CN103265796A - Controllable fully-degradable macromolecular material-based composite material and preparation method thereof - Google Patents
Controllable fully-degradable macromolecular material-based composite material and preparation method thereof Download PDFInfo
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- CN103265796A CN103265796A CN201310200371XA CN201310200371A CN103265796A CN 103265796 A CN103265796 A CN 103265796A CN 201310200371X A CN201310200371X A CN 201310200371XA CN 201310200371 A CN201310200371 A CN 201310200371A CN 103265796 A CN103265796 A CN 103265796A
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Abstract
The invention relates to a controllable fully-degradable macromolecular material-based composite material and a preparation method thereof. According to the controllable fully-degradable macromolecular material-based composite material, a degradable macromolecular material serves as a matrix; magnesium oxide, magnesium hydroxide or a mixture of magnesium oxide and magnesium hydroxide serves as an enhanced phase; and the adding amount of the magnesium oxide, magnesium hydroxide or the mixture of magnesium oxide and magnesium hydroxide accounts for 0.5-40wt% of the composite material. The controllable fully-degradable macromolecular material-based composite material has the characteristics of high biosecurity, good degradation controllability, low material cost and the like, and has a wide application prospect in the technical field of manufacturing or surface modification of medicine controlled release carriers (such as medicinal capsules) and medical treatment appliance products, especially high-additional-value implants comprising 1) surgical sutures, 2) orthopedic internal fixation devices such as bone plates, bone nails, bone nets and the like, 3) artificial bone or bone repair materials, 4) intravascular stents, 5) tissue engineering stents and the like.
Description
Technical field
The invention belongs to bio-medical novel material and medical device product manufacturing and applied technical field, relate in particular to a kind of controlled fully-degradable polymer material based composites and preparation method thereof.
Background technology
Along with The development in society and economy and growth in the living standard, the human medical treatment ﹠ health cause of just unprecedentedly paying close attention to self.The increasing of survival pressure, the quickening of rhythm of life, the aggravation of environmental pollution, the frequent generation of security incident such as food, traffic and production and local war, natural disaster etc. causes disease and wound to become human haze of can't get rid of forever.The important foundation of the important means as modern medicine---medicine equipment and integral part, biomaterial are used for reparation, replacement or the function of the diagnosis of disease and treatment, histoorgan to be promoted, and a large amount of struggles are rehabilitated in sufferer residual, dead painful edge.In recent years, global medical apparatus industry high speed development, average annual growth rate be the same period increasing speed of national economy more than 2 times, be described as " sunrise industry ", become the very active new source of economic growth of 21 century.Be example with China, China medicine equipment market speedup in 2010 is up to 23%, and market scale breaks through 1,000 hundred million yuan of high point first, becomes the second-biggest-in-the-world medicine equipment market that is only second to the U.S., and expecting market scale in 2015 will be near 3,400 hundred million yuan.Just because of biomaterial huge social like this and economic worth, its R﹠D work is subjected to showing great attention to of countries in the world government, industrial community and scientific and technological circle day by day, is successively listed in the crucial new material development plan of hi-tech by U.S., moral, day, Australia and the Chinese government.
Biomaterial is of a great variety, and up to now, what be studied exceedes thousand kinds, and extensive medical also has nearly hundred kinds.Wherein especially biodegradable polymer is good owing to biocompatibility for degradable, and under the effect of physiological environment, can progressively degrade and absorbed metabolism by body, need not second operation takes out, reduce body and mind misery and the economical load of sufferer, therefore become one of important materials of preparations such as implanted medical device and capsule for medicine.Yet, experimental study and clinical application result show: when using separately as bio-medical material, macromolecular material is except mechanical property (as intensity), bone avidity etc. are not ideal enough, also have following major defect simultaneously: degraded product (comprising intermediate product lactic acid and final product carbonic acid gas and water) is acid, it gathers the acidifying that causes local physiological environment, cause aseptic inflammation, finally influence the reconstruction of tissue/organ.
For addressing the above problem, with the HA(hydroxyapatite), β-TCP(bata-tricalcium phosphate) and the CPP(calcium polyphosphate) etc. be the inorganic materials of representative and be that the metallic substance of representative becomes focus as the research and development of the macromolecular material based composites of wild phase with pure magnesium and magnesium alloy etc.Yet itself does not have biological degradability HA, can't be applied to high-fall solution and absorb the application scenario that characteristic requires; Though β-TCP and CPP are biodegradable, price is very expensive; There are many defectives in the especially Powdered or granular product of pure magnesium and magnesium alloy when using as wild phase, and too fast as causing degrading because chemically reactive is too high, the hydrogen of one of degraded product easily produces pneumatosis harm etc.
Summary of the invention
The objective of the invention is to the subject matter that exists in existing bio-medical material and the utilisation technology thereof, a kind of controlled fully-degradable polymer material based composites and preparation method thereof is provided.
For achieving the above object, the present invention takes following technical scheme:
A kind of controlled fully-degradable polymer material based composites, it is matrix with the degradable high polymer material, is wild phase with magnesium oxide, magnesium hydroxide or its mixture; The addition of described magnesium oxide, magnesium hydroxide or its mixture accounts for the 0.5%-40% of matrix material quality.
Described degradable high polymer material is the poly-left lactic acid of artificial synthesized degradable macromolecular material PLLA(), PLGA(polylactic acid-glycolic guanidine-acetic acid) or its mixture.
A kind of preparation method of controlled fully-degradable polymer material based composites, it comprises following key step:
A) preparation of solution: preparation is solid dispersed phase with magnesium oxide, magnesium hydroxide or its mixture, is the suspension of liquid with the organic solvent based sols of degradable high polymer material; The quality of described solid dispersed phase accounts for the 0.5%-40% of solid dispersed phase and degradable high polymer material total mass; Described degradable high polymer material is PLLA, PLGA or its mixture.
B) casting of solution or coating: casting or coating step a) are joined suspension, solidify the back and obtain material requested.
The described organic solvent of step a) is a kind of in A solvent and the B solvent, and wherein the A solvent is more than one in epoxy chloropropane, methylene dichloride or the chloroform, and the B solvent is more than one uniform mixture in A solvent and acetone, ethanol or the propyl carbinol.
The described solution of step a) is solid dispersed phase in order to magnesium oxide, magnesium hydroxide or its mixture, is the suspension replacement of liquid with the molten state degradable high polymer material; The quality of described solid dispersed phase accounts for the 0.5%-40% of solid dispersed phase and degradable high polymer material total mass; Described degradable high polymer material is PLLA, PLGA or its mixture.
Magnesium oxide in material of the present invention and preparation method thereof and magnesium hydroxide can be the products of commercially available or homemade Any shape (Powdered, particulate state or sheet), size and degree of crystallinity.
PLLA in material of the present invention and preparation method thereof and PLGA can partly or entirely replace by any other known or commercially available macromolecular material with biodegradation character, as natural degradable macromolecular materials such as collagen protein, gelatin and chitosans, and other synthetic degradable high polymer material.
The existence of magnesium oxide, magnesium hydroxide or its mixture in the material of the present invention can be brought into play the active effect of at least two aspects: the potential hazard that 1) reduces even eliminate degradable high polymer material acid degradation product; 2) biodegradation rate of regulation and control degradable high polymer material.The addition of magnesium oxide, magnesium hydroxide or its mixture in the control material, purpose are the material over-all properties that obtains to expect.Result of study shows: cross when low when the consumption of magnesium oxide, magnesium hydroxide or its mixture, then modified effect is not obvious; Consumption is too high, then causes the matrix material overall performance to comprise that force of cohesion, degradation property etc. obviously worsen.Therefore, should be with its consumption control at the 0.5%-40% that accounts for the matrix material quality.
Compared with prior art, the present invention has following advantage:
(1) the high matrix material of the present invention of the biological safety of material is made up of matrix and wild phase.With regard to matrix is degradable high polymer material and since up to now on clinical medicine successful Application for many years, so its biocompatibility is unquestionable.With regard to wild phase was magnesium oxide, magnesium hydroxide or its mixture, its characteristics had two: (one) unreactiveness and chemically reactive are moderate; (2) degraded product is only by Mg
2+And H
2O forms.So-called " unreactiveness " refers to that magnesium oxide and magnesium hydroxide are higher than atomic state magnesium Thermodynamically stable, and be more stable relatively during use.So-called " chemically reactive " refers to magnesium oxide and the magnesium hydroxide degradation characteristic under physiological environment.According to the Pourbaix theory, even the higher magnesium hydroxide of thermodynamic stability in magnesium oxide and the magnesium hydroxide, its can stable existence in group water solution pH value interval also more than 11.475, and the pH value of normal body fluid is 7.40 even lower, therefore, magnesium oxide and magnesium hydroxide all can progressively be degraded under the erosion of body fluid, show the chemically reactive of appropriateness.H
2O is Source of life; Mg
2+Be that one of major element of human body (is only second to Na in the human body
+, K
+And Ca
2+Occupy the 4th, be only second to K in the cell
+Occupy the 2nd positively charged ion), participate in a series of metabolic processes in the body, healthy closely related with the keeping of life, health, form at the biological phosphorus lime stone, ground substance of bone changes, osteocyte forms and in conjunction with, knitting, and very important role (human body reaches as high as 400mg to the average daily demand of magnesium) is all being played the part of in the normal performance aspect of functions such as nerve, muscle, heart.Therefore, when magnesium oxide, magnesium hydroxide or its mixture used as the wild phase of matrix material, as long as its consumption of control and biodegradation rate, its use was useful and harmless for the host.In sum, matrix material integral body has excellent biocompatibility, safety, reliable when using as biomaterial.
(2) matrix in the material biological degradation controllability matrix material good of the present invention and wild phase are all biodegradable but degradation characteristic is different.Wherein the degradation rate of degradable high polymer material can be regulated and control in several thoughtful several years degradation cycles by its composition, relative molecular weight and material body thickness etc.; The degradation rate of magnesium oxide and magnesium hydroxide then can be controlled by its phase composite, degree of crystallinity, particle diameter and body thickness etc.Therefore, by adjusting each component proportions, can obtain to satisfy the matrix material with different degradation rates that clinical practice is used needs.
(3) material and preparation cost thereof are low, potential applied range is compared with known macromolecular material based composites wild phases such as CPP with expensive HA, β-TCP, wild phase as material of the present invention, magnesium oxide and magnesium hydroxide are the conventional chemical medicine, its applied range, industrialized mass production technology maturation, stable, therefore cheap.Material of the present invention both can be used for preparing instrument body, can be used for surface modification again.Utilize material of the present invention directly to prepare the high implants of added value (as surgical sewing thread, orthopedic fixation device tool etc.) and medicine controlled release carrier (as capsule for medicine) etc., can cushion/eliminate the disadvantageous effect of macromolecular material acid degradation product, be conducive to the normal performance of reconstruction and the medicine effect of damaged tissue/organ; Utilize material of the present invention that medical device product is carried out surface modification treatment, then can significantly improve the usage performance of product, comprise biocompatibility, biological degradability and biological activity etc.Because macromolecular material has fluid → solid conversion characteristic, be magnesium oxide, magnesium hydroxide desirable " binding agent ", it is good to possess plasticity again, the characteristics of flexible and controllable such as thickness, density and degradation property, therefore, use liquefaction → casting forming technology to carry out Composite Preparation not only simply but also economy.In sum, the market space that material of the present invention is huge because low-cost and high-performance has, application prospect is tempting.
Embodiment
Below in conjunction with preferred embodiment concrete enforcement of the present invention is described further, but enforcement of the present invention and protection domain are not limited thereto.
Embodiment 1
Be that solvent is at first prepared 25g/LPLLA solution with the chloroform, add the 5g/L magnesium hydrate powder then, mechanical stirring 1h, to obtain with the magnesium hydroxide be solid dispersed phase, be the suspension of liquid with the organic solvent based sols of PLLA.At this suspension of sheet glass top casting of cleaning, and in vacuum drying oven 60 ℃ of dry 48h of temperature control, treat that the solvent back of volatilizing fully obtains membranaceous matrix material.After above-mentioned membranaceous matrix material fragmentation, through hot compacting (175 ℃ of hot pressing temperatures, pressure 17MPa), obtaining to be of a size of 20mm * 10mm * 2.5mm, magnesium hydroxide addition, to account for the matrix material massfraction be magnesium hydroxide/PLLA block matrix material sample of 16.67%.
With the SBF(simulated body fluid) be tested media (its composition and human plasma chemical ingredients contrast situation see Table 1), control appearance face is than (ratio that the ie in solution volume is long-pending with specimen surface) 24ml/cm
2, solution regeneration interval 24h, under 37 ℃ of conditions of probe temperature, the pure PLLA block sample (control sample) of the same size that said sample and identical preparation condition are obtained carries out the test of external biological degradation property respectively.The quality change monitoring result shows: matrix material sample and the pure PLLA control sample required time of degrading fully is respectively 125d and 82d; (namely with sample effect 24h after) pH value monitoring result showed before tested media was upgraded: the matrix material sample degradation causes the highest raising 1.56 of the purer PLLA control sample of changing value of tested media pH, and the acidification effect that confirms the generation of macromolecular material degradation process is obviously weakened because of the interpolation of magnesium hydroxide.
Embodiment 2
Except changing PLLA into PLGA, magnesium hydroxide changes magnesium oxide into, organic solvent changes into outside the methylene dichloride, and the control of other condition of Composite Preparation is with embodiment 1, and the result obtains the magnesium oxide addition, and to account for the matrix material massfraction be magnesium oxide/PLGA block matrix material of 16.67%.Carry out the test of external biological degradation property with 1 pair of sample of embodiment.The quality change monitoring result shows: matrix material sample and the pure PLGA control sample required time of degrading fully is respectively 140d and 94d; (namely with sample effect 24h after) pH value monitoring result showed before tested media was upgraded: the matrix material sample degradation causes the highest raising 1.23 of the purer PLGA control sample of changing value of tested media pH, confirms that the acidification effect of macromolecular material degradation process generation is obviously weakened because of magnesian interpolation.
Embodiment 3
Except the mixture that the magnesium hydroxide of 5g/L is changed into 5g/L magnesium oxide and 5g/L magnesium hydroxide, organic solvent changes into outside the epoxy chloropropane, the control of other condition of Composite Preparation is with embodiment 1, and the result obtains magnesium oxide and magnesium hydroxide addition, and to account for the matrix material massfraction respectively be 14.29% block matrix material.Carry out the test of external biological degradation property with 1 pair of sample of embodiment.The quality change monitoring result shows: matrix material sample and the pure PLLA control sample required time of degrading fully is respectively 178d and 82d; (namely with sample effect 24h after) pH value monitoring result showed before tested media was upgraded: the matrix material sample degradation causes the changing value of tested media pH to the highest raising 1.97 of pure PLLA according to sample, and the acidification effect that confirms the generation of macromolecular material degradation process is obviously weakened because of the interpolation of magnesium oxide and magnesium hydroxide.
Embodiment 4
Except the concentration with magnesium hydroxide changes 125.6mg/L into, organic solvent changes into outside the uniform mixture (mixed volume is than being 2:1) of epoxy chloropropane and acetone, and other condition control of Composite Preparation is with embodiment 1.The result obtains the magnesium hydroxide addition, and to account for the matrix material massfraction be magnesium hydroxide/PLLA block matrix material of 0.5%.Carry out the test of external biological degradation property with 1 pair of sample of embodiment.The quality change monitoring result shows: matrix material sample and the pure PLLA control sample required time of degrading fully is respectively 94d and 82d; (namely with sample effect 24h after) pH value monitoring result showed before tested media was upgraded: the matrix material sample degradation causes the highest raising 0.24 of the purer PLLA control sample of changing value of tested media pH, and the acidification effect that confirms the generation of macromolecular material degradation process is weakened because of the interpolation of magnesium hydroxide.
Embodiment 5
Except the concentration with magnesium hydroxide changes 16.67g/L into, organic solvent changes into outside the uniform mixture (mixed volume is than being 4:1) of chloroform and dehydrated alcohol, and other condition control of Composite Preparation is with embodiment 1.The result obtains the magnesium hydroxide addition, and to account for the matrix material massfraction be magnesium hydroxide/PLLA block matrix material of 40%.Carry out the test of external biological degradation property with 1 pair of sample of embodiment.The quality change monitoring result shows: matrix material sample and the pure PLLA control sample required time of degrading fully is respectively 220d and 82d; (namely with sample effect 24h after) pH value monitoring result showed before tested media was upgraded: the matrix material sample degradation causes the highest raising 2.47 of the purer PLLA control sample of changing value of tested media pH, and the acidification effect that confirms the generation of macromolecular material degradation process is obviously weakened because of the interpolation of magnesium hydroxide.
Embodiment 6
Get the 200gPLLA solid particulate, be heated to melted state and 200 ℃ of insulations, add the 50g magnesium hydroxide powder, cast immediately after stirring, put into 60 ℃ of dry 48h of vacuum drying oven temperature control after being cooled to room temperature, treat to obtain block matrix material after solvent volatilizees fully.After above-mentioned matrix material fragmentation, through hot compacting (175 ℃ of hot pressing temperatures, pressure 17MPa), obtaining to be of a size of 20mm * 10mm * 2.5mm, magnesium hydroxide addition, to account for the matrix material massfraction be magnesium hydroxide/PLLA block matrix material sample of 20.0%.Carry out the test of external biological degradation property with 1 pair of sample of embodiment.The quality change monitoring result shows: matrix material sample and the pure PLLA control sample required time of degrading fully is respectively 197d and 85d; (namely with sample effect 24h after) pH value monitoring result showed before tested media was upgraded: the matrix material sample degradation causes the highest raising 1.87 of the purer PLLA control sample of changing value of tested media pH, confirms that the acidification effect of macromolecular material degradation process generation is obviously weakened because of magnesian interpolation.
With further reference to medicine equipment biological assessment ISO 10993 standards, with the negative contrast of widely used titanium alloy ti6al4v on the clinical medicine, it is the physiologically acceptable property testing of representative that each sample among the embodiment 1-embodiment 6 is carried out respectively with hemolysis rate and vitro cytotoxicity, and the result shows: each sample all shows the excellent biological compatibility suitable with Ti6Al4V.
Table 1: tested media and the contrast of human plasma chemical ingredients
Claims (5)
1. controlled fully-degradable polymer material based composites, it is characterized in that: being matrix with the degradable high polymer material, is wild phase with magnesium oxide, magnesium hydroxide or its mixture; The addition of described magnesium oxide, magnesium hydroxide or its mixture accounts for the 0.5%-40% of matrix material quality.
2. controlled fully-degradable polymer material based composites according to claim 1 is characterized in that: described degradable high polymer material is the poly-left lactic acid of artificial synthesized degradable macromolecular material PLLA(), PLGA(polylactic acid-glycolic guanidine-acetic acid) or its mixture.
3. the preparation method of a controlled fully-degradable polymer material based composites is characterized in that comprising following key step:
A) preparation of solution: preparation is solid dispersed phase with magnesium oxide, magnesium hydroxide or its mixture, is the suspension of liquid with the organic solvent based sols of degradable high polymer material; The quality of described solid dispersed phase accounts for the 0.5%-40% of solid dispersed phase and degradable high polymer material total mass; Described degradable high polymer material is PLLA, PLGA or its mixture;
B) casting of solution or coating: casting or coating step a) are joined suspension, solidify the back and obtain material requested.
4. the preparation method of controlled fully-degradable polymer material based composites according to claim 3, it is characterized in that: the described organic solvent of step a) is a kind of in A solvent and the B solvent, wherein the A solvent is more than one in epoxy chloropropane, methylene dichloride or the chloroform, and the B solvent is more than one uniform mixture in A solvent and acetone, ethanol or the propyl carbinol.
5. the preparation method of controlled fully-degradable polymer material based composites according to claim 3, it is characterized in that: the described solution of step a) is solid dispersed phase in order to magnesium oxide, magnesium hydroxide or its mixture, is the suspension replacement of liquid with the molten state degradable high polymer material; The quality of described solid dispersed phase accounts for the 0.5%-40% of solid dispersed phase and degradable high polymer material total mass; Described degradable high polymer material is PLLA, PLGA or its mixture.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189143A (en) * | 2016-08-08 | 2016-12-07 | 安徽红太阳新材料有限公司 | A kind of polycaprolactone macromolecule degradable material and preparation method thereof |
| CN108283729A (en) * | 2018-01-31 | 2018-07-17 | 北京化工大学 | Injectable bone repair material and preparation method thereof with controllable magnesium ion release behavior |
| CN110585481A (en) * | 2019-08-28 | 2019-12-20 | 华南师范大学 | Preparation and application of nano magnesium hydroxide regional coating polylactic acid-caprolactone scaffold for repairing spinal injury |
| CN111019173A (en) * | 2019-12-31 | 2020-04-17 | 江南大学 | Preparation method of degradable polylactic acid-glycolic acid composite material |
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| US20120070650A1 (en) * | 2010-09-16 | 2012-03-22 | Korea Institute Of Science And Technology | Biomedical implants comprising surface-modified metal particles and biodegradable polymers, its use for suppressing inflammation, and preparation method thereof |
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2013
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| US20120070650A1 (en) * | 2010-09-16 | 2012-03-22 | Korea Institute Of Science And Technology | Biomedical implants comprising surface-modified metal particles and biodegradable polymers, its use for suppressing inflammation, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张敏等: "金属氧化物对PLLA降解性能的影响", 《复合材料学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189143A (en) * | 2016-08-08 | 2016-12-07 | 安徽红太阳新材料有限公司 | A kind of polycaprolactone macromolecule degradable material and preparation method thereof |
| CN108283729A (en) * | 2018-01-31 | 2018-07-17 | 北京化工大学 | Injectable bone repair material and preparation method thereof with controllable magnesium ion release behavior |
| CN110585481A (en) * | 2019-08-28 | 2019-12-20 | 华南师范大学 | Preparation and application of nano magnesium hydroxide regional coating polylactic acid-caprolactone scaffold for repairing spinal injury |
| CN110585481B (en) * | 2019-08-28 | 2021-12-17 | 华南师范大学 | Preparation and application of nano magnesium hydroxide regional coating polylactic acid-caprolactone scaffold for repairing spinal injury |
| CN111019173A (en) * | 2019-12-31 | 2020-04-17 | 江南大学 | Preparation method of degradable polylactic acid-glycolic acid composite material |
| CN111019173B (en) * | 2019-12-31 | 2021-05-04 | 江南大学 | Preparation method of degradable polylactic acid-glycolic acid composite material |
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Application publication date: 20130828 |