CN100523082C - High-strength high-modulus absorbable calcium polyphosphate fibre/polylactide composition as intrabony fixing material and its preparing process - Google Patents
High-strength high-modulus absorbable calcium polyphosphate fibre/polylactide composition as intrabony fixing material and its preparing process Download PDFInfo
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- CN100523082C CN100523082C CNB021133093A CN02113309A CN100523082C CN 100523082 C CN100523082 C CN 100523082C CN B021133093 A CNB021133093 A CN B021133093A CN 02113309 A CN02113309 A CN 02113309A CN 100523082 C CN100523082 C CN 100523082C
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Abstract
A high-strength high-modulus absorble material as intrabony fixing material is prepared from calcium polyphosphate fibres as reinforcing component and polylactide as substrate in wt ratio of (1-80):(20-99). Its advantages include high compatibility to bone tissue, no poison and untoward effect, bio-degradable, and low cost.
Description
Technical field
The present invention relates to medically be applied to the high strength and modulus absorbability bone internal fixing matrix material of bone internal fixing, belong to prosthesis and be implanted into technical field.
Background technology
Over nearly 40 years, the prosthesis implant is in the clinical medicine widespread use.Clinical medicine facts have proved that most prosthesis implants are safety and effective to human body.The application of these prosthesis implants has greatly improved human beings'health situation and life quality.The prosthesis implant generally includes the implant (as artificial hip joint, knee joint and heart valve etc.) of permanent use.The prosthesis implant of permanent use requires by the medical material manufacturing with good biological stability, and prepares the prosthesis implant of temporary use, and it is more suitable then to adopt biodegradable to absorb medical material.
Bone internal fixing technology (comprising the treatment to trauma fracture or the orthopedic osteotomy of bone malformation) is one of the most frequently used treatment means of clinical medicine.According to the basic pathology process (comprising fracture local hematoma machineization, porosis and the moulding three phases of bone) and the famous wolfShi law of bone biomechanical of union of fracture, the biology fracture fixation requires---and in union of fracture fracture site is fixedly secured; In porotic stage (clinical healing phase) and moulding phase of bone, fracture is local should certain stress.Yet, though it is local early stage strong fixing that the biologically stable metal inside-fixture of present routine clinical use can be finished fracture, but exist: because its intensity and rigidity too high (people's bone 20-30 times), the local stress force shelter reaction that produces that causes fracturing makes fracture part, healing back osteoporosis occur and removes the easy refracture in back with dysfunction and fixture; Because metallic corrosion causes the local inflammation reaction, even causes carcinogenesis at a specified future date, so need second operation to remove; Owing to the intrinsic physical property of metal influences drawbacks such as Medical Imaging inspection such as MRI and CT.The absorbability fracture inside-fixture is because its gradually falling property biodegradable and absorptivity and physical strength, therefore meet most the requirement of fracture biology fixed in theory, and can overcome the various drawbacks of above-mentioned metal inside-fixture, also can make the patient economically and psychological the benefit.
Using self-enhancement L-polylactide from reported first such as Rokkamen in 1985 (after SR-PLLA) and poly-glycollide (SR-PGA) adsorbable bone folding internal fixation bar treatment ankle fracture obtain clinical satisfactory effect, uses the clinical report that can absorb inside-fixture treatment fracture in recent years and is on the increase.Many materials and product category comprise the internal fixation bar, pin, screw, Steel Plate For Fixation Of Fracture of three types of self-enhancement L-polylactide, poly-glycollide and multipolymers thereof etc.Because adsorbable bone is rolled over the physical strength and the insufficient rigidity (being lower than normal people's cortex bone) of inside-fixture at present, so only can be used for treating the lower non-prudent position cancellous bone fracture of sickness rate, as ankle, ancon, long bone of limbs epiphysis and craniofacial region fracture internal fixing, still can not be applied to the internal fixing of the prudent position of the high four limbs of sickness rate long bone shaft fracture.In addition, because the polymericular weight too high (100 * 10 of SR-PLLA
4Dolton), and be crystal structure, cause vivo degradation to absorb required time long (40 months); Because the polymkeric substance of SR-PLLA is non-crystal structure, too fast at implantation degradation speed in late period, cause local sterility hydrops and sinus to form; Because implanting, these macromolecule polymer materials cause foreign body reaction, local acidifying pH reduction and do not have bone conduction and synosteosis biological activity that bone is moulding to be rebuild with bone structure thereby influence.Therefore, the subject matter that needs to solve in absorbability bone fracture internal fixation material development at present and the application comprises: the physical strength and the rigidity that 1. further improve material: 2. make material have suitable vivo degradation and absorption rate; 3. make material have biological activitys such as osteoconductive and synosteosis.
Summary of the invention
The present invention is directed to the problem that prior art exists, provide a kind of and have good osseous tissue biocompatibility, body nontoxicity, no teratogenesis and mutagenesis, biodegradable high strength and modulus resorbable bone internal fixing matrix material.
At present the degradable and the absorbable polymer that mainly adopt of clinical medicine is---contain the aliphatic polyester of alpha hydroxy acid derivative, mainly comprise poly-glycollide (PGA) and polylactide (PLA) and multipolymer three major types thereof.In vivo, PGA is hydrolyzed into oxyacetic acid, and under the oxidasic effect of glycerate, oxyacetic acid is transformed into oxoethanoic acid; Change the oxygenase effect with sweet oxygen acid again and produce glycine; Sweet oxygen acid can participate in the synthetic of protein or Serine.After being converted to existing pyruvic acid, Serine can participate in tricarboxylic acid cycle.Produce lactic acid after the PLA hydrolysis, lactic acid can be metabolised to CO by carboxylic acid recycle
2, excrete by lung subsequently.These polymkeric substance and multipolymer thereof can adopt different plastic processing technologies and be prepared to fiber, film or other shape (as rod, screw, plate, folder etc.).With metal or ceramic phase ratio, its great advantage is to be easy to processing and with low cost.They have been made into operating sutures, fabric, bone inside-fixture, composite porous, slow releasing carrier of medication and three-dimensional stent material and widespread use in clinical medicine and organizational project technology of preparing.
In present technique, we adopt the calcium polyphosphate CPP fiber of controllable degradation rate, and this fiber is that the employing Chemical Composition calcium metaphosphate close with the human body bone mineral is main raw material, by adding an amount of stablizer Mg and resistance depressant prescription Zn, through pulverizing, grinding and high-temperature fusion, wire drawing, make.The structural formula of calcium polyphosphate fiber is:
The slowly process of degraded takes place in the CPP fiber in water:
This fiber and preparation technology's patent applied for thereof (application number 01101545.4).Studies show that through physics and chemistry and measuring mechanical property and biocompatibility evaluation and biological safety thereof, this fiber be a class have good osseous tissue biocompatibility, to the medical strongthener of the biodegradable absorptivity of the high strength and modulus of body nontoxicity, no teratogenesis and mutagenesis.
For improving and improve the mechanical property and the biology performance of biodegradable absorptivity fracture inside-fixture, to make it to be used for the fracture of partes corporis humani position, the internal fixing of the higher prudent position of sickness rate limbs long cannon bone shaft fracture particularly, and after finishing its strong internal fixing effect of fracturing with suitable speed degraded and absorbed, we use the ultimate principle and the technological method of matrix material, with diameter 5-50 μ mCPP fibers is reinforce, and with 20-100 * 10
4Molecular weight among the D (Mw) PLLA is the matrix thing, press CPPf/PLLA weight ratio 1-80/99-20, adopt multidirectional CPPf/PLLA pellicular cascade hot pressing CPP macrofiber or CPP staple fibre mould pressing technology to prepare serial CPPf enhanced high strength and modulus biodegradable absorptivity medical composite material.
Above-mentioned calcium polyphosphate fibre peacekeeping polylactide compound weight ratio can be preferably 2060/80-40, and perhaps more preferably 40-60/60-40.The molecular weight of polylactide (PLLA) can be preferably 40-60 * 10
4D.
Choose day degradation rate and be 0.2-4% or further be 0.8-1.5% calcium polyphosphate fiber (CPPf), diameter is preferably 5-25 μ m.
This matrix material is according to the difference of the scope of application, as is used to produce os integumentale screw and Steel Plate For Fixation Of Fracture, pipe and intramedullary needle or is used to produce cancellous bone screw or hold-down bars, and its preparation method has the part difference.
When being used to produce os integumentale screw and Steel Plate For Fixation Of Fracture, pipe and intramedullary needle, its preparation is carried out according to the following steps:
1, chooses calcium polyphosphate fiber (CPPf), be cut into the macrofiber of 10-500mm;
2, weigh;
3, taking by weighing purity is 99.9% polylactide (PLLA), in container with organic solvent 1:50-100 dissolving;
4, carry out the purifying extraction with dehydrated alcohol 1:50-200 pair polylactide (PLLA);
5, the polylactide that extraction is obtained (PLLA) particle vacuum-drying at least 24 hours in baking oven, 30-60 ℃ of temperature;
6, again with the organic solvent dissolution of polylactide (PLLA) particle with 1:50-100;
7, the manual shop of the calcium polyphosphate macrofiber that will 2. weigh through step layer is used simultaneously through 6. dissolved polylactide (PLLA) system film of step;
8, will volatilize 24 hours vacuum extraction 24 hours in baking oven again, 30-60 ℃ of temperature naturally through the organic solvent in the CPPf/PLLA film that 7. step is handled;
9, with the hot pressing of flat-bed press vacuum mold, 120-220 ℃ of temperature, pressure 20-80Mpa;
10, the demoulding, repair sample, packing, sterilization, high strength, high-modulus os integumentale screw or Steel Plate For Fixation Of Fracture, pipe and intramedullary needle.
When this matrix material was used to produce cancellous bone screw or hold-down bars, its preparation was carried out as follows:
1, chooses calcium polyphosphate fiber (CPPf), be cut into the staple fibre of 2-12mm;
2, weigh;
3, taking by weighing purity simultaneously is 99.9% polylactide (PLLA), in container with ethylene dichloride 1:50-100 dissolving;
4, will through calcium polyphosphate staple fibre (CPPf) that step 2 is weighed with 3. handle through step after polylactide (PLLA) solution mix;
5, use the mixture of the dehydrated alcohol purifying extraction step 4 of 1:100-200;
6, the organic solvent in the 5 CPPf/PLLA mixtures that obtain was volatilized 24 hours naturally at least, vacuum is carried and was pumped the machine solvent at least 24 hours in baking oven again, 30-60 ℃ of temperature;
7, with the hot pressing of flat-bed press vacuum mold, 120-200 ℃ of temperature, pressure 20-80Mpa;
8, the demoulding, repair sample, packing, sterilize the cancellous bone screw or the hold-down bars of high strength and modulus.
As strongthener, it mainly acts on and is this matrix material with the CPP fiber: 1. improve the flexural strength and the modulus in flexure of matrix material, and particularly remarkable to improving modulus in flexure; 2. the mineralogical composition owing to the material composition for preparing the CPP fiber and people's bone is close, so after adding the CPP fiber, makes CPPf/PLLA bone internal fixing matrix material have tangible osteoinductive energy; 3. because CPP degradation of fiber performance has controllability, and the degradation time of PLLA is longer, therefore after being processed into CPPf/PLLA bone inside-fixture, under the prerequisite that satisfies bone internal fixing performance requriements, the CPP fiber is at first degraded, abdicate hole, body fluid enters, increase the contact area of body fluid and PLLA, improve the degradation rate of PLLA, thereby shortened the degradation time of bone inside-fixture.
In sum, increase the quantity of CPP fiber, intensity, rigidity and the osteoinductive of CPPf/PLLA bone inside-fixture are increased, and can shorten time of degradation product in the bone, but when the quantity of CPP fiber surpasses a certain limit, its intensity, rigidity can reduce on the contrary, so the proportion relation do as one likes of CPPf/PLLA can be optimized definite.
Studies show that through physics and chemistry and measuring mechanical property and biocompatibility evaluation and biological safety thereof they are that a class has good osseous tissue biocompatibility, the body nontoxicity do not had the biodegradable absorptivity medical composite material of high strength and modulus of teratogenesis and mutagenesis.Compare with self-enhancement PGA, PLLA and multipolymer bone inside-fixture matrix material thereof, its feature performance benefit comprises:
1. strength and stiffness obviously improve, and reach 1.5 times and 1.3 times of human body cortex bone; Can be used for preparing superstrength biodegradable resorbable bone inside-fixture and bone impairment renovation material;
2. has suitable vivo degradation uptake rate;
3. have bone conduction and synosteosis performance;
4. has the video picture of X line;
5. preparation technology is easy, and cost value is cheap.
CPPf/PLLA medical composite material basic mechanical design feature detected result is as follows:
(1) matrix material physics and Mechanics Performance Testing
A. composite density is measured
The mean density that adopts direct weighing measurement method to record the Cppf/PLLA matrix material sees Table 1.
The density of table 1 CPPf/PLLA matrix material
Annotate: table 1 determination data is all represented with X ± SD.
B. fiber volume fraction is measured
Adopt the matrix material dissolving to filter the secondary weighing method and record the wherein weight of fiber: try to achieve by the relation between weight, density, the volume that fiber volume fraction is 20～45% in the CPPf/PLLA matrix material.
C. composite materials property test
On the MTS experimental machine, carry out diameter 3.2mm, the three point bending test of long 30mmCPPf/PLLA matrix material test specimen.Span is 22mm, and loading velocity is 1mm/min, the results are shown in Table 2.
Table 2 CPPf/PLLA matrix material flexural strength and modulus in flexure
(2) matrix material biodegradation character research
A. matrix material biodegradation character research
The relational result of its weight and degradation time shows when adopting external artificial degradation solution pickling process gained CPPf/PLLA matrix material to degrade under 37 ℃ in pH value 7.4 artificial degradation solutions, and the CPPf/PLLA matrix material can constantly degraded under the physiological condition in artificial degradation solution.
B. changes of mechanical properties in the matrix material biodegradation process
When the CPPf/PLLA matrix material is degraded under the physiological condition in external artificial degradation solution, the relation of its flexural strength and modulus in flexure and degradation time.The result shows that when the CPPf/PLLA matrix material was constantly degraded under the physiological condition, its flexural strength and modulus in flexure reduced gradually in artificial degradation solution.
C. Ultrastructural change in the matrix material biodegradation process
When the CPPf/PLLA matrix material is degraded under the physiological condition in external artificial degradation solution, its cross section ultrastructure sem observation is the result show, during the degraded of CPPf/PLLA matrix material external biological, its fiber is at first degraded to internal layer by skin mutually gradually, until the fibrous texture completely dissolve, and residual cavity appears; Matrix is degraded slow relatively mutually, and its quality evenly but loose relatively.Weight and changes of mechanical properties rule are consistent in The above results and its vitro degradation properties.
(3) matrix material cell biological consistency evaluation
A. matrix material is to cultivating the influence of chondrocyte's process of growth and metamorphosis
Adopt CPPf/PLLA matrix material and cultured in monolayer in vitro chondrocyte contact method, and establish experimental group, blank group and phenol solution positive controls.Go down to posterity by the WeiShi method and to cultivate the rabbit articular chondrocytes, dynamic observe the result by inverted microscope and show, the CPPf/PLLA matrix material does not have the significance influence to cultivating chondrocyte's process of growth and metamorphosis, can be compatible fully with the chondrocyte.
B. matrix material is to cultivating chondrocyte proliferation and the metabolic influence of DNA
Go down to posterity after the cultivation chondrocyte results, measure through cell counting and karstenShi fluorescence control pin EBr method cell DNA content
[9]Gained cell proliferation is than (inoculating cell number during cell count behind=every flask culture/cultivation), the relative proliferation rate of cell (=[cultivate back total cellular score/blank group for every group and cultivate the back total cellular score] * 100%) and cell DNA content.The result shows that the CPPf/PLLA matrix material does not have the significance influence to the propagation and the DNA metabolism of cultivating the chondrocyte.This matrix material does not have chondrocyte's toxicity.
C. tissue biocompatibility research
Select healthy rabbits for use, respectively the CPPf/PLLA sample is inserted around rabbit undertissue and the muscle, learn by naked eyes and conventional organization and observe evaluation CPPf/PLLA material structure biocompatibility.Result of study confirms that the CPPf/PLLA material has the favorable tissue biocompatibility; Though cause local slight inflammatory reaction in early days, inflammatory reaction disappears substantially behind the Yu Sanzhou.These CPPf/PLLA material structure biocompatibility characteristics are with research report same type of material is basic identical both at home and abroad.
(5) CPPf/PLLA material toxicology detects
With reference to American Pharmacopeia the 20th edition, preparation CPPf/PLLA sample collection fluid is carried out conventional toxicity and is detected.The result shows that this CPPf/PLLA sample does not have acute toxicity, and mouse internal organs, sperm, bone marrow stain body and micronucleus and tire mouse liver blood micronucleus are not all had obvious influence; Do not cause the mouse monster to take place.Prompting CPPf/PLLA matrix material is a kind of ideal and the bio-medical material of safety.
Embodiment
The invention will be further described below in conjunction with specific embodiment:
1. example 1: the preparation process of pin in high strength, high-modulus os integumentale screw or Steel Plate For Fixation Of Fracture, pipe and the bone:
1. choose the calcium polyphosphate fiber (CPPf) of diameter 10+1.5 μ m, degradation rate on the 1.00%, be cut into the macrofiber of 200mm;
2. weigh;
3. take by weighing 50 * 10
4D (MV) purity is 99.9% polylactide (PLLA), dissolves with organic solvent 1:80 in container;
4. use dehydrated alcohol 1:160 that polylactide (PLLA) is carried out the purifying extraction;
5. the polylactide that extraction is obtained (PLLA) particle vacuum-drying at least 24 hours (30-60 ℃ of temperature) in baking oven;
6. again with the organic solvent dissolution of polylactide (PLLA) particle with 1:80;
7. the manual shop of the calcium polyphosphate macrofiber that will 2. weigh through step layer is used simultaneously through 6. dissolved polylactide (PLLA) system film of step;
8. will volatilize naturally 24 hours through the organic solvent in the CPPf/PLLA film that 7. step is handled, again vacuum extraction 24 hours (30-60 ℃ of temperature) in baking oven;
2. use the hot pressing of flat-bed press vacuum mold, 120-200 ℃ of temperature, pressure 20-80Mpa;
3. the demoulding, repair sample, packing, sterilization, pin in high strength, high-modulus os integumentale screw or Steel Plate For Fixation Of Fracture, pipe and the bone.
Example 2: spiral shell pin or hold-down bars preparation in high strength, the high-modulus spongiosa:
1. get calcium polyphosphate fiber (CPPf), be cut into the staple fibre of 12mm;
2. weigh;
3. take by weighing purity simultaneously and be 99.9% polylactide (PLLA), in container with the ethylene dichloride dissolving of 1:80;
4. the step calcium polyphosphate staple fibre (CPPf) of 2. weighing with 3. handle through step after polylactide (PLLA) solution mix;
5. use the dehydrated alcohol purifying extraction step mixture 4. of 1:150;
Organic solvent in the CPPf/PLLA mixture that 6. will 5. obtain volatilized 24 hours naturally at least, again vacuum extraction organic solvent at least 24 hours (30-60 ℃ of temperature) in baking oven;
7. flat-bed press vacuum mold hot pressing, 120-200 ℃ of temperature, pressure 20-80Mpa;
8. the demoulding, repair sample, packing, sterilize the spongiosa inner bolt or the hold-down bars of high strength and modulus.
Below three tabulars gone out the various prescriptions that can realize and the corresponding techniques index of this matrix material.
Table 1 CPPf macrofiber high strength and modulus bone internal fixing matrix material
Table 2 CPPf staple fibre high strength and modulus bone internal fixing matrix material
Table 3 different molecular weight PLLA high strength and modulus bone internal fixing matrix material
Claims (8)
1. high strength and modulus absorbability bone internal fixing matrix material, it is characterized in that with the calcium polyphosphate fiber be reinforce, with the polylactide is the matrix thing, and calcium polyphosphate fiber and polylactide compound weight ratio are 1-80/99-20, and the molecular weight of polylactide is 20-100 * 10
4
2. matrix material according to claim 1 is characterized in that described calcium polyphosphate fibre peacekeeping polylactide compound weight ratio is 20-60/80-40.
3. matrix material according to claim 2 is characterized in that described calcium polyphosphate fibre peacekeeping polylactide compound weight ratio is 40-60/60-40.
4. according to claim 1,2 or 3 described matrix materials, the molecular weight ranges that it is characterized in that polylactide is 40-60 * 10
4
5. matrix material according to claim 4 is characterized in that the day degradation rate of described calcium polyphosphate fiber is 0.2-4%, and diameter is 5-50 μ m.
6. matrix material according to claim 5 is characterized in that the day degradation rate of described calcium polyphosphate fiber is 0.8-1.5%, and diameter is 5-25 μ m.
7. preparation is as the technology of matrix material as described in the claim 1 to 6 any, it is characterized in that preparation carries out according to the following steps:
1. choose the calcium polyphosphate fiber, be cut into the macrofiber of 10-500mm;
2. weigh;
3. take by weighing purity and be 99.9% polylactide, in container with organic solvent 1:50100 dissolving;
4. use dehydrated alcohol 1:100-200 pair polylactide to carry out the purifying extraction;
5. the polylactide particle that extraction is obtained vacuum-drying at least 24 hours in baking oven, 30-60 ℃ of temperature;
6. again with the organic solvent dissolution of polylactide particle with 1:50-100;
7. the manual shop of the calcium polyphosphate macrofiber that will 2. weigh through step layer is used simultaneously through 6. dissolved polylactide system film of step;
8. will volatilize naturally 24 hours through the organic solvent in calcium polyphosphate fiber/polylactide film that 7. step is handled, vacuum extraction 24 hours in baking oven again, 30-60 ℃ of temperature, vacuum hotpressing then, 120-200 ℃ of hot pressing temperatures make the matrix material that is used for the cortex bone internal fixing.
8. preparation is characterized in that preparing and carries out as follows as the technology of any described matrix material in the claim 1 to 6:
1. choose the calcium polyphosphate fiber, be cut into the staple fibre of 2-12mm;
2. weigh;
3. take by weighing purity simultaneously and be 99.9% polylactide, in container with ethylene dichloride 1:50-100 dissolving;
4. will through calcium polyphosphate staple fibre that 2. step weighs with 3. handle through step after polylactide solution mix;
5. use the dehydrated alcohol purifying extraction step mixture 4. of 1:50-200;
Organic solvent in the calcium polyphosphate fiber/polylactide mixture that 6. will 5. obtain volatilized 24 hours naturally at least, vacuum extraction organic solvent at least 24 hours in baking oven again, 30-60 ℃ of temperature; Vacuum hotpressing then, makes the matrix material that is used for the spongy bone internal fixing by hot pressing temperature 120-220 ℃.
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| CNB021133093A CN100523082C (en) | 2002-01-31 | 2002-01-31 | High-strength high-modulus absorbable calcium polyphosphate fibre/polylactide composition as intrabony fixing material and its preparing process |
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| US8012501B2 (en) | 2004-06-10 | 2011-09-06 | Synthes Usa, Llc | Flexible bone composite |
| CN101716369B (en) * | 2009-12-25 | 2012-09-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for calcium polyphosphate-tricalcium phosphate bone bracket |
| CN102585476B (en) * | 2012-02-21 | 2013-07-31 | 北京泰合源通生物科技有限公司 | Method for preparing glass fiber reinforced polycarbonate composite material |
| CN105818492B (en) * | 2016-03-29 | 2018-02-16 | 中材科技股份有限公司 | A kind of bioactivity phosphate base continuous glass fibre composite material for weaving and application thereof |
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