CN102319454A - Composite material used for interbody fusion cage and its preparation method - Google Patents
Composite material used for interbody fusion cage and its preparation method Download PDFInfo
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- CN102319454A CN102319454A CN201110244023A CN201110244023A CN102319454A CN 102319454 A CN102319454 A CN 102319454A CN 201110244023 A CN201110244023 A CN 201110244023A CN 201110244023 A CN201110244023 A CN 201110244023A CN 102319454 A CN102319454 A CN 102319454A
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Abstract
The invention discloses a composite material used for an interbody fusion cage and its preparation method. The composite material comprises by weight: 50-98% of poly(L-lactic acid-co-glycolic acid) (L-PLGA), and 2-50% of hydroxyapatite (HA). With high strength and good osteoinductive activity, the fusion cage of the invention can be fully degraded and absorbed in vivo, thus being a new generation of absorbable interbody fusion cage which is of high strength and high bone fusion rate and can meet clinical application requirements.
Description
Technical field
The invention belongs to medical material manufacturing technology field, be specifically related to composite and method for preparing that a kind of high strength has bioactive absorbable interbody cage.
Background technology
Shakiness is human commonly encountered diseases and the frequently-occurring disease of current society's puzzlement between intervertebral disk hernia that the spinal column regression causes and vertebral body.Behind the intervertebral disk hernia; Often cause that interpyramidal instability or interbody space narrow down, its intervertebral disk hernia thing pressuring nerve can make the people produce long-term pain, has a strong impact on patient's work and life; As time passes, even more serious consequences such as centrum olisthe even paralysis possibly appear.The patient invalid to expectant treatment needs the intervertebral fusion operative treatment usually.Autologous bone transplanting is the goldstandard of spinal fusion, but wound is distinguished in the increase confession, simultaneously because the implantation of bone piece is comparatively difficult merely, implants the back instability and causes skidding off entering canalis spinalis pressuring nerve, makes its clinical practice receive great restriction.Allogenic bone transplantation merges except that quantity is limited, and virus disseminating and immunologic rejection, moral statute also are the problems that is worth discussion.Therefore, adopting the implanted Invasive lumbar fusion device to add from the particulate fusion mode of body spongy bone is best at present selection, the effect that it can not only improve intervertebral fusion greatly, and making simultaneously to keep normally highly becomes possibility between vertebral body.
The material of making Invasive lumbar fusion device has following several kinds at present: the Invasive lumbar fusion device that uses at first clinically is the metal species material; That uses clinically at present is the titanium alloy fusion device mostly; Like Harms, BAK, TFC fusion device etc.; Though the metal fusion device has the better tissues compatibility and high support strength, in clinical practice, exist elastic modelling quantity too high, there is the compressing vertebral body to cause the possibility that is shifted or comes off; Retain in for a long time in the body, need second operation to take out; Can not judge that its interior bone merges situation from X-ray film simultaneously.For overcoming above-mentioned shortcoming, the non-metal kind material is brought into use like the Invasive lumbar fusion device that gathers carbon fiber and polyether-ether-ketone (PEEK) biological plastics and do, and it can reach the support strength with body mechanics's environment facies coupling, can be by the human body degraded and absorbed but face equally; Simultaneously, the molecule of its wearing and tearing back generation can be organized the problem that causes the local inflammation reaction around.For overcoming the above problems, therefore the absorbable interbody cage with poly-DL-lactic acid material manufacture of excellent biological compatibility and degradability has been born.
Chinese patent publication number CN1436518A and CN2561364A have announced that respectively by polylactic acid or interpolation hydroxyapatite be the fusion device development process that material is made; But its intensity and degradation property are still waiting further raising, and this fusion device lacks osteogenic activity simultaneously.People such as the Yoshihiro Hojo of Hokkaido, Japan university also reported with PLLA with without heat treated hydroxyapatite and mixed, with hot pressing formation process make Invasive lumbar fusion device (Biomaterials, 2005,26:2643-2651).But shortcomings such as these goods still exist mechanical property unstable, and the bone conduction ability is not good, and degradation speed is inappropriate.It is the Invasive lumbar fusion device of material that Chinese patent publication number CN101450015A relates to polylactic acid/ethanol copolymer PLGA and hydroxyapatite; But the mass ratio of LA and GA is 50: 50～90: 10 among the PLGA; And the hydroxyapatite that adds is merely nanoparticle; And adding content is 5～20%, and its fusion device processing method only limits to a sulfuration bed tabletting method and makes in addition; Simultaneously, because LA content is not very high (being lower than 90%) among the PLGA, the degree of crystallinity of integral material is not high enough, causes its intensity not as the PLLA homopolymer.Based on this; Design and develop a kind of higher mechanical strength that has; Simultaneously good osseo-compatible is arranged in the process that material is degraded fully, be beneficial to the growth of new bone, the bone property that can improve fusion device effectively substitutes the absorbable interbody cage of amount and bone property fusion rate; The fusion device that the fusion a new generation that promptly collect high strength, absorb fully, processus styloideus radii fusion rate characteristic is one, that performance is more excellent is used will be one of target of this area research pursuit in recent years.And be matrix with the PLGA of LA high-load monomer (greater than 90%) at present, add high-load HA and be compositions and make the document and the patent of fusion device and do not appear in the newspapers.
Summary of the invention
To above-mentioned situation, the invention provides composite and method for preparing that a kind of high strength has bioactive absorbable interbody cage.Fusion device of the present invention has high strength, good bone-inducting active, can be in vivo degraded and absorbed fully, be the absorbable interbody cage that a new generation can satisfy the clinical practice requirement with high strength, processus styloideus radii fusion rate.
The present invention takes following technical scheme: absorbable interbody cage is the composite that high polymer and inorganic component are processed, and high polymer is for gathering-L-lactic acid/ethanol copolymer (L-PLGA), and inorganic component is hydroxyapatite (HA); Gather-L-lactic acid/ethanol copolymer (L-PLGA) weight accounts for 50%～98% of composite; Hydroxyapatite weight accounts for the 2-50% of composite.
Preferably, gather-L-lactic acid/ethanol copolymer (L-PLGA) in, the mol ratio of L-lactic acid (LA) and glycolic (GA) is 91: 9～98: 2.
Preferably, hydroxyapatite (HA) is selected from one or more in micron particle, nanoparticle, the whisker.
Preferably, high polymer L-PLGA viscosity-average molecular weight is 10～800,000, preferred 20～400,000.
Preferably, hydroxyapatite (HA) is selected from the hydroxyapatite or the surperficial unmodified hydroxyapatite of surface modification.
The present invention is used for the composite high polymer L-PLGA viscosity-average molecular weight (Mn) of Invasive lumbar fusion device, the intrinsic viscosity ([η]) that under 25 ℃, in chloroform, records polymer with Ubbelohde viscometer earlier, reuse formula [η]=5.45 * 10
-4Mn
0.73Calculate, promptly obtain viscosity-average molecular weight.
The present invention is used for the composite of Invasive lumbar fusion device, and the mean diameter of hydroxyapatite micrometre particle is 0.50～10 micron, preferred 1.0～5.0 microns; The mean diameter of hydroxyapatite nano particle is 0.05～0.50 micron, preferred 0.08～0.15 micron; The mean diameter of hydroxyapatite crystal whisker is 0.50～30 micron, preferred 1.0～20 microns.
The present invention is related to be gathered-and the method for preparing of L-lactic acid/ethanol copolymer (L-PLGA) can be with reference to method for preparing (the Journal of polymer rerearch of the PLGA of people such as Wang Liansong report; 2010; 17:77-82); The method for preparing of hydroxyapatite can be with reference to people's reported method such as WangXuejing (Biomaterials, 2002; 23 (24): 4787-4791).
The method for preparing of the composite of making Invasive lumbar fusion device provided by the invention and finished product processing method are following:
(1) will gather-L-lactic acid/ethanol copolymer (L-PLGA) is dissolved in the dichloromethane; After the stirring and dissolving; Hydroxyapatite (HA) that will ultra-sonic dispersion is crossed in dichloromethane and ethanol mixed solvent adds in the above-mentioned solution; The dispersed with stirring evenly excessive dehydrated alcohol of back reuse obtains precipitate, and vacuum drying gets white powder.
(2) composite powder is passed through the injector mould molding at a certain temperature, be processed into Invasive lumbar fusion device.Invasive lumbar fusion device is the hollow shape cylinder, and its cross section is tetragon or hexagon, side-wall hole.
Compare with existing Invasive lumbar fusion device, Invasive lumbar fusion device of the present invention has the following advantages:
(1) compare with non-absorbent Invasive lumbar fusion device, its elastic modelling quantity and people's bone photo are worked as, and can not produce the stress shielding phenomenon; In inserting Invasive lumbar fusion device, obtain the fusion of bone property from the broken bone of body through the human body mechanism of normally healing, and the vertebral body of merging is when being enough to bear physiological loads, composite degradation in vivo is gradually absorbed by human body fully, does not produce any toxic side effects; Can merge situation through the x-ray observation postoperative simultaneously.
(2) with can absorb this fusion device and compare; This fusion device is by the composite manufacturing of L-PLGA and HA; Wherein, LA content of monomer very high (greater than 90%) among the L-PLGA, the crystallizing power of material is very strong; Therefore can reach the mechanical strength suitable, add a small amount of GA simultaneously its degradation speed is slightly accelerated with PLLA; In addition, HA itself is meta-alkalescence slightly, has the bone conduction performance, the acidity that produces with the L-PLGA degradation process in can be to a certain extent after compound with L-PLGA, thus avoid therefore and the inflammation in late period that produces; The HA of high level adding simultaneously also can be brought into play its osteogenic activity better, thereby the bone property that improves fusion device effectively substitutes amount and bone property fusion rate.Therefore it is to have high strength, high fusion rate, adjustable the absorbed fusion device of degradation speed.
(3) composite material and preparation method thereof of this Invasive lumbar fusion device is simple; Can guarantee to have between inorganic component and the high polymer good interface to combine; Its processing technique also can effectively prevent the thermal degradation of high polymer, thereby has guaranteed that finished product has very high mechanical strength to be enough to satisfy the requirement of Invasive lumbar fusion device mechanical property clinically.
Description of drawings
Fig. 1 is the SEM photo of hydroxyapatite.
The specific embodiment
In order to understand technical scheme of the present invention better, be further described below in conjunction with specific embodiment, but those of ordinary skill in the art will be appreciated that the present invention is not limited to these embodiment.
Embodiment 1
L-PLGA (mol ratio of LA/GA is 98/2) molecular weight of high polymer is 350,000, to account for finished weight 95%, is dissolved in the dichloromethane, and concentration is 5g/100ml; After the HA nanoparticle become suspension with mixed solvent (volume ratio is 1: the 1) ultra-sonic dispersion of ethanol and dichloromethane, use the 0.22um filter paper filtering.HA content is to account for finished weight 5% metering; Under ultrasonic agitation, L-PLGA solution and HA solution are mixed, above-mentioned complex liquid is continued ultrasonic agitation precipitate with excessive dehydrated alcohol after 2 hours, leave standstill filtration; With absolute ethanol washing 3 times, vacuum drying gets the L-PLGA/HA composite.
Through the injector mould molding, 190 ℃ of injection temperatures are processed Invasive lumbar fusion device.Invasive lumbar fusion device is the hollow shape cylinder, and its cross section is tetragon or hexagon, side-wall hole, and diameter 2mm, finished product is through test, and compressive resistance is 12250N, and elastic modelling quantity is 5.8GPa, sees table 1.
Embodiment 2
L-PLGA (mol ratio of LA/GA is 95/5) molecular weight of high polymer is 320,000, to account for finished weight 70%, is dissolved in the dichloromethane, and concentration is 8g/100ml; After the HA particle become suspension with mixed solvent (volume ratio is 2: the 1) ultra-sonic dispersion of ethanol and dichloromethane, use the 5um filter paper filtering, HA content is to account for finished weight 30%; Under ultrasonic agitation, add in the dichloromethane solution of L-PLGA; Above-mentioned complex liquid was continued ultrasonic agitation 3 hours, in above-mentioned complex liquid,, leave standstill filtration with excessive dehydrated alcohol deposition; With absolute ethanol washing 3 times, vacuum drying gets the L-PLGA/HA composite.
Through the injector mould molding, injection temperature is 200 ℃, processes Invasive lumbar fusion device.Finished product is through test, and compressive resistance is 11440N, and elastic modelling quantity is 4.9GPa, sees table 1.
Embodiment 3
L-PLGA (mol ratio of LA/GA is 92/8) molecular weight of high polymer is 320,000, and HA content is dissolved in the dichloromethane to account for finished weight 50%, and concentration is 10g/100ml; After the HA whisker become suspension with mixed solvent (volume ratio is 5: the 3) ultra-sonic dispersion of ethanol and dichloromethane, use the 20um filter paper filtering, to account for finished weight 50%; Under ultrasonic agitation, add in the dichloromethane solution of L-PLGA; Above-mentioned complex liquid was continued ultrasonic agitation 4 hours, in above-mentioned complex liquid,, leave standstill filtration with excessive petroleum ether precipitation; With absolute ethanol washing 3 times, vacuum drying gets the L-PLGA/HA composite.
Through the injector mould molding, 210 ℃ of injection temperatures are processed Invasive lumbar fusion device.Finished product is through test, and compressive resistance is 10850N, and elastic modelling quantity is 4.7GPa, sees table 1.
Embodiment 4
L-PLGA (mol ratio of LA/GA is 98/2) molecular weight of high polymer is 400,000, to account for finished weight 70%, is dissolved in the dichloromethane, and concentration is 4g/100ml; After the HA particle become suspension with mixed solvent (volume ratio is 4: the 3) ultra-sonic dispersion of ethanol and dichloromethane, use the 0.22um filter paper filtering, same; Use the 20um filter paper filtering behind the HA whisker ultra-sonic dispersion, particle and whisker weight ratio are 1: 1, and HA content accounts for finished product gross weight meter 30%; Under ultrasonic agitation, add in the dichloromethane solution of L-PLGA; Above-mentioned complex liquid was continued ultrasonic agitation 3 hours, in above-mentioned complex liquid,, leave standstill filtration with excessive petroleum ether precipitation; With absolute ethanol washing 4 times, vacuum drying gets the L-PLGA/HA composite.
Through the injector mould molding, 210 ℃ of injection temperatures are processed Invasive lumbar fusion device.Finished product is through test, and compressive resistance is 12840N, and elastic modelling quantity is 6.2GPa, sees table 1.
Embodiment 5
L-PLGA (mol ratio of LA/GA is 92/8) molecular weight of high polymer is 350,000, to account for finished weight 80%, is dissolved in the dichloromethane, and concentration is 2g/100ml; After the HA particle become suspension with mixed solvent (volume ratio is 3: the 2) ultra-sonic dispersion of ethanol and dichloromethane; Use the 5um filter paper filtering, same, use the 20um filter paper filtering behind the HA whisker ultra-sonic dispersion; Particle and whisker weight ratio are 3: 1; HA content accounts for finished product gross weight meter 20%, and other step is the same basically, and test result is seen table 1.
Embodiment 6～11 preparation processes are basically with above-mentioned embodiment, and its composition and Mechanics Performance Testing result are as shown in table 1.
The comparative example 12
L-PLGA (mol ratio of LA/GA is 95/5, and molecular weight is 300,000) is dissolved in the dichloromethane fully, and concentration is 5g/100ml, and with excessive dehydrated alcohol deposition, other step is the same, and test result is seen table 1.
PDLLA (molecular weight the is 400,000) preparation process of comparative example 13PLLA (molecular weight is 320,000) and Comparative Examples 14 is basically with embodiment 12.
Provide the method for testing of compressive resistance and elastic modelling quantity below.
Instrument: the speed constant speed is adjustable, and error is less than ± 0.5%; Negative error is not more than ± and 0.5%, the amount of deflection error is not more than ± 2% Material Testing Machine.
Experimental situation: 23 ± 2 ℃ of temperature, 60% ± 5 ℃ of humidity.
Specimen preparation: specimen is through injection moulding, length 13mm; Width 13mm.
Experimental procedure:
The size of specimen is accurately to 0.02mm;
Regulate test speed, the speed of code test is 2.0 ± 0.4mm/min;
Estimate the load of sample fracture, select load range;
Under the room temperature, sample soaked in water 1 hour, took out back 5 minutes build-in tests, when sample begins walking, write down its pressurized load, when sample deformation 30%, write down its pressurized load.
The elastic modelling quantity method of testing
Sample strip: 50mm * 7mm * 2mm
Gauge: viscoelastic analyzer (product of Rheometric corporation)
Frequency: 6.28rad/s
Beginning temperature: 0 ℃
End temp: 180 ℃
The rate of heat addition: 5 ℃/min
Distortion: 0.05%.
The mechanical property of table 1 embodiment
Need to prove, mention that in the present invention all documents quote as a reference in this application, used such as a reference separately as each piece document; Should understand in addition; The above is specific embodiment of the present invention and the know-why used; After having read foregoing of the present invention; Those skilled in the art can make various modifications and not deviate from the spirit and scope of the present invention the present invention, and the modification of these equivalents drops within protection scope of the present invention equally.
Claims (8)
1. the composite that is used for Invasive lumbar fusion device is characterized in that consisting of of this composite: gather-L-lactic acid/ethanol copolymer, hydroxyapatite; Described gathering-the weight content of L-lactic acid/ethanol copolymer in composite is 50～98%; The weight content of described hydroxyapatite in composite is 2～50%.
2. the composite that is used for Invasive lumbar fusion device as claimed in claim 1 is characterized in that: in described gathering-L-lactic acid/ethanol copolymer, L-lactic acid: the mol ratio of glycolic is 91: 9～98: 2.
3. according to claim 1 or claim 2 the composite that is used for Invasive lumbar fusion device, it is characterized in that: the viscosity-average molecular weight of described gathering-L-lactic acid/ethanol copolymer is 10～800,000.
4. the composite that is used for Invasive lumbar fusion device as claimed in claim 1 is characterized in that: the viscosity-average molecular weight of described hydroxyapatite is 20～400,000.
5. like claim 1 or the 4 described composites that are used for Invasive lumbar fusion device, it is characterized in that: described hydroxyapatite is selected from one or more in micron particle, nanoparticle or the whisker; The mean diameter of micron particle is 0.50～10 micron, and the mean diameter of nanoparticle is 0.05～0.50 micron, and the mean diameter of whisker is 0.50～30 micron.
6. the composite that is used for Invasive lumbar fusion device as claimed in claim 5 is characterized in that: the mean diameter of said hydroxyapatite micrometre particle is 1.0～5.0 microns; The mean diameter of hydroxyapatite nano particle is 0.08～0.15 micron; The mean diameter of hydroxyapatite crystal whisker is 1.0～20 microns.
7. the composite that is used for Invasive lumbar fusion device as claimed in claim 1 is characterized in that: described hydroxyapatite is selected from the hydroxyapatite or the surperficial unmodified hydroxyapatite of surface modification.
8. one kind like the said method for preparing that is used for the composite of Invasive lumbar fusion device of claim 1-7; It is characterized in that as follows: hydroxyapatite adopts the mixed solvent supersonic of ethanol and dichloromethane to disperse; Two kinds of solvent volume ratios of ethanol and dichloromethane are 1: 2～4: 1; Hydroxyapatite behind the ultra-sonic dispersion is adopted 0.22um～30um filter paper filtering; Under ultrasonic agitation, add in proportion gather with dichloromethane is dissolved-L-lactic acid/ethanol copolymer high polymeric solution in, wherein, gather-L-lactic acid/ethanol copolymer solution concentration is 2～10g/100ml; Above-mentioned complex liquid was continued ultrasonic agitation 2～4 hours; In above-mentioned complex liquid, adopt excessive dehydrated alcohol or petroleum ether precipitation, leave standstill filtration, adopt absolute ethanol washing 3～5 times; In vacuum drying oven, be dried to constant weight, make composite.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107823716A (en) * | 2017-10-31 | 2018-03-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of 3D printing Invasive lumbar fusion device composite and products thereof and application |
| CN108926740A (en) * | 2018-07-05 | 2018-12-04 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of the PLGA/ hydroxyapatite neck Invasive lumbar fusion device of octahedral figure 3D printing and application |
| CN108938150A (en) * | 2018-06-06 | 2018-12-07 | 花沐医疗技术服务(上海)有限公司 | A kind of degradable cervical vertebral fusion cage and preparation method thereof |
| CN109044571A (en) * | 2018-07-06 | 2018-12-21 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of half-moon-shaped 3D printing PLGA/ hydroxyapatite waist Invasive lumbar fusion device and application |
| CN116870258A (en) * | 2023-08-04 | 2023-10-13 | 山东大学齐鲁医院 | Composite material for cancellous bone region defect of bearing bone and preparation method thereof |
| CN116870258B (en) * | 2023-08-04 | 2024-05-17 | 山东大学齐鲁医院 | Composite material for cancellous bone region defect of bearing bone and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107823716A (en) * | 2017-10-31 | 2018-03-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of 3D printing Invasive lumbar fusion device composite and products thereof and application |
| CN108938150A (en) * | 2018-06-06 | 2018-12-07 | 花沐医疗技术服务(上海)有限公司 | A kind of degradable cervical vertebral fusion cage and preparation method thereof |
| CN108926740A (en) * | 2018-07-05 | 2018-12-04 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of the PLGA/ hydroxyapatite neck Invasive lumbar fusion device of octahedral figure 3D printing and application |
| CN109044571A (en) * | 2018-07-06 | 2018-12-21 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of half-moon-shaped 3D printing PLGA/ hydroxyapatite waist Invasive lumbar fusion device and application |
| CN116870258A (en) * | 2023-08-04 | 2023-10-13 | 山东大学齐鲁医院 | Composite material for cancellous bone region defect of bearing bone and preparation method thereof |
| CN116870258B (en) * | 2023-08-04 | 2024-05-17 | 山东大学齐鲁医院 | Composite material for cancellous bone region defect of bearing bone and preparation method thereof |
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Inventor after: Jiang Liuyun Inventor after: Pang Xiubing Inventor after: Li Qing Inventor after: Qi Xuefei Inventor after: Zhou Wei Inventor after: Wu Kan Inventor after: Xiong Chengdong Inventor before: Pang Xiubing Inventor before: Jiang Liuyun Inventor before: Li Qing Inventor before: Qi Xuefei Inventor before: Zhou Wei Inventor before: Wu Kan Inventor before: Xiong Chengdong |
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Free format text: CORRECT: INVENTOR; FROM: PANG XIUBING JIANG LIUYUN LI QING QI XUEFEI ZHOU WEI WU KAN XIONG CHENGDONG TO: JIANG LIUYUN PANG XIUBING LI QING QI XUEFEI ZHOU WEI WU KAN XIONG CHENGDONG |
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| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120118 Assignee: Shijiazhuang Ruinuo Biomedical Material Co., Ltd. Assignor: Zhejiang micro degree Medical Instrument Co., Ltd.| Chengdu Chemical Co., Ltd. Contract record no.: 2014130000152 Denomination of invention: Composite material used for interbody fusion cage and its preparation method Granted publication date: 20131030 License type: Exclusive License Record date: 20141223 |
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Change date: 20150511 Contract record no.: 2014130000152 Assignee after: HEBEI RUINUO MEDICAL INSTRUMENT CO., LTD. Assignee before: Shijiazhuang Ruinuo Biomedical Material Co., Ltd. |
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| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |