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
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- 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
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Abstract
The invention relates to injectable compound bone cement as well as a preparation method and application thereof. The preparation method comprises the following steps of S1, synthesis of nano-hydroxyapatite; S2, synthesis of P(MMA-co-MPS); S3, preparation of (MMA-co-MPS)-HA; S4, synthesis of high molecular weight PMMA (polymethyl methacrylate); S5, preparation of bone cement. According to the preparation method, amphipathy polymer P(MMA-co-MPS) is used for coupling and modifying nano hydroxyapatite, so that the nano hydroxyapatite is benefited to being dispersed in MMA (methl methacrylate) liquid phase, HA/PMMA is easier to prepare and the injectable compound bone cement has better mechanical property.
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.
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| 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 |
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| 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 | High-activity-component PMMA-based bone cement capable of being rapidly cured and preparation method and application thereof |
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Application publication date: 20140205 |