CN103550823A - Injectable compound bone cement as well as preparation method and application thereof - Google Patents
Injectable compound bone cement as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN103550823A CN103550823A CN201310545809.8A CN201310545809A CN103550823A CN 103550823 A CN103550823 A CN 103550823A CN 201310545809 A CN201310545809 A CN 201310545809A CN 103550823 A CN103550823 A CN 103550823A
- Authority
- CN
- China
- Prior art keywords
- mma
- mps
- preparation
- gained
- bone cement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Materials For Medical Uses (AREA)
Abstract
本发明涉及一种可注射复合型骨水泥的制备方法，包括以下步骤，S1.纳米羟基磷灰石的合成；S2.P（MMA-co-MPS）的合成；S3.P(MMA-co-MPS)-HA的制备；S4.高分子量PMMA的合成；S5.骨水泥的配制。本发明利用两亲性聚合物P(MMA-co-MPS)偶联修饰纳米羟基磷灰石，有利于纳米羟基磷灰石在MMA液相中的分散，使得HA/PMMA更容易调配且可获得更好的力学性能。The invention relates to a method for preparing an injectable composite bone cement, comprising the following steps: S1. Synthesis of nano-hydroxyapatite; S2. Synthesis of P (MMA-co-MPS); S3. P (MMA- co-MPS ) Preparation of MPS)-HA; S4. Synthesis of high molecular weight PMMA; S5. Preparation of bone cement. The present invention uses amphiphilic polymer P (MMA-co-MPS) to couple and modify nano-hydroxyapatite, which is beneficial to the dispersion of nano-hydroxyapatite in MMA liquid phase, making HA/PMMA easier to prepare and obtainable Better mechanical properties.
Description
Technical field
The present invention relates to bone material, more specifically, relate to compound bone cement of a kind of injectable and its preparation method and application.
Background technology
There are many shortcomings as bone filler and fixed fae body in PMMA class bone cement, as produced heat in polymerization process, near the temperature of implant site is raise; Residual monomer can cause osteonecrosis; At bone-cement interface, form fibrous tissue; Can not be absorbed, also be unfavorable for that bone grows into; Fatigue strength deficiency etc.; What is more important, along with the aggravation of aged tendency of population, to there being higher demand the service life of orthopedic implanting material; And PMMA bone cement does not possess biological activity, after implant into body, service life is about 5～10 years, and a lot of patients also face actual bodily harm and the economic loss that second operation brings, so limited its application and popularization clinically.
Summary of the invention
In order to obtain a kind of bone cement material of better effects if, first the present invention provides the preparation method of the compound bone cement of a kind of injectable, comprises the following steps:
S1. nanometer hydroxyapatite is synthetic;
Take (CaNO
3)
24H
2o and (NH
4)
2hPO
4powder dissolution is in water, under the condition of ultrasonic agitation, by (NH
4)
2hPO
4solution is added drop-wise to (CaNO
3)
24H
2in O solution, add dispersant, regulate pH, ageing, centrifugal, washing, obtains;
S2. P(MMA-co-MPS) synthetic:
Under noble gas, methyl methacrylate, azodiisobutyronitrile, silane coupler and oxolane are added in container, 60 ~ 70 ℃ of stirring reactions 6 ~ 8 hours, obtain P(MMA-co-MPS);
S3. P (MMA-
co-MPS) preparation of-HA:
The mixed solution of ethanol/water is adjusted to acidity with glacial acetic acid, by the P(MMA-co-MPS described in step S2) add wherein, then add the nanometer hydroxyapatite of S1 gained, and be adjusted to alkalescence, by product filtration drying, then use oxolane supersound washing, obtain,
S4. high molecular PMMA's is synthetic:
Polyvinyl alcohol is dissolved in distilled water, stir after lower fully dissolving, add methyl methacrylate (and dibenzoyl peroxide, be warming up to 60 ~ 100 ℃, react after 5 ~ 6h, by distillation washing 3 ~ 5 times for the product of gained, be placed in the dry 4 ~ 8h of 70 ~ 90 ℃ of baking ovens, obtain, the high molecular PMMA of gained is milled into granule, stand-by;
S5. the preparation of bone cement:
The high molecular PMMA of S4 gained is joined to the P (MMA-of S3 gained
co-MPS), in-HA, obtain.
High molecular PMMA described in step S5 and P (MMA-
co-MPS) weight ratio of-HA is 1:0.5 ~ 20.
Dispersant described in step S1 is PEG2000, and described pH is 9 ~ 11, and the time of described ageing is 12 ~ 36 hours.
In the mixed solution of the ethanol/water described in step S3, the volume ratio of second alcohol and water is 8 ~ 10:1, and described acidity is pH3 ~ 4.
(CaNO described in step S1
3)
24H
2o powder and (NH
4)
2hPO
4the mass ratio of powder is 1:1 ~ 5.
The application of the compound bone cement of injectable that same said method is prepared gained again in preparing orthopedic implanting material.
Wherein, (CaNO3)
24H
2o: four water-calcium nitrate; (NH4) 2HPO4: diammonium phosphate; PEG: Polyethylene Glycol
MMA: methyl methacrylate; PVA: polyvinyl alcohol; BPO: dibenzoyl peroxide
PMMA: polymethyl methacrylate; MPS: silane coupler; THF: oxolane;
NaOH: sodium hydroxide; Glacial acetic acid: glacial acetic acid.
The present invention has following beneficial effect:
(1) the method for the invention is of many uses, is a kind of injectable type bone cement, arbitrarily plastotype;
(2) bone cement of the present invention is easy to prepare quick, at room temperature molding, mild condition;
(3) it has good biocompatibility, and solidification process thermal discharge low (highest temperature: 40 ~ 50 ℃), can be converted into after implant into body and the similar the Nomenclature Composition and Structure of Complexes of nature bone;
(4) liberated heat is few during polymerization, reduces the contraction that polymerization causes, the mechanical property of refinforced cement.
(5) compressive strength, bending modulus, the bending strength of the PMMA/HA bone cement that the present invention synthesizes increase significantly compared to HA.Be expected to be widely used in bio-medical engineering material field as injectable pharmaceutical carrier.
The specific embodiment
Below in conjunction with specific embodiment, further describe the present invention.Unless stated otherwise, reagent, equipment and the method that the present invention adopts is the conventional commercial reagent of the art, equipment and the conventional method of using.
Embodiment 1
Take Polyethylene Glycol (PEG-2000) 30.9g and be dissolved in 1000ml distilled water, (NH
4)
2hPO
413.2g is dissolved in 500 ml distilled water.After having dissolved, PEG adds (CaNO
3)
24H
2o 47.2g.Under mechanical agitation (1300 revs/min) and ultrasonic assisting, by (NH
4)
2hPO
4be added drop-wise to (CaNO
3)
24H
2in O, regulate PH to 10～11, reaction finishes rear ageing 20 h.By the product washing obtaining 3 times, ethanol is washed 1 time, at 80 ℃, is dried, and obtains rod-like nano HA.
Embodiment 2
0.35 g polyvinyl alcohol (PVA) is dissolved in to 180 ml distilled water, stir after (380 revs/min) lower fully dissolving, add the methyl methacrylate (MMA) of 56 ml and the BPO of 0.14g, 79 ℃ are reacted 2 hours, 87 ℃ of reactions, 95 ℃ of reactions in 2 hours 2 hours, by distilled water washing 3 times for the product of gained, are placed in the dry 4h of 80 ℃ of baking ovens, then its grinding is sieved and obtain white fine powder granule PMMA, molecular weight is 700,000 left and right.
Embodiment 3
In Ar atmosphere, enclose and lower MMA 27ml, AIBN 0.11808g, MPS 7.1424g, TGA 249 μ l, THF 60ml are added in reaction bulb, after half an hour, turn off Ar gas.At 70 ℃, stirring reaction 6h obtains P (MMA-
co-MPS).By the product of gained, use ether reprecipitation 2 ~ 3 times, vacuum drying obtains sample, clays into power, and sealing is preserved, standby.
Embodiment 4
The mixed solution 110ml of preparation ethanol/water (v/v=9:1), wherein V
ethanol99ml, V
water11ml.Deionized water is made into mixed solution, and regulates pH value 3.5～4.0 with glacial acetic acid, then by appropriate P (MMA-
co-MPS) add wherein, 50 ℃ of reaction 1h, make siloxanes complete hydrolysis.The HA that gets 100ml adds wherein, with 10% NaOH, regulates PH=10 to promote condensation reaction.The product of gained is filtered, and 120 ℃ dry, by the dry ultrasonic 30min of oxolane for powder (THF), repeatedly with THF is ultrasonic, washes 3 times, and then 120 ℃ are dried, and obtain P (MMA-
co-MPS)-HA.
Embodiment 5
23
at 1 ℃, liquid component (MMA, DMT) is joined in solid constituent (HA, PMMA and BPO), stir after 1 ~ 2min, pour in mould, after solidifying, by sand papering compression experiment sample size, be L (high mm)/D (diameter mm)=2, crooked experiment sample size is for being about 75mm, wide 10mm, the lath of thick 3.3mm.
Embodiment 6
Should be 23 before all compression experiment sampling tests
more than preserving 16h under the environment of 1 ℃, at 23 ℃
at 1 ℃, by compression experiment sample, (height is 12mm
0.01mm, bottom surface diameter is 6mm
the cylinder of 0.1mm), the loading speed with 5mm/min on universal testing machine loads, and carries out compression experiment, and record causes power or 2% yield load of breaking, and this power, divided by the original cross-sectional area of cylinder, is tried to achieve to compressive strength.And calculate average compressive strength.The compressive strength of gained composite bone cement, all higher than international standard 70MPa, illustrates by P (MMA-
co-MPS) random public polymers is modified nanometer HA surface, improve dispersibility and the stability of HA in methyl methacrylate (MMA) monomer, by strengthening organic and inorganic interface interaction, obtained high-strength composite HA/PMMA bone cement material.
Before crooked experiment sampling test, should be immersed in 37
50h in the water-bath of 1 ℃
2h.By crooked experiment sample, thinking carefully that on puller system, the loading speed with 5mm/min loads, carry out three-point bending test, span
=60mm, power and displacement curve figure thereof during record fracture, calculate and try to achieve bending modulus and bending strength thereof, and ask its meansigma methods.The bending strength of the compound bone cement of H-HA/PMMA is higher than international standard 50MPa.The bending modulus of H-HA/PMMA bone cement is along with H-HA content is without significant change, but its value is all higher than 1.8GPa.
Embodiment 7
In Ar atmosphere, enclose and lower MMA 27ml, AIBN 0.11808g, MPS 7.1424g, TGA 249 μ l, THF 60ml are added in reaction bulb, after half an hour, turn off Ar gas.At 70 ℃, stirring reaction 6h obtains P (MMA-co-MPS).By the product of gained, use ether reprecipitation 2 ~ 3 times, vacuum drying obtains sample, clays into power, and sealing is preserved, standby.
Embodiment 8
The mixed solution 110ml of preparation ethanol/water (v/v=9:1), V ethanol 90ml wherein, V water 10ml.Deionized water is made into mixed solution, and regulates pH value 3.5～4.0 with glacial acetic acid, then the P of 0.5g (MMA-co-MPS) is added wherein, and 50 ℃ of reaction 1h, make siloxanes complete hydrolysis.Get 100ml HA emulsion (16g HA powder is dissolved in 400ml deionized water) and add wherein, with 10% NaOH, regulate PH to 10 to promote condensation reaction.The product of gained is filtered, and 120 ℃ dry, by the dry ultrasonic 30min of oxolane for powder (THF), repeatedly with THF is ultrasonic, washes 3 times, and then 120 ℃ are dried, and obtain P (MMA-co-MPS)-HA.
Embodiment 9
The mixed solution 100ml of preparation ethanol/water (v/v=9:1), V ethanol 90ml wherein, V water 10ml.Deionized water is made into mixed solution, and regulates pH value 3.5～4.0 with glacial acetic acid, then the P of 1.5g (MMA-co-MPS) is added wherein, and 50 ℃ of reaction 1h, make siloxanes complete hydrolysis.The HA that gets 100ml adds wherein, with 10% NaOH, regulates PH=10 to promote condensation reaction.The product of gained is filtered, and 120 ℃ dry, by the dry ultrasonic 30min of oxolane for powder (THF), repeatedly with THF is ultrasonic, washes 3 times, and then 120 ℃ are dried, and obtain P (MMA-co-MPS)-HA.
Embodiment 10
The mixed solution 100ml of preparation ethanol/water (v/v=9:1), V ethanol 90ml wherein, V water 10ml.Deionized water is made into mixed solution, and regulates pH value 3.5～4.0 with glacial acetic acid, then the P of 2.5g (MMA-co-MPS) is added wherein, and 50 ℃ of reaction 1h, make siloxanes complete hydrolysis.The HA that gets 100ml adds wherein, with 10% NaOH, regulates PH=10 to promote condensation reaction.The product of gained is filtered, and 120 ℃ dry, by the dry ultrasonic 30min of oxolane for powder (THF), repeatedly with THF is ultrasonic, washes 3 times, and then 120 ℃ are dried, and obtain P (MMA-co-MPS)-HA.
Embodiment 11
The HA that HA in embodiment 1, embodiment 3, embodiment 4,0.5g P (MMA-co-MPS) are modified, and P (MMA-co-MPS)-HA that 2.5g modifies is dissolved in MMA respectively.During ultrasonic rear standing 1min, L-HA and H-HA can form the suspension of homogeneous in MMA solvent, and especially H-HA can disperse uniformly, do not observe the aggregate of sedimentation; After standing 5min, the basic sedimentation of HA, and be all suspended in solvent through the HA major part of finishing, only have the phenomenon of small part sedimentation, this phenomenon shows the HA after finishing, has improved dispersibility and stability in MMA solvent.More than analyze and obtain: the stability of HA in MMA solvent and dispersibility are by by force to weak putting in order as H-HA>L-HA>HA.Illustrate that HA, after P (MMA-co-MPS) finishing, has improved dispersibility and the stability of HA in MMA solvent, improve the compatibility of HA and PMMA matrix material.
Embodiment 12
Crooked experiment sample size is for being about 75mm, wide 10mm, the lath of thick 3.3mm.Before laboratory sample test, should be immersed in 37
50h in the water-bath of 1 ℃
2h.By crooked experiment sample, thinking carefully that on puller system, the loading speed with 5mm/min loads, carry out three-point bending test, span 60mm.Can see that HA is dispersed in PMMA matrix uniformly.
Embodiment 13
The first step, takes 30.9g (CaNO
3)
24H
2o and 13.2g (NH
4)
2hPO
4powder is dissolved in respectively in deionized water, is mixed with 0.2mol/L (CaNO
3)
24H
2o solution and 0.2mol/L (NH
4)
2hPO
4solution.
Second step, under ultrasonic auxiliary and 1300rad/min mechanical agitation, by (NH
4)
2hPO
4be added drop-wise to (CaNO
3)
24H
2in O, and adopt PEG2000 as dispersant, with ammonia, regulate PH to 10.
The 3rd step, drips and finishes rear ageing 24 h.To obtain centrifugal 10000 r/min of product, 20min, washes 3 times to obtain nanometer hydroxyapatite.
The nanometer hydroxyapatite microscopic pattern of preparation is bar-shaped, scattered; Be about 120nm, wide about 30nm(draw ratio is about (5:1).
Embodiment 14
The first step, takes 8.856g (CaNO
3)
24H
2o and 2.971g (NH
4)
2hPO
4powder is dissolved in respectively in deionized water, is mixed with 0.2mol/L (CaNO
3)
24H
2o solution and 0.2mol/L (NH
4)
2hPO
4solution.
Second step, under ultrasonic auxiliary and 1100rad/min mechanical agitation, by (NH
4)
2hPO
4be added drop-wise to (CaNO
3)
24H
2in O, and adopt PEG2000 as dispersant, with ammonia, regulate PH to 10.
The 3rd step, drips and finishes rear ageing 24 h.To obtain centrifugal 10000 r/min of product, 20min, washes 3 times to obtain nanometer hydroxyapatite.
Microscopic pattern is needle-like, is about 80nm.
Embodiment 15
The first step, at room temperature, by (the CaNO of 9.54g
3)
24H
2o adds in the 80mL Aqueous Solutions of Polyethylene Glycol (4w%t) having dissolved in advance.
Second step, configuration 0.8mol/L (NH
4)
2hPO
4solution 30mL regulates pH value 10 with ammonia simultaneously in dropping process.
The 3rd step, is added dropwise to complete rear continuation and stirs 30min ageing 24h.
The nanometer hydroxyapatite microscopic pattern of preparation is needle-like, is about 60nm.
Embodiment 16
The first step, 3.02g (CaNO
3)
24H
2o adds 2.5ml ammonia after being dissolved in the deionized water of 40ml, mixes ultrasonic.
Second step, 1.454g (NH
4)
2hPO
4after being dissolved in 60ml deionized water, under ultrasonic auxiliary and 1100rad/min mechanical agitation, be slowly added dropwise in the mixed liquor of first step gained, and with PEG2000 as dispersant, accurately regulate PH to 9.
The 3rd step, drips and finishes rear ageing 24h.Product is centrifugal, wash 3 times.
The nanometer hydroxyapatite microscopic pattern of preparation is bar-shaped, is about 150nm, wide about 30nm.
Claims (6)
1. a preparation method for the compound bone cement of injectable, is characterized in that, comprises the following steps:
S1. nanometer hydroxyapatite is synthetic;
Take (CaNO
3)
24H
2o and (NH
4)
2hPO
4powder is dissolved in the water respectively, under the condition of ultrasonic agitation, by (NH
4)
2hPO
4solution is added drop-wise to (CaNO
3)
24H
2in O solution, add dispersant, regulate pH, ageing, centrifugal, washing, obtains;
S2. P(MMA-co-MPS) synthetic:
Under noble gas, methyl methacrylate, azodiisobutyronitrile, silane coupler and oxolane are added in container, 60 ~ 70 ℃ of stirring reactions 6 ~ 8 hours, obtain P(MMA-co-MPS);
S3. P (MMA-
co-MPS) preparation of-HA:
The mixed solution of ethanol/water is adjusted to acidity with glacial acetic acid, by the P(MMA-co-MPS described in step S2) add wherein, then add the nanometer hydroxyapatite of S1 gained, and be adjusted to alkalescence, by product filtration drying, then use oxolane supersound washing, obtain,
S4. high molecular PMMA's is synthetic:
Polyvinyl alcohol is dissolved in distilled water, stir after lower fully dissolving, add methyl methacrylate (and dibenzoyl peroxide, be warming up to 60 ~ 100 ℃, react after 5 ~ 6h, by distillation washing 3 ~ 5 times for the product of gained, be placed in the dry 4 ~ 8h of 70 ~ 90 ℃ of baking ovens, obtain, the high molecular PMMA of gained is milled into granule, stand-by;
S5. the preparation of bone cement:
The high molecular PMMA of S4 gained is joined to the P (MMA-of S3 gained
co-MPS), in-HA, obtain.
2. preparation method according to claim 1, is characterized in that, high molecular PMMA and P (MMA-described in step S5
co-MPS) weight ratio of-HA is 1:0.5 ~ 20.
3. preparation method according to claim 1, is characterized in that, the dispersant described in step S1 is PEG2000, and described pH is 9 ~ 11, and the time of described ageing is 12 ~ 36 hours.
4. according to right, you require the preparation method described in 1, it is characterized in that, in the mixed solution of the ethanol/water described in step S3, the volume ratio of second alcohol and water is 8 ~ 10:1, and described acidity is pH3 ~ 4.
5. preparation method according to claim 1, is characterized in that, (the CaNO described in step S1
3)
24H
2o powder and (NH
4)
2hPO
4the mass ratio of powder is 1:1 ~ 5.
6. the compound bone cement of injectable of preparing gained according to claim 1 application in preparing orthopedic implanting material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310545809.8A CN103550823A (en) | 2013-11-07 | 2013-11-07 | Injectable compound bone cement as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310545809.8A CN103550823A (en) | 2013-11-07 | 2013-11-07 | Injectable compound bone cement as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103550823A true CN103550823A (en) | 2014-02-05 |
Family
ID=50005291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310545809.8A Pending CN103550823A (en) | 2013-11-07 | 2013-11-07 | Injectable compound bone cement as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103550823A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104548199A (en) * | 2015-01-14 | 2015-04-29 | 石家庄铁道大学 | Hard biotissue replacement and repair material and preparation method thereof |
| WO2015067091A1 (en) * | 2013-11-07 | 2015-05-14 | 中山大学 | Modified nano-hydroxyapatite, and preparation method and application thereof |
| CN106620843A (en) * | 2016-11-22 | 2017-05-10 | 天津大学 | Composite bone cement with bioactivity and antibacterial activity as well as preparation method and application |
| CN112494721A (en) * | 2020-12-09 | 2021-03-16 | 中山大学 | High-activity-component PMMA-based bone cement capable of being rapidly cured and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2074956A1 (en) * | 1993-11-18 | 1995-09-16 | Levante Ind Quirurgicas | Hip prosthesis which replaces the proximal part of the femur |
| CN1563176A (en) * | 2004-04-13 | 2005-01-12 | 复旦大学 | Method for preparing high heat-resistant organic-inorganic composite material |
| WO2005011763A1 (en) * | 2003-07-31 | 2005-02-10 | Korea Institute Of Geoscience And Mineral Resources | Mixture for producing a bioactive bone cement and method for producing a bioactive bone cement using the same |
| US20050256220A1 (en) * | 2004-05-14 | 2005-11-17 | Ceravic Sas | Polymer cement for percutaneous vertebroplasty |
| CN101390813A (en) * | 2008-10-30 | 2009-03-25 | 同济大学 | Preparation method and application of dental composite resin containing functional monomer PMDM and modified hydroxyapatite |
| CN101700416A (en) * | 2009-10-28 | 2010-05-05 | 山东轻工业学院 | A kind of preparation method of hydroxyapatite composite material |
| CN101934097A (en) * | 2010-08-19 | 2011-01-05 | 马文 | Injectable composite bone cement of hydroxyapatite-PMMA containing strontium, preparation method and application thereof |
| CN103108660A (en) * | 2010-07-26 | 2013-05-15 | 华沙整形外科股份有限公司 | Calcium particle-embedded, snap-to-dough, high-viscosity bone cement |
-
2013
- 2013-11-07 CN CN201310545809.8A patent/CN103550823A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2074956A1 (en) * | 1993-11-18 | 1995-09-16 | Levante Ind Quirurgicas | Hip prosthesis which replaces the proximal part of the femur |
| ES2074956B1 (en) * | 1993-11-18 | 1996-05-16 | Levante Ind Quirurgicas | HIP PROSTHESE THAT REPLACES THE PROXIMAL PART OF THE FEMUR. |
| WO2005011763A1 (en) * | 2003-07-31 | 2005-02-10 | Korea Institute Of Geoscience And Mineral Resources | Mixture for producing a bioactive bone cement and method for producing a bioactive bone cement using the same |
| CN1563176A (en) * | 2004-04-13 | 2005-01-12 | 复旦大学 | Method for preparing high heat-resistant organic-inorganic composite material |
| US20050256220A1 (en) * | 2004-05-14 | 2005-11-17 | Ceravic Sas | Polymer cement for percutaneous vertebroplasty |
| CN101390813A (en) * | 2008-10-30 | 2009-03-25 | 同济大学 | Preparation method and application of dental composite resin containing functional monomer PMDM and modified hydroxyapatite |
| CN101700416A (en) * | 2009-10-28 | 2010-05-05 | 山东轻工业学院 | A kind of preparation method of hydroxyapatite composite material |
| CN103108660A (en) * | 2010-07-26 | 2013-05-15 | 华沙整形外科股份有限公司 | Calcium particle-embedded, snap-to-dough, high-viscosity bone cement |
| CN101934097A (en) * | 2010-08-19 | 2011-01-05 | 马文 | Injectable composite bone cement of hydroxyapatite-PMMA containing strontium, preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| E.BOURGEAT-LAMI ET AL.: "Synthesis and Characterization of SiOH-Functionalized Polymer Latexes Using Methacryloxy Propyl Trimethoxysilane in Emulsion Polymerization", 《MACROMOLECULES》 * |
| SHYH MING KUO ET AL.: "Evaluating Chitosan/β-Tricalcium Phosphate/Poly(methyl methacrylate) Cement Composites as Bone-Repairing Materials", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 姚伟涛等: "一种可注射性骨水泥在骨组织内的降解状态", 《中国临床康复》 * |
| 段昕等: "新型可注射可降解磷酸钙骨水泥的生物相容性", 《中国组织工程研究》 * |
| 滕海军等: "注射型磷酸钙骨水泥和PMMA在椎体成形术中的生物力学研究", 《中国矫形外科杂志》 * |
| 苏蔷薇等: "复合型生物活性骨水泥的制备与性能研究", 《广东省生物医学工程学会成立32周年纪念大会暨2012广州（国际）生物医学工程学术大会论文集》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015067091A1 (en) * | 2013-11-07 | 2015-05-14 | 中山大学 | Modified nano-hydroxyapatite, and preparation method and application thereof |
| CN104548199A (en) * | 2015-01-14 | 2015-04-29 | 石家庄铁道大学 | Hard biotissue replacement and repair material and preparation method thereof |
| CN106620843A (en) * | 2016-11-22 | 2017-05-10 | 天津大学 | Composite bone cement with bioactivity and antibacterial activity as well as preparation method and application |
| CN112494721A (en) * | 2020-12-09 | 2021-03-16 | 中山大学 | High-activity-component PMMA-based bone cement capable of being rapidly cured and preparation method and application thereof |
| CN112494721B (en) * | 2020-12-09 | 2021-11-16 | 中山大学 | A kind of fast curing high active component PMMA-based bone cement and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Roshanbinfar et al. | Carbon nanotube doped pericardial matrix derived electroconductive biohybrid hydrogel for cardiac tissue engineering | |
| CN111072997B (en) | A kind of high-strength self-healing hydrogel based on modified hyaluronic acid and preparation method thereof | |
| CN105796478B (en) | High-strength, self-healing, injectable composite colloidal gel materials assembled from nano-colloidal particles, and preparation methods and applications thereof | |
| CN103550823A (en) | Injectable compound bone cement as well as preparation method and application thereof | |
| CN104324419A (en) | Injectable nano-hydroxyapatite/chitosan composite hydrogel as well as preparation method and application thereof | |
| CN102250390A (en) | Alginate hydrogel microcarrier and preparation method thereof | |
| CN103058645B (en) | High-strength magnetic calcium-phosphate-based bone cement and preparation method thereof | |
| CN102718991A (en) | High strength injectable hydrogel and preparation method thereof | |
| Yang et al. | Preparation of methacrylated hyaluronate/methacrylated collagen sponges with rapid shape recovery and orderly channel for fast blood absorption as hemostatic dressing | |
| CN107118373A (en) | A kind of POSS PEG hybridized hydrogels, its preparation method and application | |
| WO2020252957A1 (en) | Degradable regenerative medical material for promoting tissue in-situ regeneration and preparation method therefor | |
| CN112089886A (en) | A kind of hydrogel and preparation method thereof | |
| CN102058903B (en) | Method for preparing oriented and porous natural polymer/calcium phosphate composite materials | |
| Wang et al. | Cryoprinting of nanoparticle-enhanced injectable hydrogel with shape-memory properties | |
| CN112494513A (en) | Cerium dioxide nanoparticles and preparation method and application thereof | |
| CN119661873B (en) | A mechanoelectrically coupled hydrogel microsphere with stable mechanical properties and low-loss transduction, and its preparation method and application | |
| Wang et al. | Slide‐Ring Structured Stress‐Electric Coupling Hydrogel Microspheres for Low‐Loss Transduction Between Tissues | |
| Gao et al. | Hybrid hydrogels containing gradients in gold nanoparticles for localized delivery of mesenchymal stem cells and enhanced nerve tissues remodeling in vivo | |
| Jensen et al. | Biocompatible composite hydrogel with on-demand swelling-shrinking properties for 4D bioprinting | |
| CN103656739A (en) | Composite bone cement with high content of hydroxyapatite, and preparation method and application thereof | |
| CN101693124A (en) | Preparation method of polylactic acid/chitosan/carbon fiber porous supports | |
| CN115246940A (en) | A high-strength fatigue-resistant conductive drug-loaded hydrogel and its application | |
| CN106046399A (en) | Preparation method of surface-mineralized chitosan microsphere | |
| CN103627213A (en) | Preparation method of modified nano hydroxyapatite | |
| CN107496984B (en) | Nano-dicalcium silicate/nano-silver loaded chitosan gel and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140205 |
|
| WD01 | Invention patent application deemed withdrawn after publication |