CN106188361A - Injectable type bone is filled by the preparation method of bioactivity glass composite - Google Patents
Injectable type bone is filled by the preparation method of bioactivity glass composite Download PDFInfo
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- CN106188361A CN106188361A CN201610630475.8A CN201610630475A CN106188361A CN 106188361 A CN106188361 A CN 106188361A CN 201610630475 A CN201610630475 A CN 201610630475A CN 106188361 A CN106188361 A CN 106188361A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/06—Flowable or injectable implant compositions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The invention discloses the preparation method of a kind of injectable type bone filling bioactivity glass composite, with tetraethyl orthosilicate, triethyl phosphate, NaNO3、Ca(NO3)2.4H2O、Mg(NO3)2Raw material makees precursor, polyvinyl alcohol and polydimethylsiloxane as pore creating material, prepares bioactivity glass gel by sol-gal process under catalyst action, scrubbed, dry, grind after obtain porous bioglass micropowder；Described porous bioglass micropowder carries out polyreaction with the mixed solution of N N-isopropylacrylamide, obtains paste injectable type bone filling bioactivity glass composite.The preparation method of injectable type bone filling bioactivity glass composite of the present invention, solves that existing filling material of bone intensity is low, there is the problem in space when using and between defective tissue, have sufficient intensity and can fit tightly with bone, good biocompatibility.
Description
Technical field
The invention belongs to biological medical polymer material technical field, specifically, relate to a kind of injectable type bone and fill
Preparation method with bioactivity glass composite.
Background technology
Biological activity bone renovating material is the biomedical material with porous bioglass as primary raw material.This material
High chemical-biological activities, material surface can occur quick ion-exchange reactions in aqueous, finally in material surface shape
Becoming to be similar to hydroxyapatite (HCA) layer of body bone tissue, HCA layer can be relatively after implanting at osseous tissue defect for material
Form chemical bonding with the osseous tissue lived in short time and play critical effect, thus Cranial defect or diseased bone tissue are played
Good repair, its application prospect is the most optimistic, and market forces are the hugest.The chemical composition of bio-vitric and human bone
Bone is similar to, and has good biocompatibility and degradability, can effectively facilitate histo-differentiation, knitting after implanting human body.So
And existing glass micropowder intensity is difficult to take into account with activity, and existing artificial bone repair materials is mostly block or powder is solid
, there is space as during filling material of bone and between defective tissue in body, it is difficult to matrix perfect adaptation, causes repairing effect not
It is highly desirable.
Summary of the invention
In view of this, the present invention is directed to existing filling material of bone intensity low, use time and defective tissue between there is space
Problem, it is provided that the preparation method of a kind of injectable type bone filling bioactivity glass composite, have sufficient intensity and
Can fit tightly with bone, good biocompatibility.
In order to solve above-mentioned technical problem, the invention discloses a kind of injectable type bone filling bioactivity glass and be combined
The preparation method of material, with tetraethyl orthosilicate, triethyl phosphate, NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2Before raw material is made
Body, polyvinyl alcohol and polydimethylsiloxane, as pore creating material, prepare biology by sol-gel process under catalyst action
Activity glass gel, scrubbed, dry, grind after obtain porous bioglass micropowder；Described porous bioglass
Micropowder carries out polyreaction with the mixed solution of NIPA, obtains paste injectable type bone filling biological activity
Glass composite material.
Further, said method comprises the following steps:
Step 1, prepares bioactivity glass gel；
With tetraethyl orthosilicate, triethyl phosphate, NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2Five kinds of raw materials are front body
Body, polyvinyl alcohol and polydimethylsiloxane, as pore creating material, prepare biology by sol-gel process under catalyst action and live
Property glass gels；
Step 2, the bioactivity glass gel that will obtain, scrubbed, gradient increased temperature is dried, grind after obtain multiporous biological
Activity glass micropowder；
Step 3, prepares bioactivity glass micropowder/poly-N-isopropyl acrylamide composite
Described porous bioglass powder is dispersed in water, adds NIPA, stir molten
Xie Hou, carries out polyreaction under initiator effect, is washed by polymerizate, obtains bioactivity glass micropowder/poly-after drying
NIPA composite, i.e. paste injectable type bone are filled and are used bioactivity glass composite.
Further, described tetraethyl orthosilicate, triethyl phosphate, NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2Matter
Amount ratio is 16～20 1～3 7～9 11～14 1.
Further, the consumption of described polyvinyl alcohol is the 20～36wt% of precursor quality, described polydimethylsiloxanes
The consumption of alkane is the 16～28wt% of precursor quality.
Further, described catalyst is 10 1 with the mol ratio of precursor, and described catalyst is salpeter solution or Fructus Citri Limoniae
Acid solution, the concentration of salpeter solution is 2M, and the concentration of citric acid solution is 5mM.
Further, described gradient increased temperature is dried particularly as follows: 60 DEG C of dry 12h, then heats to 200 DEG C of dry 5h, then
It is warming up to 700 DEG C of dry 2h.
Further, described porous bioglass powder is 1 9～2 with the mass ratio of NIPA
8, total solid content is 7.5wt%～10.0wt%.
Further, described initiator is potassium peroxydisulfate-tetramethylethylenediamine oxidation-reduction trigger system, described initiation
Agent molal quantity is the 0.5～2% of NIPA, and wherein potassium peroxydisulfate is 12 with the mol ratio of tetramethylethylenediamine.
Further, the temperature of described polyreaction is 15 DEG C, and the time is 10～15min.
Further, described polyreaction is carried out under inert gas shielding.
Compared with prior art, the present invention can obtain and include techniques below effect:
(1) present invention is by adding micro Mg, the intensity of Ca element raising glass micropowder, simultaneously at the work of compounding pore creating material
Under with, prepare highly active porous bioglass micropowder, overcome the defect that existing filling material of bone intensity is low.
(2) present invention will be by having NIPA (NIPAM) monomer and the multiporous biological activity of Thermo-sensitive
Glass micropowder is combined, and polymerization obtains the injectable type PNIPAM/ equal phase composite materials of glass micropowder of paste.This material is used for bone
During filling, owing to having mobility, can well with fill mate；Raw due to a little higher than PNIPAM/ of body temperature again
The phase transition temperature of thing activity glass micropowder compound system, after being injected into human body, composite can shrink hardening and with people's bone
Fit tightly together, overcome existing bulk or powder filling material of bone in use and exists space between defective tissue
Problem.
(3) biocompatibility that bioactivity glass micropowder is good with human body and high chemical-biological activities can be with people
Bone growth together and has transmission Biomedia attribute, thus Cranial defect or diseased bone tissue are played good reparation
Effect.
Certainly, the arbitrary product implementing the present invention it is not absolutely required to reach all the above technique effect simultaneously.
Detailed description of the invention
Embodiments of the present invention are described in detail, thereby to the present invention how application technology hands below in conjunction with embodiment
Section solves technical problem and reaches the process that realizes of technology effect and can fully understand and implement according to this.
The preparation method of injectable type bone filling bioactivity glass composite of the present invention, specifically includes following step
Rapid:
Step 1, prepares bioactivity glass gel；
With tetraethyl orthosilicate (TEOS), triethyl phosphate (TEP), NaNO3、Ca(NO3)2.4H2O、Mg(NO3)2Five kinds former
Material is precursor, and polyvinyl alcohol (PVA) and polydimethylsiloxane (PDMS) are as pore creating material, by molten under catalyst action
Glue-gel method prepares bioactivity glass gel；
Wherein, described tetraethyl orthosilicate, triethyl phosphate, NaNO3、Ca(NO3)2.4H2O、Mg(NO3)2Mass ratio be
16～20 1～3 7～9 11～14 1, preferably 18.6 1.8 8.0 12.3 1, this proportion can make obtained life
The composition of thing activity glass is similar to the hydroxyapatite of body bone tissue (HA) layer.
Preferably, described polyvinyl alcohol consumption is 20～36wt% (relative to precursors), the use of polydimethylsiloxane
Amount is 16～28wt% (relative to precursors), chooses this proportion and can slow down the catabolic process of whole pore creating material, it is to avoid
The caving in of material when higher Content of Pore-forming Agents, thus improve the porosity of glass micropowder.
Preferably, described catalyst is any one in salpeter solution, citric acid solution, catalyst and the mol ratio of precursor
Being 10 1, nitric acid preferred concentration is the salpeter solution of 2M, and citric acid preferred concentration is the citric acid solution of 5mM.Catalyst is nitre
During acid, at 35 DEG C, carry out sol gel reaction；When catalyst is citric acid, at 20 DEG C, carry out sol gel reaction.
Step 2, the bioactivity glass gel that will obtain, scrubbed, gradient increased temperature is dried, grind after obtain multiporous biological
Activity glass micropowder；
Further, described gradient increased temperature is dried particularly as follows: 60 DEG C of dry 12h, then heats to 200 DEG C of dry 5h, then
It is warming up to 700 DEG C of dry 2h.
The benefit of this kind of heating mode: the speed that 1. solvent is removed finally determines the porosity distribution of gel, the most favourable
In the material obtaining even pore distribution；2. be conducive to further condensation reaction, improve the consistency of material, and then improve mechanics
Intensity.
Step 3, prepares bioactivity glass micropowder/poly-N-isopropyl acrylamide composite
Described porous bioglass powder is dispersed in water, adds NIPA (NIPAM),
After stirring and dissolving, under initiator effect, carry out polyreaction, polymerizate is washed, to obtain bioactivity glass after drying micro-
Powder/poly-N-isopropyl acrylamide composite, i.e. paste injectable type bone are filled and are used bioactivity glass composite.
Preferably, the mass ratio of described porous bioglass powder and NIPA be 1 9～2 8,
Total solid content is 7.5wt%～10.0wt%, chooses this proportion and resulting materials can be made to have certain fluidity, simultaneously
Ensure that material has enough mechanical strengths.
Preferably, described initiator is potassium peroxydisulfate (KPS)-tetramethylethylenediamine (TEMDA) redox initiator body
System, described initiator molal quantity is the 0.5～2% of NIPA, chooses this proportion and is advantageous in that: 1. makes
Poly-N-isopropyl acrylamide (PNIPAM) degree of polymerization is moderate, it is ensured that material has enough mechanical strengths；2. rate of polymerization is made to fit
In, it is simple to the control of course of reaction；3. material is made to have suitable phase transition temperature.
Wherein the mol ratio of KPS Yu TEMDA is 12, and this ratio can make each initiator molecule the most only produce one
Individual free radical, is so conducive to obtaining the polymerizate that molecular weight distribution is narrower.
Preferably, the temperature of described polyreaction is 15 DEG C, and the time is 10～15min.
Further, described polyreaction is carried out under inert gas shielding, and described noble gas includes but not limited to: nitrogen
Gas and argon.
Embodiment 1
Step 1, prepares bioactivity glass gel
With tetraethyl orthosilicate (TEOS), triethyl phosphate (TEP), NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2For front
Body, described TEOS, TEP, NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2Mass ratio be 18.6 1.8 8.0 12.3 1, with
Nitric acid is catalyst, and aqueous solution of nitric acid (concentration the is 2M) mol ratio total with five kinds of presomas is 10 1, polyvinyl alcohol (PVA)
And polydimethylsiloxane (PDMS) is as pore creating material, described PVA consumption is 36wt% (relative to precursor), PDMS consumption is
16wt% (relative to precursor), prepares bioactivity glass gel by sol-gel process at 35 DEG C；
Step 2, the bioactivity glass gel that will obtain, scrubbed, gradient increased temperature is dried (60 DEG C/12h → 200 DEG C/5h
→ 700 DEG C/2h), grind after obtain high intensity, high activity porous bioglass micropowder；
Step 3, prepares bioactivity glass micropowder/poly-N-isopropyl acrylamide composite
By magnetic agitation after sonic oscillation, described porous bioglass powder is dispersed in water, obtains glass
Glass micropowder suspension, and it is passed through N under liquid level2；Controlling temperature is 15 DEG C, is added by NIPA (NIPAM) monomer
Entering in glass micropowder suspension, described porous bioglass powder is 19 with the mass ratio of NIPA, always
Solid content be 7.5wt%, stirring make NIPAM fully dissolve, then by N2Change into being passed through from liquid level, to reduce gas in solution
Body burden；
Disposably add potassium peroxydisulfate (KPS)-tetramethylethylenediamine (TEMDA) oxidation-reduction trigger system, described initiation
Agent integral molar quantity is 0.5% relative to NIPA, and wherein the mol ratio of KPS Yu TEMDA is 1:2, makees at initiator
Polyreaction 10min is carried out, with obtaining bioactivity glass micropowder/poly-N-after washing with alcohol polymerizate, lyophilization under with
N-isopropylacrylamide composite, i.e. paste injectable type bone are filled and are used bioactivity glass composite.
Embodiment 2
Step 1, prepares bioactivity glass gel
With tetraethyl orthosilicate (TEOS), triethyl phosphate (TEP), NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2For front
Body, described TEOS, TEP, NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2Mass ratio be 16 1.5 7 11 1, with nitric acid be
Catalyst, aqueous solution of nitric acid (concentration the is 2M) mol ratio total with five kinds of presomas is 10 1, polyvinyl alcohol (PVA) and poly-diformazan
Radical siloxane (PDMS) is as pore creating material, and described PVA consumption is 32wt% (relative to precursor), PDMS consumption is 20wt%
(relative to precursor), prepares bioactivity glass gel by sol-gel process at 35 DEG C；
Step 2, the bioactivity glass gel that will obtain, scrubbed, gradient increased temperature is dried (60 DEG C/12h → 200 DEG C/5h
→ 700 DEG C/2h), grind after obtain high intensity, high activity porous bioglass micropowder；
Step 3, prepares bioactivity glass micropowder/poly-N-isopropyl acrylamide composite
By magnetic agitation after sonic oscillation, described porous bioglass powder is dispersed in water, obtains glass
Glass micropowder suspension, and it is passed through N under liquid level2；Controlling temperature is 15 DEG C, is added by NIPA (NIPAM) monomer
Entering in glass micropowder suspension, described porous bioglass powder is 19 with the mass ratio of NIPA, always
Solid content be 10wt%, stirring make NIPAM fully dissolve, then by N2Change into being passed through from liquid level, to reduce gas in solution
Body burden；
Disposably add potassium peroxydisulfate (KPS)-tetramethylethylenediamine (TEMDA) oxidation-reduction trigger system, described initiation
Agent integral molar quantity is 1% relative to NIPA, and wherein the mol ratio of KPS Yu TEMDA is 1:2, in initiator effect
Under carry out polyreaction 15min, with obtaining after washing with alcohol polymerizate, lyophilization, bioactivity glass micropowder/poly-N-is different
Propylacrylamide composite, i.e. paste injectable type bone are filled and are used bioactivity glass composite.
Embodiment 3
Step 1, prepares bioactivity glass gel
With tetraethyl orthosilicate (TEOS), triethyl phosphate (TEP), NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2For front
Body, described TEOS, TEP, NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2Mass ratio be 20 39 14 1, with citric acid be
Catalyst, aqueous citric acid solution (concentration the is 5mM) mol ratio total with five kinds of presomas is 10 1, polyvinyl alcohol (PVA) and poly-
Dimethyl siloxane (PDMS) is as pore creating material, and described PVA consumption is 28wt% (relative to precursor), PDMS consumption is
24wt% (relative to precursor), prepares bioactivity glass gel by sol-gel process at 20 DEG C；
Step 2, the bioactivity glass gel that will obtain, scrubbed, gradient increased temperature is dried (60 DEG C/12h → 200 DEG C/5h
→ 700 DEG C/2h), grind after obtain high intensity, high activity porous bioglass micropowder；
Step 3, prepares bioactivity glass micropowder/poly-N-isopropyl acrylamide composite
By magnetic agitation after sonic oscillation, described porous bioglass powder is dispersed in water, obtains glass
Glass micropowder suspension, and it is passed through N under liquid level2；Controlling temperature is 15 DEG C, is added by NIPA (NIPAM) monomer
Entering in glass micropowder suspension, described porous bioglass powder is 1.5 with the mass ratio of NIPA
8.5, total solid content is 7.5wt%, and stirring makes NIPAM fully dissolve, then by N2Change into being passed through from liquid level, molten to reduce
Gas content in liquid；
Disposably add potassium peroxydisulfate (KPS)-tetramethylethylenediamine (TEMDA) oxidation-reduction trigger system, described initiation
Agent integral molar quantity is 1.5% relative to NIPA, and wherein the mol ratio of KPS Yu TEMDA is 1:2, makees at initiator
Polyreaction 15min is carried out, with obtaining bioactivity glass micropowder/poly-N-after washing with alcohol polymerizate, lyophilization under with
N-isopropylacrylamide composite, i.e. paste injectable type bone are filled and are used bioactivity glass composite.
Embodiment 4
Step 1, prepares bioactivity glass gel
With tetraethyl orthosilicate (TEOS), triethyl phosphate (TEP), NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2For front
Body, described TEOS, TEP, NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2Mass ratio be 17 1 7.5 13 1, with citric acid
For catalyst, aqueous citric acid solution (concentration the is 5mM) mol ratio total with five kinds of presomas is 10 1, polyvinyl alcohol (PVA) and
Polydimethylsiloxane (PDMS) is as pore creating material, and described PVA consumption is 20wt% (relative to precursor), PDMS consumption is
16wt% (relative to precursor), prepares bioactivity glass gel by sol-gel process at 20 DEG C；
Step 2, the bioactivity glass gel that will obtain, scrubbed, gradient increased temperature is dried (60 DEG C/12h → 200 DEG C/5h
→ 700 DEG C/2h), grind after obtain high intensity, high activity porous bioglass micropowder；
Step 3, prepares bioactivity glass micropowder/poly-N-isopropyl acrylamide composite
By magnetic agitation after sonic oscillation, described porous bioglass powder is dispersed in water, obtains glass
Glass micropowder suspension, and it is passed through N under liquid level2；Controlling temperature is 15 DEG C, is added by NIPA (NIPAM) monomer
Entering in glass micropowder suspension, described porous bioglass powder is 1.5 with the mass ratio of NIPA
8.5, total solid content is 10wt%, and stirring makes NIPAM fully dissolve, then by N2Change into being passed through from liquid level, molten to reduce
Gas content in liquid；
Disposably add potassium peroxydisulfate (KPS)-tetramethylethylenediamine (TEMDA) oxidation-reduction trigger system, described initiation
Agent integral molar quantity is 2% relative to NIPA, and wherein the mol ratio of KPS Yu TEMDA is 1:2, in initiator effect
Under carry out polyreaction 12min, with obtaining after washing with alcohol polymerizate, lyophilization, bioactivity glass micropowder/poly-N-is different
Propylacrylamide composite, i.e. paste injectable type bone are filled and are used bioactivity glass composite.
Embodiment 5
Step 1, prepares bioactivity glass gel
With tetraethyl orthosilicate (TEOS), triethyl phosphate (TEP), NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2For front
Body, described TEOS, TEP, NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2Mass ratio be 18.6 1.8 8.0 12.3 1, with
Nitric acid is catalyst, and aqueous solution of nitric acid (concentration the is 2M) mol ratio total with five kinds of presomas is 10 1, polyvinyl alcohol (PVA) and
Polydimethylsiloxane (PDMS) is as pore creating material, and described PVA consumption is 32wt% (relative to precursor), PDMS consumption is
20wt% (relative to precursor), prepares bioactivity glass gel by sol-gel process at 35 DEG C；
Step 2, the bioactivity glass gel that will obtain, scrubbed, gradient increased temperature is dried (60 DEG C/12h → 200 DEG C/5h
→ 700 DEG C/2h), grind after obtain high intensity, high activity porous bioglass micropowder；
Step 3, prepares bioactivity glass micropowder/poly-N-isopropyl acrylamide composite
By magnetic agitation after sonic oscillation, described porous bioglass powder is dispersed in water, obtains glass
Glass micropowder suspension, and it is passed through N under liquid level2；Controlling temperature is 15 DEG C, is added by NIPA (NIPAM) monomer
Entering in glass micropowder suspension, described porous bioglass powder is 28 with the mass ratio of NIPA, always
Solid content be 7.5wt%, stirring make NIPAM fully dissolve, then by N2Change into being passed through from liquid level, to reduce gas in solution
Body burden；
Disposably add potassium peroxydisulfate (KPS)-tetramethylethylenediamine (TEMDA) oxidation-reduction trigger system, described initiation
Agent integral molar quantity is 1.5% relative to NIPA, and wherein the mol ratio of KPS Yu TEMDA is 1:2, makees at initiator
Polyreaction 10min is carried out, with obtaining bioactivity glass micropowder/poly-N-after washing with alcohol polymerizate, lyophilization under with
N-isopropylacrylamide composite, i.e. paste injectable type bone are filled and are used bioactivity glass composite.
Embodiment 6
Step 1, prepares bioactivity glass gel
With tetraethyl orthosilicate (TEOS), triethyl phosphate (TEP), NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2For front
Body, described TEOS, TEP, NaNO3、Ca(NO3)2·4H2O、Mg(NO3)2Mass ratio be 18.6 1.8 8.0 12.3 1, with
Citric acid is catalyst, and aqueous citric acid solution (concentration the is 5mM) mol ratio total with five kinds of presomas is 10 1, polyvinyl alcohol
(PVA) and polydimethylsiloxane (PDMS) is as pore creating material, described PVA consumption is 32wt% (relative to precursor), PDMS
Consumption is 28wt% (relative to precursor), prepares bioactivity glass gel by sol-gel process at 20 DEG C；
Step 2, the bioactivity glass gel that will obtain, scrubbed, gradient increased temperature is dried (60 DEG C/12h → 200 DEG C/5h
→ 700 DEG C/2h), grind after obtain high intensity, high activity porous bioglass micropowder；
Step 3, prepares bioactivity glass micropowder/poly-N-isopropyl acrylamide composite
By magnetic agitation after sonic oscillation, described porous bioglass powder is dispersed in water, obtains glass
Glass micropowder suspension, and it is passed through N under liquid level2；Controlling temperature is 15 DEG C, is added by NIPA (NIPAM) monomer
Entering in glass micropowder suspension, described porous bioglass powder is 28 with the mass ratio of NIPA, always
Solid content be 9wt%, stirring make NIPAM fully dissolve, then by N2Change into being passed through from liquid level, to reduce gas in solution
Content；
Disposably add potassium peroxydisulfate (KPS)-tetramethylethylenediamine (TEMDA) oxidation-reduction trigger system, described initiation
Agent integral molar quantity is 2% relative to NIPA, and wherein the mol ratio of KPS Yu TEMDA is 1:2, in initiator effect
Under carry out polyreaction 15min, with obtaining after washing with alcohol polymerizate, lyophilization, bioactivity glass micropowder/poly-N-is different
Propylacrylamide composite, i.e. paste injectable type bone are filled and are used bioactivity glass composite.
The phase transition temperature of embodiment of the present invention gained composite is 33～35 DEG C, near the physiological temp of people, its
Volume sweell(ing)-shrinkage factor is 5～10%, and after injecting defect of human body bone tissue, change in volume is less, can be tight with matrix
In conjunction with.After high-temperature shrinkage, the comprcssive strength of resulting materials is 6.2～7.0MPa, is better than the mechanics of pure 45S5 porous blocks material
Intensity (3.9MPa).
Use said method, by bioactivity glass micropowder and the relative amount of PNIPAM and choosing of water content, system
Must be suitable to inject (having certain fluidity), have suitable phase transition temperature (being applicable to body temperature), have sufficient intensity and have relatively
The bone filling bioactivity glass composite of little swelling-shrinkage factor.
As employed some vocabulary in the middle of description and claim to censure special component or method.Art technology
Personnel are it is to be appreciated that same composition may be called with different nouns in different regions.This specification and claims are not
In the way of the difference of title is used as distinguishing composition." comprising " as mentioned by the middle of description and claim in the whole text is
One open language, therefore " comprise but be not limited to " should be construed to." substantially " refer in receivable range of error, this area
Technical staff can solve described technical problem in the range of certain error, basically reaches described technique effect.Description is follow-up
It is described as implementing the better embodiment of the present invention, for the purpose of right described description is the rule so that the present invention to be described, not
In order to limit the scope of the present invention.Protection scope of the present invention is when being as the criterion depending on the defined person of claims.
Also, it should be noted term " includes ", " comprising " or its any other variant are intended to nonexcludability
Comprise, so that include that the commodity of a series of key element or system not only include those key elements, but also include the most clearly
Other key elements listed, or also include the key element intrinsic for this commodity or system.In the feelings not having more restriction
Under condition, statement " including ... " key element limited, it is not excluded that in the commodity including described key element or system also
There is other identical element.
Described above illustrate and describes some preferred embodiments of invention, but as previously mentioned, it should be understood that invention is not
It is confined to form disclosed herein, is not to be taken as the eliminating to other embodiments, and can be used for other combinations various, amendment
And environment, and can be carried out by above-mentioned teaching or the technology of association area or knowledge in invention contemplated scope described herein
Change.And the change that those skilled in the art are carried out and change are without departing from the spirit and scope of invention, the most all should weigh appended by invention
In the protection domain that profit requires.
Claims (10)
1. injectable type bone is filled by the preparation method of bioactivity glass composite, it is characterised in that with positive silicic acid tetrem
Ester, triethyl phosphate, NaNO3、Ca(NO3)2.4H2O、Mg(NO3)2Raw material makees precursor, polyvinyl alcohol and polydimethylsiloxane
As pore creating material, under catalyst action, prepare bioactivity glass gel, scrubbed, dry, grinding by sol-gel process
After obtain porous bioglass micropowder；Described porous bioglass micropowder is molten with the mixing of NIPA
Liquid carries out polyreaction, obtains paste injectable type bone filling bioactivity glass composite.
2. injectable type bone as claimed in claim 1 is filled by the preparation method of bioactivity glass composite, its feature
It is, comprises the following steps:
Step 1, prepares bioactivity glass gel；
With tetraethyl orthosilicate, triethyl phosphate, NaNO3、Ca(NO3)2.4H2O、Mg(NO3)2Five kinds of raw materials are precursor, poly-second
Enol and polydimethylsiloxane, as pore creating material, prepare bioactivity glass by sol-gel process under catalyst action
Gel；
Step 2, the bioactivity glass gel that will obtain, scrubbed, gradient increased temperature is dried, grind after obtain multiporous biological activity
Glass micropowder；
Step 3, prepares bioactivity glass micropowder/poly-N-isopropyl acrylamide composite
Described porous bioglass powder is dispersed in water, adds NIPA, after stirring and dissolving,
Under initiator effect, carry out polyreaction, polymerizate is washed, obtains bioactivity glass micropowder/poly-N-isopropyl after drying
Base acrylamide composite, i.e. paste injectable type bone are filled and are used bioactivity glass composite.
3. injectable type bone as claimed in claim 2 is filled by the preparation method of bioactivity glass composite, its feature
It is, described tetraethyl orthosilicate, triethyl phosphate, NaNO3、Ca(NO3)2.4H2O、Mg(NO3)2Mass ratio be 16～20 1
～3 7～9 11～14 1.
4. injectable type bone as claimed in claim 2 is filled by the preparation method of bioactivity glass composite, its feature
Being, the consumption of described polyvinyl alcohol is the 20～36wt% of precursor quality, and the consumption of described polydimethylsiloxane is front
The 16～28wt% of body quality.
5. injectable type bone as claimed in claim 2 is filled by the preparation method of bioactivity glass composite, its feature
Being, described catalyst is 10 1 with the mol ratio of precursor, and described catalyst is salpeter solution or citric acid solution, and nitric acid is molten
The concentration of liquid is 2M, and the concentration of citric acid solution is 5mM.
6. injectable type bone as claimed in claim 2 is filled by the preparation method of bioactivity glass composite, its feature
Being, described gradient increased temperature is dried particularly as follows: 60 DEG C of dry 12h, then heats to 200 DEG C of dry 5h, then is warming up to 700 DEG C and does
Dry 2h.
7. injectable type bone as claimed in claim 2 is filled by the preparation method of bioactivity glass composite, its feature
Being, described porous bioglass powder is 1 9～2 8 with the mass ratio of NIPA, and total solid content is
7.5wt%～10.0wt%.
8. injectable type bone as claimed in claim 2 is filled by the preparation method of bioactivity glass composite, its feature
Being, described initiator is potassium peroxydisulfate-tetramethylethylenediamine oxidation-reduction trigger system, and described initiator molal quantity is N-
The 0.5～2% of N-isopropylacrylamide, wherein potassium peroxydisulfate is 12 with the mol ratio of tetramethylethylenediamine.
9. injectable type bone as claimed in claim 2 is filled by the preparation method of bioactivity glass composite, its feature
Being, the temperature of described polyreaction is 15 DEG C, and the time is 10～15min.
10. injectable type bone as claimed in claim 2 is filled by the preparation method of bioactivity glass composite, its feature
Being, described polyreaction is carried out under inert gas shielding.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103006444A (en) * | 2011-09-28 | 2013-04-03 | 韩冰 | Use of gel material in therapeutic process of dental disease |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103006444A (en) * | 2011-09-28 | 2013-04-03 | 韩冰 | Use of gel material in therapeutic process of dental disease |
Non-Patent Citations (1)
| Title |
|---|
| 陈文娟,周丽赟,王德平,黄文旵,姚爱华: "生物玻璃的原位复合及其生物活性", 《材料研究学报》 * |
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