic acid copolymer, the degradable glass fiber plays a role in reinforcing the polylactic acid copolymer, and the obtained absorbable glass fiber reinforced polylactic acid composite material has higher strength; meanwhile, the absorbable glass fiber reinforced polylactic acid composite material can obtain excellent mechanical properties by adjusting the proportion of the three monomer units of L-lactide, D, L-lactide and trimethylene carbonate in the polylactic acid copolymer. Therefore, when the craniomaxillofacial nail plate system with the same mechanical strength is designed, the craniomaxillofacial nail plate system made of the absorbable glass fiber reinforced polylactic acid composite material can have smaller size and is more convenient to use than the craniomaxillofacial nail plate system made of the pure polylactic acid material or the glass fiber reinforced polylactic acid composite material disclosed in the related technology. In addition, the absorbable glass fiber reinforced polylactic acid composite material provided by the embodiment of the invention adopts the glass fiber and polylactic acid copolymer with good degradability, so that the absorbable glass fiber reinforced polylactic acid composite material and the craniomaxillofacial nail plate system provided by the embodiment of the invention can be completely degraded; in addition, the degradation rate of the absorbable glass fiber reinforced polylactic acid composite material is controllable, degradation products are mutually neutralized, accumulation of acidic products is avoided, and the problem of aseptic inflammation caused by implant degradation can be solved.
The absorbable glass fiber reinforced polylactic acid composite material comprises 60-85% of polylactic acid copolymer and 15-40% of degradable glass fiber, wherein the total mass of the composite material is 100%. When the content of the polylactic acid copolymer is higher than 85%, and the content of the degradable glass fiber is lower than 15%, the mechanical property of the composite material is reduced; and when the content of the polylactic acid copolymer is less than 60% and the content of the degradable glass fiber is more than 40%, the degradation of the composite material is too fast. Preferably, in some embodiments, 70-80% polylactic acid copolymer and 20-30% degradable glass fibers are included, based on 100% total mass of the composite.
In an embodiment of the present invention, the polylactic acid copolymer includes 70 to 80% of L-lactide (LLA), 16 to 26% of D, L-lactide (DLLA) and 3 to 11% of trimethylene carbonate (TMC) based on 100% of the total mass of the polylactic acid copolymer. That is, the absorbable glass fiber reinforced polylactic acid composite material can obtain the mechanical properties required by the present invention only if the polylactic acid copolymer is composed of the monomers of the above types and content ranges. After the polymerization of the above three monomers, the obtained polylactic acid copolymer has higher strength and good plasticity, and the processing temperatures of the respective polymers of L-lactide (LLA), D, L-lactide (DLLA) and trimethylene carbonate (TMC) are different, so that uniform mixing under the same temperature condition can not be realized. The copolymer of the invention can be selected from copolymers of at least two components to blend, and can be uniformly mixed at the same processing temperature, so that the mechanical properties of the product are improved.
If other types of monomers, such as glycolide or caprolactone, are used for the polylactic acid copolymer, the mechanical properties of the obtained composite material are reduced. If the polylactic acid copolymer is a copolymer of any two monomers of L-lactide (LLA), D, L-lactide (DLLA) and trimethylene carbonate (TMC), the mechanical properties or plasticity of the composite material are also reduced. If the content of the monomer adopted by the polylactic acid copolymer is not within the range defined by the embodiment of the invention, the mechanical property of the obtained composite material is also lower.
In the embodiment of the invention, the absorbable glass fiber reinforced polylactic acid composite material can obtain different mechanical properties by adjusting the proportion of three monomer units in the polylactic acid copolymer, and if the proportion of L-lactide (LLA) is higher, the strength of the polylactic acid copolymer is higher, but the brittleness is also higher; the higher the trimethylene carbonate (TMC) content, the better the polylactic acid copolymer is shaped. Thus, to obtain the absorbable glass fiber reinforced polylactic acid composite having good overall properties, it is preferred that in some embodiments, the polylactic acid copolymer comprises 70-73% L-lactide (LLA), 21-25.5% D, L-lactide (DLLA), and 4.5-6% trimethylene carbonate (TMC), based on 100% of the total mass of the polylactic acid copolymer.
In some embodiments, the polylactic acid copolymer has a number average molecular weight of 60000-200000g/mol. If the number average molecular weight of the polylactic acid copolymer is too small, the mechanical property of the product can be quickly reduced in the degradation process, and the mechanical support of the fracture part can not be realized, and if the number average molecular weight of the polylactic acid copolymer is too large, the bone healing rate can not be matched.
In some embodiments, the degradable glass fibers comprise 67-69% silica, 8-9% calcium oxide, 13-14% sodium oxide, 5-6% magnesium oxide, 1-2% phosphorus pentoxide, 0-0.2% aluminum oxide, 0-5.4% boron oxide, 0-0.1% titanium oxide, 0-0.1% strontium oxide, 0-0.1% iron oxide, 0-0.1% barium oxide, based on 100% total mass of the degradable glass fibers. The degradable glass fiber with the components and the proportion has more obvious reinforcing effect on the polylactic acid copolymer, and is beneficial to obtaining the absorbable glass fiber reinforced polylactic acid composite material with higher strength. Meanwhile, the degradable glass fiber with the components and the proportion has better degradability, and is beneficial to complete degradation of the absorbable glass fiber reinforced polylactic acid composite material.
The embodiment of the invention discovers that the glass fiber plays a role in reinforcing the absorbable glass fiber reinforced polylactic acid composite material, the glass fiber length is in the range of 50-1000 mu m, and the absorbable glass fiber reinforced polylactic acid composite material has better mechanical property. When the length of the glass fiber is too short, the mechanical property of the absorbable glass fiber reinforced polylactic acid composite material is poor. When the length of the glass fiber is too long, the injection molding is difficult and the processing is not facilitated. More preferably, in some embodiments, the degradable glass fibers have a glass fiber length of 100-500 μm, and within this range, the longer the glass fiber length, the better the mechanical properties of the absorbable glass fiber-reinforced polylactic acid composite.
The embodiment of the invention also provides a preparation method of the absorbable glass fiber reinforced polylactic acid composite material, which comprises the following steps: and extruding the granules of the polylactic acid copolymer and the degradable glass fiber together in an extruder to obtain the absorbable glass fiber reinforced polylactic acid composite material.
The absorbable glass fiber reinforced polylactic acid composite material is prepared by adopting an extruder extrusion process, and the method has the advantages of simple steps, convenient operation and convenient industrialized popularization.
The embodiment of the invention also provides a craniomaxillofacial nail plate system which is made of the absorbable glass fiber reinforced polylactic acid composite material.
Craniomaxillofacial nail plate systems of embodiments of the present invention include, but are not limited to, bone plates, screws, and the like. The mechanical property of the craniomaxillofacial nail plate system is superior to that of a pure polylactic acid material nail plate system with the same size, for example, the tensile breaking load of the absorbable glass fiber reinforced polylactic acid composite material bone plate is 80-460N, the bone plate can be heated and molded by water bath, and the molding temperature is 55-75 ℃; the maximum torque of the absorbable glass fiber reinforced polylactic acid composite screw is 30-300Nmm. The tensile breaking load of the traditional polylactic acid material bone plate is 60-410N, and the maximum torque of the traditional polylactic acid material screw is 20-270Nmm. In view of the excellent mechanical properties of the craniomaxillofacial pegging system of the embodiments of the present invention, it can be prepared into pegging systems of various shapes, such as bone plate type including straight plates of 2-20 holes, 7-hole plates of C-type, left L-type, right L-type, X-type; accordingly, the screw is used in cooperation with various plate-type bone plates.
The craniomaxillofacial nail plate system provided by the embodiment of the invention has excellent mechanical properties, and is mainly characterized in that the absorbable glass fiber reinforced polylactic acid composite material provided by the embodiment of the invention is adopted: on one hand, the absorbable glass fiber reinforced polylactic acid composite material contains glass fibers, the glass fibers have higher modulus and strength, force is conducted between the glass fibers and the polymer through interfaces, the longer the glass fibers are, the more interfaces are combined with polylactic acid, the larger the bonding force between the glass fibers and the polylactic acid is, and the strength of the composite material is also higher; on the other hand, the polylactic acid copolymer composed of monomers with specific composition and content ratio is selected in the absorbable glass fiber reinforced polylactic acid composite material to replace the traditional pure polylactic acid material, so that the mechanical property of the absorbable glass fiber reinforced polylactic acid composite material is obviously improved.
The traditional polylactic acid material nail plate system has larger size, for example, the thickness of the polylactic acid material bone plate is 0.6-1.7mm, the width is 5.8-8.5mm, and the length is 20-105mm; the bone plate is provided with nail holes, and the aperture is 1.5-3.0mm; the length of the polylactic acid material screw is 5-23mm, and the diameter is 1.5-2.8mm. The craniomaxillofacial nail plate system provided by the embodiment of the invention has mechanical properties superior to those of pure polylactic acid material nail plate systems with the same size, so that the craniomaxillofacial nail plate system provided by the embodiment of the invention can have smaller size when the craniomaxillofacial nail plate system with the same mechanical properties is designed. Specifically, the thickness of the absorbable glass fiber reinforced polylactic acid composite material bone plate is 0.5-1.5mm, the width is 5.8-8.0mm, and the length is 20-100mm; the bone plate is provided with nail holes, and the aperture is 1.4-2.6mm; the length of the absorbable polymer composite material screw is 5-21mm, and the diameter is 1.4-2.6mm.
The embodiment of the invention also provides a preparation method of the craniomaxillofacial nail plate system, which comprises the following steps:
(1) Extruding the granules of the polylactic acid copolymer and the degradable glass fiber together in an extruder to obtain the absorbable glass fiber reinforced polylactic acid composite material, or directly mixing the granules of the polylactic acid copolymer and the degradable glass fiber to obtain mixed granules;
(2) Adding the absorbable glass fiber reinforced polylactic acid composite material or the mixed granules obtained in the step (1) into a charging barrel of an injection molding machine, and performing injection molding through a mold to obtain the craniomaxillofacial nail plate system.
The preparation method of the craniomaxillofacial nail plate system provided by the embodiment of the invention can be used for obtaining the craniomaxillofacial nail plate system through the combination of an extrusion process and an injection process, can also be independently completed through the injection process, is flexible, has simple steps and is suitable for industrial popularization.
The invention can adjust the length of glass fiber in the granules by changing the processing form and processing technology of the granules, thereby changing the length of glass fiber in the products. The applicant found that: in the craniomaxillofacial nail plate system obtained by the injection molding process alone, the average glass fiber length is higher than that of a product obtained by combining the extrusion process and the injection molding process, so that the mechanical property of the prepared product is more excellent.
Further, in some embodiments, the preparation method of the craniomaxillofacial nail plate system of the embodiments of the present invention specifically includes the following steps:
(1) Adding the granules of the polylactic acid copolymer into a hopper of a feeder of an extruder, setting the heating temperature of the extruder to 160-220 ℃, setting the rotating speed of the extruder to 50-100rpm, setting the rotating speed of the feeder to 1-5rpm, and starting a screw and the feeder when the temperature reaches the set temperature; when the extruder die head comes out of the resin, putting the degradable continuous glass fiber into an intermediate or terminal observation port of the extruder, continuously extruding and naturally cooling the material strips of the composite material, collecting the material strips, and then granulating the extruded material strips of the composite material to obtain the granules of the absorbable glass fiber reinforced polylactic acid composite material;
(2) Adding the granules of the absorbable glass fiber reinforced polylactic acid composite material into a charging barrel of an injection molding machine, and performing injection molding through a mold to obtain the craniomaxillofacial nail plate system, wherein the heating temperature of the injection molding machine is 180-235 ℃, the injection pressure is 600-1900bar, the cooling time is 4-15s, and the mold temperature is 30-60 ℃.
Further, in some embodiments, the preparation method of the craniomaxillofacial nail plate system of the embodiments of the present invention specifically includes the following steps:
(1) Directly mixing granules of the polylactic acid copolymer and the degradable glass fiber to obtain mixed granules;
(2) Adding the mixed granules into a charging barrel of an injection molding machine, and performing injection molding through a mold to obtain the craniomaxillofacial nail plate system, wherein the heating temperature of the injection molding machine is 180-235 ℃, the injection pressure is 600-1900bar, the cooling time is 4-15s, and the mold temperature is 30-60 ℃.
The present invention will be described in detail with reference to the following examples and drawings.
The degradable glass fibers used in examples 1-9 below were purchased from Arctic Biomaterials Oy and included 68% silica, 8.5% calcium oxide, 13.5% sodium oxide, 5.5% magnesium oxide, 1.5% phosphorus pentoxide, 0.1% aluminum oxide, 2.5% boron oxide, 0.1% titanium oxide, 0.1% strontium oxide, 0.1% iron oxide, 0.1% barium oxide, based on 100% of the total mass of the degradable glass fibers.
Example 1
An absorbable glass fiber reinforced polylactic acid composite material craniomaxillofacial bone plate and a preparation method thereof are provided: polylactic acid copolymer (85 g PLDLLA) (LLA: DLLA=70:30) and PLT (LLA: TMC=70:30) were uniformly mixed and fed into an extruder feeder (position see FIG. 1), 3 bundles of 136tex continuous glass fibers were fed into a screw from an intermediate view port (position see FIG. 1) of the extruder, at a screw temperature of 165 ℃, a screw speed of 50rpm and a feed speed of 2rpmContinuously extruding and granulating under the process condition of rotating speed to obtain glass fiber reinforced polylactic acid composite material particles, wherein the polylactic acid copolymer comprises the following components: DLLA: tmc=70: 25.5:4.5. the composite particles were added to an injection molding machine at a mold temperature of 40 c and an injection pressure of 1000bar, and injection molded with a 6-well plate mold at a processing temperature of 185 c for a cooling time of 10s to obtain a composite 6-well bone plate, as shown in fig. 2. Wherein the thickness of the 6-hole plate is 1.27mm, the width is 6.6mm, the length is 36mm, the content of polylactic acid copolymer in the 6-hole bone plate is 80%, the average content of glass fiber is 20%, the average length of glass fiber is 190 mu m, the intrinsic viscosity of the 6-hole bone plate is 1.55dL/g, the average tensile breaking load is 286.3N, the bending load is 23.7N, and the impact strength is 21.4kJ/m 2 。
Example 2
An absorbable glass fiber reinforced polylactic acid composite material craniomaxillofacial bone plate and a preparation method thereof are provided: 80g PLDLLA (LLA: DLLA=70:30) and 20g PLT (LLA: TMC=70:30) of a polylactic acid copolymer were uniformly mixed and fed into an extruder feeder (position see FIG. 1), 3 bundles of 136tex continuous glass fibers were fed into a screw from a middle viewing port (position see FIG. 1) of the extruder, and continuously extruded and pelletized under the process conditions of a screw temperature of 165 ℃, a screw speed of 50rpm and a feeding speed of 2rpm, to obtain glass fiber reinforced polylactic acid composite particles, wherein the polylactic acid copolymer has a composition of LLA: DLLA: tmc=70: 24:6. adding the composite material particles into an injection molding machine, wherein the mold temperature is 40 ℃, the injection pressure is 1000bar, and the composite material 6-hole bone plate is obtained by injection molding with a 6-hole plate mold at the processing temperature of 185 ℃ and the cooling time is 10 s. Wherein the content of polylactic acid copolymer in the 6-hole bone plate is 80%, the average content of glass fiber is 20%, the average length of the glass fiber is 190 mu m, the intrinsic viscosity of the 6-hole bone plate is 1.57dL/g, the average tensile breaking load is 244.8N, the bending load is 20N, and the impact strength is 22.7kJ/m 2 . Since trimethylene carbonate (TMC) contains a soft segment, the higher the TMC content in the polylactic acid copolymer, the lower the mechanical properties and the higher the toughness, the tensile breaking load and bending load of the 6-hole bone plate of this example are lower than those of example 1, and the impact strength is higher than that of example 1.
Example 3
An absorbable glass fiber reinforced polylactic acid composite material craniomaxillofacial bone plate and a preparation method thereof are provided: 90g PLDLLA (LLA: DLLA=70:30) and 10g PLT (LLA: TMC=70:30) of a polylactic acid copolymer were uniformly mixed and fed into an extruder feeder (position see FIG. 1), 3 bundles of 136tex continuous glass fibers were fed into a screw from a middle viewing port (position see FIG. 1) of the extruder, and continuously extruded and pelletized under the process conditions of a screw temperature of 165 ℃, a screw speed of 50rpm and a feeding speed of 2rpm, to obtain glass fiber reinforced polylactic acid composite particles, wherein the polylactic acid copolymer has a composition of LLA: DLLA: tmc=70: 27:3. adding the composite material particles into an injection molding machine, wherein the mold temperature is 40 ℃, the injection pressure is 1000bar, and the composite material 6-hole bone plate is obtained by injection molding with a 6-hole plate mold at the processing temperature of 185 ℃ and the cooling time is 10 s. Wherein the content of polylactic acid copolymer in the 6-hole bone plate is 79%, the average content of glass fiber is 21%, the average length of glass fiber is 190 mu m, the intrinsic viscosity of the 6-hole bone plate is 1.45dL/g, the average tensile breaking load is 223.1N, the bending load is 19.4N, and the impact strength is 21.0kJ/m 2 . Because of the lower trimethylene carbonate (TMC) content, the polylactic acid copolymer has poorer compatibility with glass fibers, resulting in lower mechanical properties, and the higher PLDLLA content results in a material having higher brittleness, the tensile breaking load, bending load and impact strength of the 6-hole bone plate of this example are lower than those of example 1.
Example 4
An absorbable glass fiber reinforced polylactic acid composite material craniomaxillofacial bone plate and a preparation method thereof are provided: 50g of polylactic acid composite material PLDLLA (LLA: DLLA=70:30) containing 40% glass fibers, 38g of PLDLLA (LLA: DLLA=70:30) and 12g of PLT (LLA: TMC=70:30) are uniformly mixed, and then are directly added into an injection molding machine, the mold temperature is 40 ℃, the injection pressure is 1000bar, and the composite material 6-hole bone plate is obtained by injection molding with a 6-hole plate mold in example 4 at the processing temperature of 185 ℃ and the cooling time is 10 s. Wherein the polylactic acid copolymer composition of the 6-pore plate is LLA: DLLA: tmc=70: 25.5: the 4.5,6 orifice plate had a polylactic acid copolymer content of 80%, an average glass fiber content of 20%, an average glass fiber length of 400 μm, a viscosity of 1.6dL/g in the 6 orifice plate, an average tensile break load of 307.2N, and a bending load of 25.3N. Because the glass fiber in the composite material plays a role in reinforcing, the longer the glass fiber is, the greater the strength of the composite material is, so the mechanical property of the bone plate of the embodiment is greater than that of the embodiment 1.
Example 5
An absorbable glass fiber reinforced polylactic acid composite material craniomaxillofacial bone plate and a preparation method thereof are provided: 80g PLDLLA (LLA: DLLA=70:30) and 20g PLT (LLA: TMC=70:30) of a polylactic acid copolymer were uniformly mixed and fed into an extruder feeder (position see FIG. 1), 6 bundles of 136tex continuous glass fibers were fed into a screw from a middle viewing port (position see FIG. 1) of the extruder, and continuously extruded and pelletized under the process conditions of a screw temperature of 165 ℃, a screw speed of 50rpm and a feeding speed of 2rpm, to obtain glass fiber reinforced polylactic acid composite particles, wherein the polylactic acid copolymer has a composition of LLA: DLLA: tmc=70: 24:6. adding the composite material particles into an injection molding machine, wherein the mold temperature is 40 ℃, the injection pressure is 1000bar, and the composite material 6-hole bone plate is obtained by injection molding with a 6-hole plate mold at the processing temperature of 185 ℃ and the cooling time is 10 s. Wherein, in the 6-hole bone plate, the content of the polylactic acid copolymer is 60 percent, the average content of glass fiber is 40 percent, the average length of the glass fiber is 190 mu m, the viscosity of the 6-hole bone plate is 1.4dL/g, the average tensile breaking load is 292.5N, and the bending load is 24.1N. In the embodiment, the glass fiber content is increased, and the mechanical property of the composite material is increased, so that the tensile breaking load of the 6-hole bone plate is higher than that of the embodiment 2.
Example 6
An absorbable glass fiber reinforced polylactic acid composite material craniomaxillofacial bone plate and a preparation method thereof are provided: polylactic acid copolymer 54g PLDLLA (LLA: DLLA=80:20) and PLT 10g (LLA: TMC=70:30) were uniformly mixed and fed into an extruder feeder (position see FIG. 1), 3 bundles of 165tex continuous glass fibers were fed into a screw from an extruder middle viewing port (position see FIG. 1), and continuously extruded and pelletized under the process conditions of screw temperature of 185 ℃, screw speed of 50rpm and feeding speed of 2rpm, to obtain glass fiber reinforced polylactic acid composite particles, wherein the polylactic acid copolymer has the composition LLA: DLLA: tmc=78.4: 16.9:4.7. the composite material was fed into an injection molding machine at a mold temperature of 45 c and an injection pressure of 1800bar, and injection molded with a 4-hole plate mold at a processing temperature of 205 c for a cooling time of 10s, to obtain a composite material 4-hole bone plate, as shown in fig. 3. The content of polylactic acid copolymer in the bone plate is 70%, the average content of glass fiber is 30%, the average length of glass fiber in the bone plate is 270 mu m, the intrinsic viscosity of polylactic acid copolymer in the 4-hole bone plate is 1.54dL/g, the average tensile breaking load of the 4-hole bone plate is 104.9N, and the bending strength is 94MPa.
Example 7
An absorbable glass fiber reinforced polylactic acid composite material craniomaxillofacial bone plate and a preparation method thereof are provided: polylactic acid copolymer 54g PLDLLA (LLA: DLLA=80:20) and PLT 10g (LLA: TMC=70:30) were uniformly mixed and fed into an extruder feeder (position see FIG. 1), 3 bundles of 165tex continuous glass fibers were fed into a screw from an extruder middle viewing port (position see FIG. 1), and continuously extruded and pelletized under the process conditions of a screw temperature of 190 ℃, a screw speed of 50rpm and a feeding speed of 2rpm, to obtain glass fiber reinforced polylactic acid composite particles, wherein the polylactic acid copolymer has a composition of LLA: DLLA: tmc=78.4: 16.9:4.7. adding the composite material into an injection molding machine, wherein the mold temperature is 45 ℃, the injection pressure is 1800bar, and the composite material 4-hole bone plate is obtained by injection molding with a 4-hole plate mold at the processing temperature of 205 ℃ and the cooling time is 10 s. Wherein the width of the 4-hole bone plate is 5.8mm, the thickness is 1mm, the length is 20.8mm, the content of polylactic acid copolymer in the 4-hole bone plate is 70%, the content of glass fiber is 30%, and the average length of glass fiber is 270 μm. The intrinsic viscosity of the polylactic acid copolymer in the 4-hole bone plate was 1.38dL/g, the average tensile breaking load of the 4-hole bone plate was 94.2N, and the bending strength was 85MPa. Since the screw temperature is higher than that of example 6, the polylactic acid copolymer matrix undergoes more thermal degradation during processing, and the molecular weight of the processed matrix remains less than that of example 6, the intrinsic viscosity is lower than that of example 6, and the mechanical properties are also lower than those of example 6. And adding glass fibers from an observation port section in the middle of the extruder, wherein the length distribution of the glass fibers in the obtained product is shown in fig. 4 and 5, and the distribution state of the glass fibers in the bone plate corresponding to the obtained composite material is shown in fig. 6.
Example 8
An absorbable glass fiber reinforced polylactic acid composite material craniomaxillofacial bone plate and a preparation method thereof are provided: polylactic acid copolymer 54g PLDLLA (LLA: DLLA=80:20) and PLT (LLA: TMC=70:30) were uniformly mixed and fed into an extruder feeder (position see FIG. 1), 3 bundles of 165tex continuous glass fibers were fed into a screw from an extruder feed zone viewing port (position see FIG. 1), and continuously extruded and pelletized under the process conditions of a screw temperature of 190 ℃, a screw speed of 50rpm and a feed speed of 2rpm, to obtain glass fiber reinforced polylactic acid composite particles, wherein the polylactic acid copolymer had a composition of LLA: DLLA: tmc=78.4: 16.9:4.7. adding the composite material into an injection molding machine, wherein the mold temperature is 45 ℃, the injection pressure is 1800bar, and the composite material 4-hole bone plate is obtained by injection molding with a 4-hole plate mold at the processing temperature of 205 ℃ and the cooling time is 10 s. Wherein the width of the 4-hole bone plate is 5.8mm, the thickness is 1mm, the length is 20.8mm, the content of polylactic acid copolymer in the 4-hole bone plate is 70%, the content of glass fiber is 30%, and the average length of glass fiber is 180 μm. The intrinsic viscosity of the polylactic acid copolymer in the 4-hole bone plate was 1.27dL/g, the average tensile breaking load of the 4-hole bone plate was 82.5N, and the bending strength was 78.2MPa. And adding glass fibers from an observation port of a feeding section of the extruder, wherein the length distribution of the glass fibers in the obtained product is shown in fig. 7 and 8.
Example 9
An absorbable glass fiber reinforced polylactic acid composite material craniomaxillofacial bone plate and a preparation method thereof are provided: 50g of polylactic acid composite material PLDLLA (LLA: DLLA=70:30), 34g of PLDLLA (70:30) and 16g of PLT (LLA: TMC=70:30) containing 40% glass fibers are uniformly mixed, and then are directly added into an injection molding machine for injection molding, the mold temperature is 40 ℃, the injection pressure is 1000bar, and the injection molding is carried out at the processing temperature of 205 ℃ by using a screw mold, and the cooling time is 10s, so that a composite material screw is obtained, as shown in fig. 9. Wherein the external thread diameter of the screw is 2.0mm, the length of the screw is 11mm, the content of polylactic acid copolymer in the screw is 80%, the average content of glass fiber is 20%, the average length of glass fiber is 400 mu m, and the composition of polylactic acid copolymer is LLA: DLLA: tmc=70: 24:6. the average torque of the composite screw was 60Nmm. The effect of the shaped six-hole bone plate of example 1 and the 2.0mm diameter screw of this example was fixed to the mandible at 60℃as shown in FIG. 10.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. An absorbable glass fiber reinforced polylactic acid composite material, which is characterized in that the composite material comprises 60-85% of polylactic acid copolymer and 15-40% of degradable glass fiber based on 100% of the total mass of the composite material, wherein the polylactic acid copolymer comprises 70-80% of L-lactide, 16-26% of D, L-lactide and 3-11% of trimethylene carbonate based on 100% of the total mass of the polylactic acid copolymer.
2. The absorbable glass fiber reinforced polylactic acid composite material of claim 1, wherein the polylactic acid copolymer comprises 70-73% L-lactide, 21-25.5% D, L-lactide, and 4.5-6% trimethylene carbonate, based on 100% total mass of the polylactic acid copolymer.
3. The absorbable glass fiber reinforced polylactic acid composite material of claim 1 or 2, wherein the polylactic acid copolymer has a number average molecular weight of 60000-200000g/mol.
4. The absorbable glass fiber reinforced polylactic acid composite of claim 1, wherein the degradable glass fiber comprises 67-69% silica, 8-9% calcium oxide, 13-14% sodium oxide, 5-6% magnesium oxide, 1-2% phosphorus pentoxide, 0-0.2% aluminum oxide, 0-5.4% boron oxide, 0-0.1% titanium oxide, 0-0.1% strontium oxide, 0-0.1% iron oxide, 0-0.1% barium oxide, based on 100% total mass of the degradable glass fiber.
5. The absorbable glass fiber reinforced polylactic acid composite material of claim 1 or 4, wherein the degradable glass fiber has a glass fiber length of 50-1000 μιη.
6. The absorbable glass fiber reinforced polylactic acid composite material of claim 5, wherein the degradable glass fiber has a glass fiber length of 100-500 μm.
7. The absorbable glass fiber reinforced polylactic acid composite material of claim 1, wherein the composite material comprises 70-80% of the polylactic acid copolymer and 20-30% of the degradable glass fiber, based on 100% of the total mass of the composite material.
8. The method for preparing the absorbable glass fiber reinforced polylactic acid composite material according to any one of claims 1 to 7, comprising the following steps: and extruding the granules of the polylactic acid copolymer and the degradable glass fiber together in an extruder to obtain the absorbable glass fiber reinforced polylactic acid composite material.
9. A craniomaxillofacial pegboard system made from the absorbable fiberglass-reinforced polylactic acid composite material of any one of claims 1-7.
10. The method of preparing a craniomaxillofacial pegboard system according to claim 9, comprising the steps of:
(1) Extruding the granules of the polylactic acid copolymer and the degradable glass fiber together in an extruder to obtain the absorbable glass fiber reinforced polylactic acid composite material, or directly mixing the granules of the polylactic acid copolymer and the degradable glass fiber to obtain mixed granules;
(2) Adding the absorbable glass fiber reinforced polylactic acid composite material or the mixed granules obtained in the step (1) into a charging barrel of an injection molding machine, and performing injection molding through a mold to obtain the craniomaxillofacial nail plate system.
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