CN110237310A - A kind of absorbable interference screw fixation and preparation method thereof - Google Patents
A kind of absorbable interference screw fixation and preparation method thereof Download PDFInfo
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- CN110237310A CN110237310A CN201910591168.7A CN201910591168A CN110237310A CN 110237310 A CN110237310 A CN 110237310A CN 201910591168 A CN201910591168 A CN 201910591168A CN 110237310 A CN110237310 A CN 110237310A
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- tricalcium phosphate
- interference screw
- screw fixation
- vicryl rapide
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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
- A61L31/02—Inorganic materials
- A61L31/028—Other inorganic materials not covered by A61L31/022 - A61L31/026
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
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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
- A61L31/148—Materials at least partially resorbable by the body
Abstract
The present invention relates to medical material tech fields, more particularly, to a kind of absorbable interference screw fixation and preparation method thereof.The absorbable interference screw fixation is mainly made of Vicryl Rapide and modified bata-tricalcium phosphate；The method of the modification includes: to be activated bata-tricalcium phosphate in phosphoric acid.The present invention, so that bata-tricalcium phosphate and Vicryl Rapide have good interface compatibility, makes absorbable interference screw fixation have good mechanical property by being modified processing to bata-tricalcium phosphate；Meanwhile after modification, bata-tricalcium phosphate is matched with the degradation rate of Vicryl Rapide, and can finally be excreted, through absorption of human body, metabolism to human body without adverse side effect.
Description
Technical field
The present invention relates to medical material tech fields, more particularly, to a kind of absorbable interference screw fixation and preparation method thereof.
Background technique
Cruciate ligament is clinical common one of diseases of knee joint, currently, the bone of cruciate ligament before and after treatment
The method that section performs the operation frequently with cruciate ligament reconstruction under arthroscope is dug in shin bone and femur position for installing tendon and ligament
Tunnel, then the inner wall of osseous tunnel will be fixed on interference screw at the top of tendon and ligament.Wherein, interference screw used can be by
Metal material, high molecular material etc. are prepared.
Traditional metal interference screw although mechanical strength and fatigue performance with higher, can meet clinical operation pair
The demand of its performance, but after metal material implantation human body, metal material cannot degrade in vivo, therefore need to carry out after curing
Second operation is drawn off, and causes secondary injury to patient.In recent years, degradable interference screw relies on its unique advantage, by
Extensive concern, but there is also a series of problems, for example, pure polyacids type can absorb interface nail, degradation speed is too fast, and
A large amount of lactic acid can be generated in degradation process, lactic acid is caused to accumulate, to cause a series of inflammatory problems.Hydroxyapatite
(HA) with the compound interface screw of polylactic acid composition, it can effectively solve the problems, such as that pure polylactic acid degradation speed is too fast, but hydroxyl
Apatite (HA) is substantially non-degradable in human body.Bata-tricalcium phosphate/polylactic acid compound interface screw, bata-tricalcium phosphate are human body bone
The main inorganic constituents of bone, can be absorbed degradation in human body, but the degradation of the degradation speed of bata-tricalcium phosphate and polylactic acid
Speed mismatches, and restricts its application development.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of absorbable interference screw fixation, to solve interface existing in the prior art
The technical problems such as screw degradation rate mismatch.
The second object of the present invention is to provide a kind of preparation method of absorbable interference screw fixation, and preparation method is simple, system
The absorbable interference screw fixation mechanical property with higher and biodegradability obtained.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of absorbable interference screw fixation, mainly by Vicryl Rapide 70-90% and modified bata-tricalcium phosphate system
At；
The method of the modification includes: to be activated bata-tricalcium phosphate in phosphoric acid.
The present invention is by being modified processing to bata-tricalcium phosphate, so that bata-tricalcium phosphate and Vicryl Rapide
With good interface compatibility, make absorbable interference screw fixation that there is good mechanical property.
Meanwhile after modification, bata-tricalcium phosphate is matched with the degradation rate of Vicryl Rapide, and can be through people
Body is absorbed, is metabolized, and is finally excreted, to human body without adverse side effect.
Preferably, the absorbable interference screw fixation is mainly by Vicryl Rapide 70-90 according to parts by weight
Part is made with modified bata-tricalcium phosphate 10-30 parts.
As in various embodiments, the dosage of Vicryl Rapide can be 70 parts, 72 parts, 75 parts, 78
Part, 80 parts, 82 parts, 85 parts, 88 parts, 90 parts etc.；The dosage of modified bata-tricalcium phosphate can be 10 parts, 12 parts, 15 parts, 18
Part, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 40 parts etc..
Wherein, Vicryl Rapide refers to the polymer being copolymerized using glycolide and lactide as monomer.
Lactide includes any one of L- lactide, D- lactide or two kinds of mixing.
It is preferred that monomer residue (glycolide, lactide) total amount should be not more than as mass fraction in the copolymer
2.0%；Dissolvent residual (total amount) answers < 1000ppm, and content of beary metal (in terms of lead, except tin) answers≤10ppm, and tin residual quantity is answered
≤ 150ppm, water residual quantity answer≤0.5%, Trace Element Arsenic≤3 μ g/g, cadmium≤5 μ g/g, mercury≤5 μ g/g, lead≤30 μ g/g.
Calcium phosphorus atoms ratio is Ca/P=1.50 in bata-tricalcium phosphate.
Preferably, the weight average molecular weight of the Vicryl Rapide is 20,000-20 ten thousand, preferably 5-15 ten thousand.
As in various embodiments, the weight average molecular weight of Vicryl Rapide can be 20,000,2.5 ten thousand, 3
Ten thousand, 3.5 ten thousand, 40,000,4.5 ten thousand, 50,000,5.5 ten thousand, 60,000,6.5 ten thousand, 70,000,7.5 ten thousand, 80,000,8.5 ten thousand, 90,000,9.5 ten thousand, 100,000,
10.5 ten thousand, 110,000,11.5 ten thousand, 120,000,12.5 ten thousand, 130,000,13.5 ten thousand, 140,000,14.5 ten thousand, 150,000,15.5 ten thousand, 160,000,16.5
Ten thousand, 170,000,17.5 ten thousand, 180,000,18.5 ten thousand, 190,000,19.5 ten thousand, 200,000 etc..
In a preferred embodiment of the invention, the molecular weight distribution of the Vicryl Rapide is 1.5-4.0,
Preferably 1.5-3.0.
As in various embodiments, the molecular weight distribution of Vicryl Rapide can for 1.5,1.8,2.0,
2.2,2.5,2.8,3.0,3.2,3.5,3.8,4.0 etc..
Using the Vicryl Rapide of above-mentioned weight average molecular weight and molecular weight distribution, help to make its with it is modified
Bata-tricalcium phosphate has the degradation rate to match, combines good mechanical property.
Preferably, 25 DEG C of inherent viscosities of the Vicryl Rapide are 1.0-2.5dL/g, preferably 1.25-
2.0dL/g。
Preferably, 20 DEG C of specific rotatory powers of the Vicryl Rapide are 2.5 ° of -2.5 °~﹢.
The present invention also provides a kind of preparation methods of absorbable interference screw fixation, include the following steps:
The modified bata-tricalcium phosphate that will be activated in phosphoric acid, in proportion with Vicryl Rapide
It is blended, molding.
Preferably, the phosphoric acid is dilute phosphoric acid solution.The specially aqueous solution of phosphoric acid.It is furthermore preferred that the phosphoric acid,diluted is molten
The mass fraction of liquid is 5-20%, further preferably 2-10%.
Preferably, the mass ratio of the bata-tricalcium phosphate and dilute phosphoric acid solution is 1 ﹕ (2-4), more preferably 1 ﹕ (2-3).
In a specific embodiment of the invention, dilute phosphoric acid solution can be added into bata-tricalcium phosphate, phosphoric acid,diluted is being added
It is stirring while adding during solution, it is uniformly mixed it.
Preferably, the time of the activation processing is 1-2h.
Preferably, the method for the activation processing includes: that bata-tricalcium phosphate is stirred processing in phosphoric acid, vacuum filtration
After be dried in vacuo.In a specific embodiment of the invention, distillation water washing can be used after vacuum filtration, remove extra phosphorus
Acid；Further in being dried in vacuo more than for 24 hours or for 24 hours under room temperature.
Preferably, the temperature of the blending is 20-25 DEG C；The time of the blending is 60-180min.
In a specific embodiment of the invention, specific blending operations include: that preparatory glycolide lactide of preparing is copolymerized
The solution of object is proportionally added into modified bata-tricalcium phosphate, is ultrasonically treated 0.5-2h, stirs 0.5-1h；In this way can
It is dispersed in modified bata-tricalcium phosphate in the solution of Vicryl Rapide.After being uniformly dispersed, it is dry that freezing can be used
Dry mode is dried, and removes solvent, obtains that particle is blended.
Wherein, Vicryl Rapide is dissolved in appropriate solvent in advance, the optional chloroform of solvent, acetone, methanol,
Tetrahydrofuran, benzene, n,N-Dimethylformamide and hexafluoroisopropanol obtain Vicryl Rapide solution.Optionally,
Solid content is 10-40wt%.As in different embodiments, can for 10wt%, 15wt%, 20wt%, 25wt%,
30wt%, 35wt%, 40wt% etc..
Wherein, refer in proportion, in the solution of Vicryl Rapide admittedly containing Vicryl Rapide with
Modified bata-tricalcium phosphate is respectively 70-90 parts and 10-40 parts in parts by weight therebetween.
Type can be made by Shooting Technique after modified bata-tricalcium phosphate is blended in proportion with Vicryl Rapide
Bar obtained is oriented drawing process processing by material such as bar.
Preferably, the Shooting Technique includes the following steps: that particle will be blended to be mixed with the nucleating agent for being scattered in organic solvent
It closes uniformly, removes organic solvent, carry out low crystallization, then carry out injection molding.Wherein, injection temperature is preferably 140-260
DEG C, mold temperature is preferably 50-240 DEG C.
Wherein, nucleating agent uses Conventional nucleating agents.
Preferably, the quality of the nucleating agent is 0.05-20%, the preferably 0.1-10% that the quality of particle is blended, more
Preferably 2-6%.
In a specific embodiment of the invention, organic solvent can be removed by way of evaporating under vacuum or normal pressure,
Preferable temperature is 20-80 DEG C.
In a specific embodiment of the invention, the temperature of low crystallization is 50-140 DEG C, and crystallinity is made to be no more than 50%.
As in different embodiments, the temperature of minuent crystallization can be 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100
DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C etc..Crystallinity can be made to be no more than 50%, more preferably no more than 30%, Ke Yiwei
10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% etc..
Wherein, the method for low crystallization preferably includes: titanium dioxide, oxidation being added into the mixture for removing organic solvent
Calcium or magnesia regulate and control crystallinity.The additional amount of titanium dioxide, calcium oxide or magnesia can be 0.01-0.1wt%.
Preferably, after molding, obtained profile is oriented stretch processing.It is furthermore preferred that stretching ratio is 1.1-1.5
Times.
It is handled by above-mentioned orientation stretching, obtains highly oriented material, the mechanical strength of material can be further increased.
After orientation stretching processing, it is machined out, obtains absorbable interference screw fixation.The shape of screw can be according to practical need
It asks and is adjusted.
Compared with prior art, the invention has the benefit that
(1) bata-tricalcium phosphate is modified processing, improves bata-tricalcium phosphate and second by absorbable interference screw fixation of the invention
The compatibility of lactide lactide copolymer, and make bata-tricalcium phosphate and Vicryl Rapide that there is the degradation speed to match
Rate；
(2) preparation method of absorbable interference screw fixation of the invention, easy to operate, reproducible, what is be prepared inhales
Receive biodegradability interference screw mechanical property with higher and matched.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is Vicryl Rapide provided in an embodiment of the present invention (Copolymer), is modified bata-tricalcium phosphate
The degradation rate figure of (modified β-TCP), bata-tricalcium phosphate (unmodified β-TCP).
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
The preparation method of the absorbable interference screw fixation of the present embodiment, includes the following steps:
(1) bata-tricalcium phosphate particle 100g is taken, 250g mass fraction is added for 10% phosphoric acid,diluted, at blended under agitation activation
Reason, vacuum filtration, solid is dried in vacuo, and obtains modified bata-tricalcium phosphate；
(2) modified bata-tricalcium phosphate 80g obtained in step (1) is taken, is total to solid containing the glycolide lactide for being 30wt%
The chloroformic solution of polymers handles 1h under conditions of 25 DEG C in ultrasonic oscillator, then stirs 1h and obtains mixed solution, will
Mixed solution carries out freeze-drying process, removes solvent, obtains that particle is blended；
Wherein, in the chloroformic solution of Vicryl Rapide, Vicryl Rapide content is 640g；Chloroform
May be replaced by any one of acetone, methanol, tetrahydrofuran, benzene, n,N-Dimethylformamide and hexafluoroisopropanol or
A variety of mixing；
(3) 5g nucleating agent is blended to particle 100g to be uniformly mixed with obtained in step (2), is subsequently placed in vacuum drying oven
In, the titanium dioxide of 0.05wt% is added after solvent evaporating completely in 40-50 DEG C of evaporation removing solvent, to obtained particle
Low crystallization, crystallinity 25% are carried out at 60 DEG C；
Particle after low crystallization is directly subjected to injection molding and obtains bar, injection temperature is 160 DEG C, and mold temperature is
100 DEG C, then the self-reinforcing process that bar is oriented stretching is handled, 1.5 times of stretching ratio；
(4) material by oriented stretch processing obtained in step (3) is machined out, and obtains absorbable interface spiral shell
Nail.
Wherein, the weight average molecular weight of the Vicryl Rapide of the present embodiment is 100,000, molecular weight distribution 2.0,
(25 DEG C) of inherent viscosity are 2.0dL/g, and (20 DEG C) of specific rotatory power are 0.5 °.
The partial size of bata-tricalcium phosphate is 0.5 μm.
Embodiment 2
The preparation method of the absorbable interference screw fixation of the present embodiment, includes the following steps:
(1) bata-tricalcium phosphate particle 100g is taken, 250g mass fraction is added for 10% phosphoric acid,diluted, at blended under agitation activation
Reason, vacuum filtration, solid is dried in vacuo, and obtains modified bata-tricalcium phosphate；
(2) modified bata-tricalcium phosphate 50g obtained in step (1) is taken, is total to solid containing the glycolide lactide for being 30wt%
The chloroformic solution of polymers handles 1h under conditions of 25 DEG C in ultrasonic oscillator, then stirs 1h and obtains mixed solution, will
Mixed solution carries out freeze-drying process, removes solvent, obtains that particle is blended；
Wherein, in the chloroformic solution of Vicryl Rapide, Vicryl Rapide content is 450g；
(3) 5g nucleating agent is blended to particle 100g to be uniformly mixed with obtained in step (2), is subsequently placed in vacuum drying oven
In, the titanium dioxide of 0.05wt% is added after solvent evaporating completely in 40-50 DEG C of evaporation removing solvent, to obtained particle
Low crystallization, crystallinity 25% are carried out at 60 DEG C；
Particle after low crystallization is directly subjected to injection molding and obtains bar, injection temperature is 160 DEG C, and mold temperature is
100 DEG C, then the self-reinforcing process that bar is oriented stretching is handled, stretching ratio is 1.5 times；
(4) material by oriented stretch processing obtained in step (3) is machined out, and obtains absorbable interface spiral shell
Nail.
Wherein, the weight average molecular weight of the Vicryl Rapide of the present embodiment is 100,000, molecular weight distribution 2.0,
(25 DEG C) of inherent viscosity are 2.0dL/g, and (20 DEG C) of specific rotatory power are 0.5 °.
The partial size of bata-tricalcium phosphate is 0.5 μm.
Embodiment 3
The preparation method of the absorbable interference screw fixation of the present embodiment, includes the following steps:
(1) bata-tricalcium phosphate particle 100g is taken, 250g mass fraction is added for 10% phosphoric acid,diluted, at blended under agitation activation
Reason, vacuum filtration, solid is dried in vacuo, and obtains modified bata-tricalcium phosphate；
(2) modified bata-tricalcium phosphate 70g obtained in step (1) is taken, is total to solid containing the glycolide lactide for being 30wt%
The chloroformic solution of polymers handles 1h under conditions of 25 DEG C in ultrasonic oscillator, then stirs 1h and obtains mixed solution, will
Mixed solution carries out freeze-drying process, removes solvent, obtains that particle is blended；
Wherein, in the chloroformic solution of Vicryl Rapide, Vicryl Rapide content is 490g；(3)
Particle 100g is blended with obtained in step (2) in 5g nucleating agent to be uniformly mixed, is subsequently placed in vacuum drying oven, in 40-50 DEG C
The titanium dioxide of 0.05wt% is added after solvent evaporating completely in evaporation removing solvent, carries out at 60 DEG C to obtained particle
Minuent crystallization, crystallinity 25%；
Particle after low crystallization is directly subjected to injection molding and obtains bar, injection temperature is 160 DEG C, and mold temperature is
100 DEG C, then the self-reinforcing process that bar is oriented stretching is handled, stretching ratio is 1.5 times；
(4) material by oriented stretch processing obtained in step (3) is machined out, and obtains absorbable interface spiral shell
Nail.
Wherein, the weight average molecular weight of the Vicryl Rapide of the present embodiment is 100,000, molecular weight distribution 2.0,
(25 DEG C) of inherent viscosity are 2.0dL/g, and (20 DEG C) of specific rotatory power are 0.5 °.
The partial size of bata-tricalcium phosphate is 0.5 μm.
Embodiment 4
The preparation method of the present embodiment reference implementation example 1, difference be only that, the Vicryl Rapide of the present embodiment
Weight average molecular weight be 20,000, molecular weight distribution is that 2.0 inherent viscosities (25 DEG C) are 1.5dL/g, and specific rotatory power (20 DEG C) is
0.5°。
Embodiment 5
The preparation method of the present embodiment reference implementation example 1, difference be only that, the Vicryl Rapide of the present embodiment
Weight average molecular weight be 200,000, molecular weight distribution 2.0, (25 DEG C) of inherent viscosity are 2.0dL/g, and specific rotatory power (20 DEG C) is
0.5°。
Embodiment 6
The preparation method of the present embodiment reference implementation example 1, difference be only that, the Vicryl Rapide of the present embodiment
Weight average molecular weight be 150,000, molecular weight distribution 2.0, (25 DEG C) of inherent viscosity are 3.0dL/g, and specific rotatory power (20 DEG C) is
0.5°。
Embodiment 7
The preparation method of the present embodiment reference implementation example 1, difference be only that, molecular weight distribution 1.0, inherent viscosity (25
DEG C) it is 1.0dL/g, (20 DEG C) of specific rotatory power are 0.5 °.
Comparative example 1
The preparation method of comparative example reference implementation example 1, difference are: comparative example 1 hands over bata-tricalcium phosphate and glycolide third
Ester is directly blended, and bata-tricalcium phosphate is without modification.
Experimental example
For the mechanical property and degradability of the interference screw that the comparative illustration embodiment of the present invention and comparative example obtain, test
Method reference standard YY/T 0509-2009, test result is as follows table.
The inherent viscosity (dL/g) of 1 interference screw of table with degradation time variation
| Number | 0 week | 4 weeks | 12 weeks | 26 weeks |
| Embodiment 1 | 1.25±0.05 | 1.17±0.05 | 1.04±0.05 | 0.97±0.05 |
| Embodiment 2 | 1.24±0.05 | 1.13±0.05 | 1.00±0.05 | 0.85±0.05 |
| Embodiment 3 | 1.25±0.05 | 1.15±0.05 | 1.01±0.05 | 0.90±0.05 |
| Embodiment 4 | 0.55±0.05 | 0.40±0.05 | 0.33±0.05 | 0.30±0.05 |
| Embodiment 5 | 1.58±0.05 | 1.51±0.05 | 1.43±0.05 | 1.38±0.05 |
| Embodiment 6 | 1.47±0.05 | 1.30±0.05 | 1.22±0.05 | 1.07±0.05 |
| Embodiment 7 | 1.25±0.05 | 1.10±0.05 | 0.85±0.05 | 0.33±0.05 |
| Comparative example 1 | 1.25±0.05 | 1.1±0.05 | 0.87±0.05 | 0.70±0.05 |
The molecular weight distribution of 2 interference screw of table with degradation time variation
The pullout of strength of 3 interference screw of table with degradation time variation
| Number | 0 week | 4 weeks | 12 weeks | 26 weeks |
| Embodiment 1 | > 1200N | > 1000N | > 860N | > 645N |
| Embodiment 2 | > 1105N | > 950N | > 806N | > 610N |
| Embodiment 3 | > 1160N | > 985N | > 834N | > 632N |
| Embodiment 4 | > 900N | > 850N | > 750N | > 575N |
| Embodiment 5 | > 1400N | > 1200N | > 935N | > 750N |
| Embodiment 6 | > 1300N | > 1100N | > 890N | > 700N |
| Embodiment 7 | > 1200N | > 900N | > 780N | > 550N |
| Comparative example 1 | > 950N | > 800N | > 735N | > 525N |
By above-mentioned test result it is found that can be found by table 1 and 2, under the conditions of degrading different time, intrinsic viscosity
And certain variation has occurred in molecular weight distribution, illustrates that the sample has biodegradability；By table 3 it is found that in degradation 26 weeks
Pullout of strength is still greater than 450N afterwards, illustrates in degradation process, which still has enough mechanical properties, guarantees its function
Property is not destroyed.
The present invention carries out the degradation rate of Vicryl Rapide, modified bata-tricalcium phosphate, bata-tricalcium phosphate
Test, test result are shown in Fig. 1.As can be known from Fig. 1, the degradation rate of the degradation rate of modified bata-tricalcium phosphate and copolymer
It more matches, illustrates the problem of improving degradation rate between the two matching by modified method.
Wherein, bata-tricalcium phosphate is directly blended with poly (glycolide-co-lactide) without modification, finds its blending
Unevenly, easily there is stress concentration phenomenon, directly affect its degradation and Mechanics Performance Testing；In addition to this, weight average molecular weight
Size influences its biodegradability and mechanical property, and weight average molecular weight is too low, and mechanical strength is too low, and degradation speed is too fast,
Weight average molecular weight is excessively high, influences its processing performance, is unfavorable for processing.Therefore need to debug suitable weight average molecular weight.
About the ratio regulation of blend, the selection of viscosity and mechanical property and degradation rate with the variation of degradation time
Etc., entire technique is rigorous complexity, needs to be regulated and controled in all directions.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of absorbable interference screw fixation, which is characterized in that mainly by Vicryl Rapide and modified bata-tricalcium phosphate
It is made；
The modified bata-tricalcium phosphate is the bata-tricalcium phosphate handled by phosphoric acid activation.
2. absorbable interference screw fixation according to claim 1, which is characterized in that mainly by glycolide according to parts by weight
70-90 parts of lactide copolymer are made with modified bata-tricalcium phosphate 10-40 parts.
3. absorbable interference screw fixation according to claim 1, which is characterized in that the weight of the Vicryl Rapide
Average molecular weight is 20,000-20 ten thousand；
Preferably, the weight average molecular weight of the Vicryl Rapide is 5-15 ten thousand.
4. absorbable interference screw fixation according to claim 1, which is characterized in that point of the Vicryl Rapide
Son amount is distributed as 1.5-4.0；
Preferably, the molecular weight distribution 1.5-3.0 of the Vicryl Rapide.
5. absorbable interference screw fixation according to claim 1, which is characterized in that the 25 of the Vicryl Rapide
DEG C inherent viscosity is 1.0-2.5dL/g；
Preferably, 25 DEG C of inherent viscosities of the Vicryl Rapide are 1.25-2.0dL/g；
Preferably, 20 DEG C of specific rotatory powers of the Vicryl Rapide are 2.5 ° of -2.5 °~﹢.
6. the preparation method of the described in any item absorbable interference screw fixations of claim 1-5, which is characterized in that including walking as follows
It is rapid:
The modified bata-tricalcium phosphate that will be activated in phosphoric acid, it is total in proportion with Vicryl Rapide
It is mixed, molding.
7. the preparation method of absorbable interference screw fixation according to claim 6, which is characterized in that the phosphoric acid is phosphoric acid,diluted
Solution；
Preferably, the mass fraction of the dilute phosphoric acid solution is 5%-20%.
8. the preparation method of absorbable interference screw fixation according to claim 6, which is characterized in that the side of the activation processing
Method includes: that bata-tricalcium phosphate is stirred in phosphoric acid, filters, dries.
9. the preparation method of absorbable interference screw fixation according to claim 6, which is characterized in that the temperature of the blending is
20-25℃；
Preferably, the time of the blending is 60-180min；
Preferably, the mode of the blending includes: the preparatory solution for preparing Vicryl Rapide, is proportionally added into modification
Bata-tricalcium phosphate is ultrasonically treated 0.5-2h, stirs 0.5-1h.
10. the preparation method of absorbable interference screw fixation according to claim 6, which is characterized in that the molding mode
Include: to be uniformly mixed the material after blending with nucleating agent, after minuent crystallization, carries out injection molding；
Preferably, the temperature of the injection molding is 140-260 DEG C；
Preferably, the mold temperature of the injection molding is 50-240 DEG C；
Preferably, after molding, obtained profile is oriented stretch processing；
It is furthermore preferred that the stretching ratio of the orientation stretching processing is 1.1-1.5 times.
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| CN112933300A (en) * | 2021-02-03 | 2021-06-11 | 北京天星博迈迪医疗器械有限公司 | Absorbable fixed graft and preparation method thereof |
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