CN101342384A - Composite polymer bone-renovation material containing ceramic component and preparation method thereof - Google Patents
Composite polymer bone-renovation material containing ceramic component and preparation method thereof Download PDFInfo
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- CN101342384A CN101342384A CNA2008100458851A CN200810045885A CN101342384A CN 101342384 A CN101342384 A CN 101342384A CN A2008100458851 A CNA2008100458851 A CN A2008100458851A CN 200810045885 A CN200810045885 A CN 200810045885A CN 101342384 A CN101342384 A CN 101342384A
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Abstract
The present invention relates to a bone-repairing composite polymer material containing a ceramic ingredient and a preparation method thereof. The bone-repairing composite polymer material is composed of the calcium phosphate ceramic ingredient and a polybasic amino acid polymer ingredient, wherein, the mass ratio of the calcium phosphate ceramic ingredient is between 5 percent and 30 percent, and the rest is the polybasic amino acid polymer ingredient. Epsilon-aminocaproic acid is polymerized with at least two other types of amine acids to form the polybasic amino acid polymer ingredient, wherein, the mole ratio of the epsilon-aminocaproic acid in the polybasic amino acid polymer ingredient is between 50 percent and 90 percent, and the rest is the other amine acids including aminoacetic acid, lactamic acid, phenylalanine, lysine and proline. Under the protection of a inert gas, the materials, the amine acids and the calcium phosphate, are sufficiently and uniformly dispersed into water and then heated, so that various forms of waters can be removed from the materials, and finally, the materials are polymerized in two steps, respectively under a temperature between 200 DEG C and 220 DEG C and a temperature between 230 DEG C and 250 DEG C. The bone-repairing composite polymer material, which has excellent mechanical property, bioactivity, biocompatibility and controllable degradation property, can be perfectly combined with the interface of the bone tissue, and moreover, the degradation product is non-toxic and non-irritant.
Description
Technical field
The present invention relates to a kind of composite polymer bone-renovation material that contains ceramic component and preparation method thereof, specifically is a kind of bone renovating material of being made up of the ceramic component and the polynary amino acid polymer of calcium phosphate salt and preparation method thereof.
Background technology
Substitution material as the repair and reconstruction of sclerous tissueses such as human body bone injury comprises polytype synthos such as hydroxyapatite (HA), calcium phosphate, all is the material that has been widely used.
Hydroxyapatite (HA) is the synthos of sedimentation constant maximum.Hydroxylapatite ceramic has high mechanical strength, and comprcssive strength reaches 500～1000MPa, and bending strength reaches 115～200MPa, and Young's modulus reaches 80～110GPa.Therefore the inorganic constituents of the phosphorus/ca proportion of hydroxyapatite and human body bone is similar, has excellent biological compatibility, has been widely used in the reparation of osseous tissue clinically and substitutes.Be characterized in human body, not having substantially tangible degraded.
The calcium phosphate salt ceramic component of various ways is the big class in the multiple ceramic-like composition that has been used in bone reparation and bone reconstruction at present, as Ca (H
2PO
4)
2(MCP), CaHPO
3(CPI), Ca
2P
2O
7(CPP), CaHPO
42H
2O (DCP), CaHPO
4(ADCP), Ca
8H
2(PO
4)
65H
2O (OCP), Ca
3(PO
4)
2(TCP), Ca
10(PO
4)
6(HO)
2(HA), Ca
10(PO
4)
6F
2(FA), CaOCa
3(PO
4)
2(TTCP) and Ca
10(PO
4)
6O (OXA) etc. are characterized in having good biological activity and biocompatibility.Tricalcium phosphate (TCP) particularly as wherein etc., the calcium-phosphorus ratio of its composition is 1.5, has good biology performance, can transmitting tissue grow, promptly have bone conductibility, behind its moulding material implanting to human body, can form synostosis (being biological activity) with body tissue in a short time.Tricalcium phosphate has two kinds of crystal phase structures, β-type and α-types.Bata-tricalcium phosphate is the low temperature phase, and stable existence is below room temperature to 1120 ℃.Type alpha tricalcium phosphate then is the high temperature phase, and stable existence in 1120 ℃～1470 ℃ scopes can meta exist under anhydrous room temperature.Tricalcium phosphate has and the different biological property of hydroxyapatite (HA), and maximum difference is exactly that biodegradation can take place for it.Implanting can be by bio-absorbable, and in general the degradation rate of α-type tricalcium phosphate is greater than β-type, and is easy to take place hydrolysis and changes the apatite phase into.α-type tricalcium phosphate good than β-type aspect biocompatibility, more better than HA aspect biological activity.
In addition, the calcium hydrogen phosphate pottery (ADCP) in the calcium phosphate salt ceramic component because of its good biocompatibility, can degrade fully, surrounding tissue is not had the foreign body stimulation, also is considered to be one of the most promising bone transplantation substitute material.
Except that the above-mentioned inorganic repair materials of various ceramic-like, reparation in human body hard tissue damage and disease at present also has widely-used with reconstruction, and show the macromolecule base polymer material of the tissue repair of excellent properties, can comprise non-degradation-type and biodegradation type two big classes.Non-degradation-type macromolecular material can stable for extended periods of time in biotic environment, does not degrade, crosslinked etc., and has good physical and mechanical properties, mainly comprises as polyethylene, polypropylene, polyacrylate, aromatic esters, polysiloxanes, polyformaldehyde etc.As polyether-ether-ketone (PEEK) is a kind of compatible hard tissue substituting material of good biological mechanics that is considered to have, and extensively uses in fields such as spinal column reparation rectification; Ultra-high molecular weight polyethylene (UHMWPE) also has been widely used in artificial joint.These macromolecular materials are biologically inerts, can implant for a long time, are generally only stablizing the bearing position use, and function is limited aspect hard tissue repair and reconstruction.
The biodegradation type macromolecular material comprises natural macromolecular material (as collagen, chitin, cellulose etc.) and synthetic controlled degradation polymer such as linear aliphatic adoption ester, polyvinyl alcohol etc., and structural deterioration and performance regression can take place under the biotic environment effect these materials.At present the subject matter of the natural macromolecular material that uses be intensity low, rejection arranged.Synthetic degradable high polymer material (as polylactic acid etc.), its degradation in vivo speed can not control, degradation processes and mechanical property can not be mated, catabolite produces side effect such as stimulation, inflammation to tissue; And the intensity of degradable aliphatic polyester series material is low, the reconstruction that can not satisfy bearing position.In addition, though polyamide (PA) has the amido link-N-C=O identical with protein, result of study shows that synthesizing polyamides PA-66 commonly used can not be degraded by esterase, only can be degraded, and palliating degradation degree is very low by papain, trypsin and Chymotrypsin; The degraded of PA-6 is also very difficult.The oligomer that has only the degree of polymerization≤6 just may by the Flavobacterium bacterial strain (P-EI of K172, F-EII, E-III), pseudomonas strain NK87 (P-EII) and episilon amino caproic acid hydrolyzing oligomer enzyme (E-III) degraded.Occurring in nature is by materials such as biosynthetic protein and polypeptide silkworm silk, collagens, it all has the structure of PA, and these materials all are biological controlled degradations.
The good toughness of simple macromolecular material, but lack biological activity; Simple ceramic material has good biological activity but the toughness deficiency.Above-mentioned ceramic-like inorganic constituents and high molecular polymer constituents are mutually combined the compound bone renovating material that forms then with the two advantage.This currently reported and/or use class composite is as polylactic acid/calcium phosphate, polylactic acid/hydroxy apatite, nylon 66/ hydroxyapatite, Merlon/hydroxyapatite, collagen/calcium phosphate etc.Wherein, polylactic acid and collagen are degraded, but as the macromolecule phase, the degradation speed of polylactic acid is wayward, the mechanical property deficiency of collagen, and serviceability temperature is low, and these have all limited the use of material.The composite that nondegradable macromolecule such as nylon 66, Merlon etc. and Ca-P ceramic form is then because of being nondegradable, and after implanting, existence steady in a long-term is restricted the regeneration of autologous tissue.
The controlled degradation bone renovating material can be kept enough intensity and hardness in the knitting process, can support the external force of fracture site normal physiological activity, degraded gradually after union of fracture, external force can be transferred to gradually on the body bone, thereby make its function return to the level of normal bone naturally, thereby this type of repair materials becomes one of hot research in recent years, and the performance of material has been had higher requirement, as having excellent biological compatibility, have no adverse reaction with tissue and cell; Have the good mechanical performance, in the knitting process, should be able to keep enough intensity and hardness, enough supports can be provided, to support the external force of fracture site normal physiological activity; Should have controlled degradation property, can regulate, and catabolite should nontoxic, nonirritant degradation cycle; Also should have good hydrophilicity, help cell and tissue characteristics with the aspects such as interaction of material.
Summary of the invention
At above-mentioned situation, the present invention will provide a kind of composite polymer bone-renovation material that contains ceramic component of new model, to improve the problem and shortage of present same type of material, satisfy medical science and use needs in hard tissue repair and the reconstruction field clinically.On this basis, the present invention also will provide said this to contain the preparation method of the composite polymer bone-renovation material of ceramic component.
The composite polymer bone-renovation material that contains ceramic component of the present invention, ceramic component and polynary amino acid polymer by the calcium phosphate salt are formed, the mass ratio of calcium phosphate salt ceramic component is 5%～30%, all the other are polynary amino acid polymer composition, said polynary amino acid polymer composition is for be polymerized by episilon amino caproic acid and two kinds of other aminoacid at least, wherein the molar ratio of episilon amino caproic acid is 50%～90% of a component of polymer, all the other are said other aminoacid, and wherein the mole of every seed amino acid should be no less than 1% of polynary amino acid polymer composition, said other aminoacid is glycine, alanine, phenylalanine, lysine, proline, the structure of said this bone renovating material is suc as formula shown in (I)
CaM in the formula (I) is the ceramic component of calcium phosphate salt; R
1, R
2For containing amino fat-based, m=1～6, n=180～320 in identical or different said other aminoacid.
The ceramic component of said calcium phosphate salt in the above-mentioned bone renovating material (CaM in the formula (I)) can comprise the calcium salt composition of the above-mentioned currently reported and/or various ways phosphoric acid that uses, as Ca (H
2PO
4)
2(MCP), CaHPO
3(CPI), Ca
2P
2O
7(CPP), CaHPO
42H
2O (DCP), CaHPO
4(ADCP), Ca
8H
2(PO
4)
65H
2O (OCP), Ca
3(PO
4)
2(TCP), Ca
10(PO
4)
6(HO)
2(HA), Ca
10(PO
4)
6F
2(FA), CaOCa
3(PO
4)
2(TTCP) and Ca
10(PO
4)
6O (OXA) etc.In these phosphoric acid salt compositions, except that HA, FA, TTCP and OXA, all be degradable composition.Degradable synthos can dissolve and discharge calcium, phosphonium ion under people's humoral effect, can promote bone growth and healing.But this class material is usually used in quickly-healing, and repair at the position that does not need to provide mechanics to support for a long time.
Because tricalcium phosphate pottery wherein (comprises β-TCP and α-TCP, particularly α-TCP) and calcium hydrogen phosphate pottery (ADCP) ceramic component, has good biology performance, good biocompatibility, degraded fully, therefore non-stimulated to surrounding tissue, the ceramic component of said calcium phosphate salt is preferably a kind of in tricalcium phosphate ceramic component or the calcium hydrogen phosphate ceramic component.
Said component of polymer in the above-mentioned bone renovating material, generally speaking to adopt the form that become with 2～5 kinds of said other aminoacid polymerizations by episilon amino caproic acid, when particularly the viscosity of this bone renovating material in the time of 240 ℃ is 1000～4000PaS, can both have effect preferably, can be so that this bone renovating material can have the degradation speed or the cycle of good mechanical performance and may command and adjusting.For example, can make the comprcssive strength in the mechanical performance index of bone renovating material of gained reach 60～150Mpa, bending strength is 40～90Mpa, tensile strength is 60～130Mpa, elastic modelling quantity is 1～8Gpa etc., water absorption rate can reach 8～25%, will very help organizing and the interaction of cell with material.Soaked for 12 weeks in in-vitro simulated body fluid after, the degraded weight-loss ratio of this bone renovating material can be regulated and control in 5%～60% scope as required.
For further improving biological activity and the biocompatibility and the human body acceptability of above-mentioned bone renovating material, reduce the catabolite zest and/or to the adverse effect of human body, the present invention is above-mentioned to contain said other aminoacid in the composite polymer bone-renovation material of ceramic component, all select for use to be the acceptable aminoacid of human body, as natural amino acids such as corresponding L-alanine, L-phenylalanine, L-lysine, L-proline in said each seed amino acid.
The above-mentioned preparation method that contains the composite polymer bone-renovation material of ceramic component, be after raw material synthos, episilon amino caproic acid are reached at least two kinds of other aminoacid water homodisperse, be heated to≤remove the various forms of moisture that are present in the mixture material under 200 ℃ of conditions, under 200 ℃～220 ℃ conditions, carry out earlier the prepolymerization reaction then, be warming up to again under 230 ℃～250 ℃ conditions and carry out polyreaction.The mass ratio of said synthos composition is 5%～30% in the raw material; The mole dosage ratio of said episilon amino caproic acid is 50%～90% of whole aminoacid integral molar quantities, all the other are other aminoacid, and wherein the mole dosage ratio of every seed amino acid should be no less than 1% of whole aminoacid integral molar quantities, and said other aminoacid is glycine, alanine, phenylalanine, lysine, proline.To processed and each step polyreaction of raw material, all should under protection, carry out and finish in the preparation process as noble gases such as nitrogen commonly used.
Test shows that generally speaking, it all is permission and feasible in the scope that prepolymerization reaction in the above-mentioned preparation process and polymerization reaction time are controlled at 1～5 hour respectively, and the yield of its polymerizate generally all can reach more than 95%.According to result of the test, generally can be in the preparation process by the change of reaction mass viscosity increase, and/or situation about darkening, and/or different modes such as said response time, each step polyreaction process is controlled, particularly said this polyreaction being controlled at above-mentionedly when making end-product reach viscosity in the time of 240 ℃ to be 1000～4000PaS, is even more ideal.
By the composite purity height that aforesaid way prepares, good uniformity, free from foreign meter, yield generally can reach more than 95%, and the content of inorganic calcium phosphate phase salt ceramic component is good with calculating charge ratio anastomose property, and good reproducibility is highly stable.
Because the structure main chain in the above-mentioned bone renovating material has very strong polarity and rigidity, thereby can have excellent mechanical property, and by each aminoacid of peptide key connecting, have the chemical constitution of similar human body protein in the structure, catabolite is oligopeptide or aminoacid micromolecule.Test shows, by changing and regulate the mass percent of raw material calcium phosphate salt ceramic component, and/or the molar ratio of the episilon amino caproic acid in the polymer moieties and other natural amino acid, and/or pass through the molecular weight that controlling reaction time changes the product polymer, can change and regulate the mechanical property and/or the degradation speed of gained repair materials product.For example, increase the mass percent of the ceramic component of calcium phosphate salt, and/or make m value increase in the said structure formula (I) (promptly increasing the content of the episilon amino caproic acid in the polymeric material composition), can improve the mechanical property of gained repair materials product, corresponding its degradation speed that slows down; N value increases in the said structure formula (I), promptly prolongs polymerization reaction time, increases product degree of polymerization and molecular weight, mechanical property that also can corresponding raising product with slow down degradation speed.Therefore, proportion of composing and/or polymerization reaction time by suitable adjustment and change polymeric material just can obtain meeting the mechanical property requirements of use and/or the above-mentioned composite bone repairing material of degradation speed.
Because the inorganic phase that the present invention is above-mentioned to be contained in the composite polymer bone-renovation material of ceramic component partly is the verified material with good biological safety, degradable is calcium ion and corresponding phosphate anion under humoral effect; The chemical constitution that then has similar human body protein in the polymer moieties, thereby biomechanical property and the biological activity and the compatibility with excellence, and has a good hydrophilicity, help organizing interaction with cell and storeroom, catabolite is near neutral oligopeptide or aminoacid micromolecule, or be that carbon dioxide and water are discharged through metabolic degradation further, safety is very high.Zoopery is the result show: this material non-toxic, non-stimulated, nothing allergy, no any untoward reaction between material and the tissue.Behind this polymer bone-renovation material implantable bioartificial body, under the effect of body tissue, can progressively degrade according to the degradation speed cycle of design in advance.Thereby be a kind of have controllable degradation speed, with from the biomechanical property of body bone coupling and the bionic biomedical and the tissue engineering material of the good biological activity and the compatibility, improved existing deficiency of present similar repair materials and problem.
The specific embodiment below in conjunction with embodiment is described in further detail foregoing of the present invention again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made all should comprise within the scope of the invention.
The specific embodiment
Example 1～8
Phosphate in each example, episilon amino caproic acid and glycine, alanine, phenylalanine, lysine, raw material such as proline and consumption are as shown in table 1 respectively.Raw material is added in the 250ml three-necked bottle, add water 100ml, dehydration under 200 ℃ of conditions (can whether begin mode such as fusion and judge whether processed is finished) by observing aminoacid.Be warming up to 220 ℃ after dehydration is finished, carry out prepolymerization under the molten state, be warming up to 230 ℃ then and proceed polyreaction, get degradable composite material.The time in two steps of prepolymerization and polyreaction, the yield of polyreaction and relevant mechanical properties index, gained composite soak the weight-loss ratio of degrading behind the 12w etc. in simulated body fluid, distinguish as shown in table 1.
Example 9
With HA 25g, episilon amino caproic acid 105g, and phenylalanine, glycine, proline is respectively 14g, 3g, the raw material of 5g adds in the 250ml three-necked bottle, add water 100ml, dewater under 200 ℃ of conditions, dehydration is warming up to 220 ℃ after finishing, frit reaction 3 hours, continue to be warming up to 230 ℃ of reactions 3 hours, get degradable composite material, yield is 96%.The viscosity of gained composite is 3100PaS (240 ℃), and comprcssive strength is 106Mpa, and tensile strength is 96Mpa, bending strength 71Mpa, elastic modelling quantity 2.6Gpa; After in simulated body fluid, soaking 12w, weightless 11.4%.
Example 10
With ADCP 25g, episilon amino caproic acid 96g, and glycine, lysine is respectively 4g, the raw material of 20g adds in the 250ml three-necked bottle, add water 100ml, in 200 ℃ of dehydrations down, dehydration is warming up to 220 ℃ after finishing, frit reaction 3 hours, continue to be warming up to 230 ℃ of reactions 3 hours, get degradable composite material, yield is 97%.The viscosity of polymer is 3200PaS (240 ℃) in the gained composite, and comprcssive strength is 102Mpa, and tensile strength is 95Mpa, bending strength 60Mpa, elastic modelling quantity 2.6Gpa; After in simulated body fluid, soaking 12w, weightless 15.4%.
Example 11
With Ca
2P
2O
7(CPP) 45g, episilon amino caproic acid 105g and alanine, phenylalanine, glycine, proline is respectively 6g, 7g, 1g, the raw material of 5g adds in the 250ml three-necked bottle, adds water 100ml, in 200 ℃ of dehydrations down, dehydration is warming up to 220 ℃ after finishing, and frit reaction 2 hours continues to be warming up to 230 ℃ of reactions 4 hours, get degradable composite material, yield is 97%.The viscosity of degradable composite material is 3200PaS (240 ℃) in the gained material, and comprcssive strength is 102Mpa, and tensile strength is 95Mpa, bending strength 60Mpa, elastic modelling quantity 2.6Gpa; After in simulated body fluid, soaking 12w, weightless 15.4%.
Comparative Examples 1
HA25g, episilon amino caproic acid 108g, glycine, alanine, phenylalanine, lysine, proline is respectively 0.55g, 3.5g, 3g, 1g, 3g add in the 250ml three-necked bottle, add water 100ml, 200 ℃ of dehydrations down, dehydration is warming up to 220 ℃ after finishing, fusion was reacted 3 hours, continued to be warming up to 230 ℃, reacted 5 hours, and got composite products, yield is 95%.The viscosity of products obtained therefrom is 3700PaS (240 ℃), and comprcssive strength is 146Mpa, and tensile strength is 119Mpa, bending strength 91Mpa, elastic modelling quantity 6.6Gpa; After in simulated body fluid, soaking 12w, weightless 0.7%.Because the episilon amino caproic acid consumption too high (greater than 95%) in the composite is during because of the non-degradable of phosphate own, so this composite is difficult to degraded.
Comparative Examples 2
DCP 30g, episilon amino caproic acid 45.5g, glycine, alanine, phenylalanine, lysine, proline is respectively 3.75g, 24.92g, 16.5g, 2.92g, 5.75g, add in the 250ml three-necked bottle, add water 100ml, 200 ℃ of dehydrations down are warming up to 220 ℃ afterwards, carry out the prepolymerization reaction after the fusion after 1 hour, continue to be warming up to 230 ℃ and carried out polyreaction 2 hours, get polymer product, yield 96.8%.After testing, the comprcssive strength of the polymer product of gained is 49Mpa, and tensile strength is 41Mpa, bending strength 37Mpa, elastic modelling quantity 0.8Gpa; Soak 12w in simulated body fluid after, weight-loss ratio is 71.7%.This composite is because of episilon amino caproic acid content low (be lower than total amino acid content 50%), and polymerization reaction time is short, and phosphate itself is also capable of being fast degraded, and so the mechanical property of material is relatively poor, it is too fast to degrade, and is difficult to satisfied requirement as bone renovating material.
Claims (10)
1. the composite polymer bone-renovation material that contains ceramic component, it is characterized in that forming by the ceramic component and the polynary amino acid polymer of calcium phosphate salt, the mass ratio of calcium phosphate salt ceramic component is 5%～30%, all the other are polynary amino acid polymer composition, said polynary amino acid polymer composition is for be polymerized by episilon amino caproic acid and two kinds of other aminoacid at least, wherein the molar ratio of episilon amino caproic acid is 50%～90% of a component of polymer, all the other are said other aminoacid, and the mole in wherein every seed amino acid should be no less than 1% of polynary amino acid polymer composition, said other aminoacid is glycine, alanine, phenylalanine, lysine, proline, the structure of said this bone renovating material is suc as formula shown in (I)
CaM in the formula (I) is the ceramic component of calcium phosphate salt; R
1, R
2For containing amino fat-based, m=1～6, n=180～320 in identical or different said other aminoacid.
2. the composite polymer bone-renovation material that contains ceramic component as claimed in claim 1, the ceramic component that it is characterized in that said calcium phosphate salt are a kind of in tricalcium phosphate ceramic component or the calcium hydrogen phosphate ceramic component.
3. the composite polymer bone-renovation material that contains ceramic component as claimed in claim 1 is characterized in that other aminoacid in the said polymer composition is the acceptable aminoacid of human body.
4. the composite polymer bone-renovation material that contains ceramic component as claimed in claim 1 is characterized in that the said polymer composition is polymerized by episilon amino caproic acid and two kinds of said other aminoacid at least.
5. as the described composite polymer bone-renovation material that contains ceramic component of one of claim 1 to 4, the viscosity when it is characterized in that 240 ℃ of said repair materials is 1000～4000PaS.
6. the preparation method that contains the composite polymer bone-renovation material of ceramic component; it is characterized in that the raw material synthos; after episilon amino caproic acid reaches at least two kinds of other aminoacid water homodisperse; be heated to≤remove the various forms of moisture that are present in the mixture material under 200 ℃ of conditions; under 200 ℃～220 ℃ conditions, carry out earlier the prepolymerization reaction then; be warming up to again under 230 ℃～250 ℃ conditions and carry out polyreaction; the processed of raw material; prepolymerization and polyreaction are all carried out under inert gas shielding; the mass ratio of said synthos composition is 5%～30% in the raw material; the mole dosage ratio of said episilon amino caproic acid is 50%～90% of whole aminoacid integral molar quantities; all the other are other aminoacid; and wherein the mole dosage ratio of every seed amino acid should be no less than 1% of whole aminoacid integral molar quantities, and said other aminoacid is glycine; alanine; phenylalanine; lysine; proline.
7. the preparation method that contains the composite polymer bone-renovation material of ceramic component as claimed in claim 6 is characterized in that said other aminoacid is the acceptable aminoacid of human body.
8. the preparation method that contains the composite polymer bone-renovation material of ceramic component as claimed in claim 6 is characterized in that other used aminoacid is 2～5 kinds.
9. the preparation method that contains the composite polymer bone-renovation material of ceramic component as claimed in claim 6 is characterized in that said prepolymerization reaction and polymerization reaction time are 1～5 hour respectively.
10. as the described preparation method that contains the composite polymer bone-renovation material of ceramic component of one of claim 6 to 9, it is characterized in that the viscosity of said polyreaction control end-product in the time of 240 ℃ is 1000～4000PaS.
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| CN103007343A (en) * | 2013-01-16 | 2013-04-03 | 重庆医科大学 | Hard tissue repair and substitute material and preparation method thereof |
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| CN103007343B (en) * | 2013-01-16 | 2014-06-25 | 重庆医科大学 | Hard tissue repair and substitute material and preparation method thereof |
| WO2016070501A1 (en) * | 2014-11-04 | 2016-05-12 | 四川国纳科技有限公司 | Multi-(amino acid) polymer-hydroxyapatite bone repair material, supporting-type implant and preparation method |
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