CN102886069A - Method for preparing sol-gel bioglass-high polymer hybrid material - Google Patents
Method for preparing sol-gel bioglass-high polymer hybrid material Download PDFInfo
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Abstract
The invention discloses a method for preparing a sol-gel bioactive glass-high polymer hybrid material. The method comprises the following steps of: modifying the functional group of a high polymer molecular chain terminal group to form a silicon alkoxy group on the terminal group; mixing high polymer modified by using the end group with a precursor solution of sol-gel bioactive glass for realizing cohydrolysis and dehydration copolymerization reactions between a high-polymer alcoxyl terminal group and a sol-gel bioactive glass precursor alcoxyl group to obtain a bioactive glass network structure with a high polymer molecular chain structure; and aging, dehydrating, drying and performing thermal treatment to obtain a sol-gel bioactive glass and high polymer molecular hybridized composite material. The composite material can be applied to repair of bone tissues, soft tissues and the like. A material system contains a high-polymer component, so that the toughness of the hybrid material is remarkably improved in comparison to the conventional sintering method and sol-gel bioactive glass, and preparation of large-sized repairing materials and products is facilitated.
Description
Technical field
The present invention relates to the inorganic-organic hybridization technical field of composite materials, be specifically related to collosol and gel bioactivity glass-polymer hybridisation material preparation method.
Background technology
Osseous tissue is the histoorgan that body weight for humans is wanted, and its major function is motion, supports and the protection health, also is the hemopoietic organ that body weight for humans is wanted simultaneously, and the vitals of storing calcium phosphorus ore thing.The damaged of osseous tissue will produce great impact to health and daily life.
But owing to congenital and traumatic reason, orthopaedics, dentistry, decorative sursery, plastic surgery etc. clinically, the damaged case of bone that causes resected bone to cause by reasons such as bone tumor, bone cysts is very many.After the osseous tissue excision, not only cause the disappearance of correlation function, simultaneously because the excision of osseous tissue, change with anatomical structure, the mechanical structure relation of surrounding tissue, cause easily that also the corresponding complication of surrounding tissue occurs.Such as the hearing disability that causes after the upper jaw bone excision; It is involutory unusual etc. that osteoarthritis of elbow, joint appear in the impact of resection of radial head postoperative; Behind the thoracic vertebra tumor resection, flexion deformity, dislocation etc. may appear in vertebra, again cause paraplegia.Therefore, in sacrectomy, usually need corresponding filling material of bone to substitute the osseous tissue of excision, still preserved after surgery with the partial function that guarantees corresponding defective tissue.
At present the clinical bone filling renovation material commonly used osseous tissue that mainly contains biogenic is as from body bone, homogeneous allogenic bone or xenogenesis bone; The Corallium Japonicum Kishinouye of natural material such as modification etc.; And synthetic inorganic material, such as calcium sulfate, calcium carbonate, hydroxyapatite, tricalcium phosphate and bio-vitric etc.In general, best from body filling renovation material repairing effect, but have the limited problem of supply.Allogeneic and foreign material also have preferably repairing effect, but owing to there is the problem of immunity and pathology, also are not widely used clinically.The calcium phosphate material of natural origin, and the inorganic material wide material sources of synthetic class, steady chemical structure is widely used at present clinically.But find also that in application process inorganic material is because the characteristic of self molecular structure, repair materials exists the shortcomings such as fragility is large, difficult processing, power applications inconvenience, bone renovating material that neither be best.Bioactivity glass is a kind of have good biocompatibility and bioactive mineral-type bioactive materials, a series of surface reactions can occur rapidly at implant site in it, formation and bone and soft tissue can both produce the hydroxyapatite layer of good combination, promote the regeneration of osseous tissue, be subject to related researcher's attention.But bio-vitric belongs to inorganic material, still has the problems such as fragility is large, difficult processing, power applications inconvenience.
Organic/inorganic composite material can improve the mouldability of material, the mechanical property of controlled material and biology performance to a certain extent.But at present the composite of research all is large-sized hybrid material, such as the composite of the more degradable polyester family macromolecule of present research with inorganic material formation such as hydroxyapatite, tricalcium phosphate, bio-vitrics.Only resting on hydridization on the large scale still can't satisfy and must possess biologic activity, degradability, mechanics Adapter Property requirement simultaneously to the bone filling renovation material.The hydridization of small scale, namely the hydridization on nanoscale and molecular level is only final solution to the method for the biological degradable composite of above-mentioned multi-functional demand.
Although the material of large scale hydridization and small scale hydridization is the same at composition with arranging of atom or molecule, but the hybrid material that organic polymer and inorganic material form at molecular level, because its special molecular structure characteristics, can realize simultaneously at material internal coexistence and the combination of dissimilar chemical bonds, chemical bond such as the ionic bond of high molecular covalent bond and inorganic material, and this combination is at molecular level, combination on the nanoscale, so that material can both have the characteristic of inorganic material, simultaneously also can have the organic macromolecule characteristics, organic as the component state of aggregation, the nanostructured of inorganic phase small scale hydridization shows distinctive nanometer cooperative effect, the new material that forms can also have than in the past independent macromolecule, the performance that inorganic material is more excellent, thereby obtain the new material of unique properties, show the required good performance of many people.
The preparation of sol-gel bioglass is to be hydrolyzed into the silicon hydroxyl by alcoxyl key in the polysiloxane precursor body, again by the condensation dehydration of silicon hydroxyl, forms the macromole silica network complex of bio-vitric.Composition principle based on above-mentioned sol-gel bioglass, the macromolecule end group is carried out end group with the group that contains the silicon alkoxyl to be modified, hydrolysis by the silicon alkoxyl forms the silicon hydroxyl, and carry out cocondensation with the silicon hydroxyl groups in the sol-gel glasses presoma, realize the molecular hybrid of macromolecule and the network combined body of bio-vitric.By organic and inorganic molecular hybrid ratio, and the control of organic principle strand length, realize the comprehensive adjustment to hybrid material biological activity and mechanical property, the molecular hybrid inorganic-organic bioactivity glass composite that preparation has the clinical practice meaning.
Summary of the invention
The object of the invention is to overcome the deficiency that fragility is large, power applications is inconvenient of existing collosol and gel bioactivity glass, collosol and gel bioactivity glass-polymer hybridisation composite manufacture method is provided.
Purpose of the present invention is achieved through the following technical solutions:
Collosol and gel bioactivity glass-polymer hybridisation material preparation method comprises the steps:
(1) macromolecule and isocyanate group alkylalkoxy silane are reacted, obtain the macromolecule of oxyalkylsiloxane base end-blocking;
The aqueous solution of the macromolecule of the oxyalkylsiloxane base end-blocking that (2) step (1) is obtained and the precursor of bioactivity glass mixes, and carries out cohydrolysis and dehydration polyreaction;
Wherein the high molecular mass percent of oxyalkylsiloxane base end-blocking is 60% ~ 10%, and the mass percent of the presoma of bio-vitric is 40% ~ 90%;
(3) product that step (2) is obtained carries out carrying out dried behind the ripening;
(4) product that step (3) is obtained is heat-treated, and obtains bio-vitric-polymer hybridisation material.
The reaction temperature of the described cohydrolysis of step (2) and dehydration polyreaction is 4 ℃ ~ 40 ℃, and the pH value scope is 4 ~ 9, and the response time is no less than 2 hours.
Described pH value adopts hydrochloric acid, ammonia, sodium hydroxide or potassium hydroxide to regulate.
The reaction temperature of the described ripening of step (3) is 4 ℃ ~ 100 ℃.
The described heat treated temperature of step (4) is 100 ℃ ~ 800 ℃.
The described macromolecule of step (1) is two hydroxyls, aminoterminal based high molecular or polyhydroxy, aminoterminal based high molecular, and number-average molecular weight is 100 ~ 20000.
Step (2) also adds medicine, bioactive molecule solution, slow releasing preparation, genophore or the elecrtonegativity macromolecule with therapeutical effect.
The described isocyanate group alkylalkoxy silane of step (1) is monoalkoxy, bis-alkoxy or tri-alkoxy.
It is 30% ~ 80% SiO that the precursor of bioactivity glass comprises mass percent
2, mass percent is 10% ~ 40% CaO, mass percent is 1% ~ 10% P
2O
5, mass percent is 0 ~ 20% NaO.
The described drying of step (3) is lyophilization or supercritical drying.
Compare with current material, the present invention has following advantage and effect:
(1) traditional sol-gel bioglass is in the ageing drainage procedure, ftracture easily, be difficult to prepare massive material, and after adopting organic molecule to carry out hydridization, the fractionated polymer subchain can be in ageing process stable silicon oxygen network structure, reduce and avoid subsiding and ftracture of material, be beneficial to the material for preparing bulk.Secondly, owing to have high molecular structure in the system, the fragility of material reduces greatly, and toughness and processing characteristics improve.
(2) the collosol and gel bioactivity glass of the present invention's preparation-polymer hybridisation composite has kept the excellent properties (external mineralization experiments result shows that this repair materials can form calcium phosphorus precipitation on the surface in simulated body fluid) of sol-gel bioglass, a series of surface reactions can occur at implant site in expection, form the class bone calcium phosphorus precipitation that produces good combination with bone, promote the regeneration of osseous tissue.
Description of drawings
Fig. 1 is the sol-gel bioglass-polymer hybridisation material of present embodiment preparation and the infared spectrum of Polyethylene Glycol (PEG).
Fig. 2 is PEG 7 days surperficial SEM figure of mineralising in simulated body fluid.
Fig. 3 is the glue gel bio-vitric-polymer hybridisation material 7 days surperficial SEM pictures of mineralising in simulated body fluid of present embodiment preparation.
Fig. 4 be present embodiment preparation glue gel bio-vitric-polymer hybridisation material surface deposits can spectrogram.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Be that the Polyethylene Glycol (PEG) 200 of hydroxyl reacts with 37.2g isocyanate group triethoxysilane with the both-end base of 16g, obtain the Polyethylene Glycol that the 53.4g end group contains ethyl-silicone.This molecule of 53.4g and 15.6g tetraethoxysilane, 1.8g triethyl phosphate, 18.8g lime nitrate are together put into 50 ml waters, with the dilute hydrochloric acid adjust pH to 6.8 of 1M, in the time of 15 ℃, stir 3h with 800 rev/mins of magnetic stirring apparatuss, carry out cohydrolysis reaction.Get cohydrolysis product 10ml, add the 0.2g hyaluronic acid, the 100ng bone morphogenic protein BMP-2 in solution, mix homogeneously.4 ℃ of ageings placed-20 ℃ of refrigerator 7d after 10 days, and then lyophilization was processed 48 hours, after 3 hours, obtained end product in 800 ℃ of heat treatments again.
Fig. 1 is the sol-gel bioglass-polymer hybridisation material of present embodiment preparation and the infared spectrum (sol-gel bioglass that the corresponding present embodiment of curve A prepares among the figure-polymer hybridisation material of PEG, the corresponding PEG of curve B), can find out that from infared spectrum wave number is 1719cm
-1The absworption peak at place is in PEG and the bio-vitric hydridization process, the characteristic absorption peak of its chemical bond amide group.
Fig. 2 is PEG 7 days surperficial SEM figure of mineralising in simulated body fluid.Fig. 3 is the glue gel bio-vitric-polymer hybridisation material 7 days surperficial SEM pictures of mineralising in simulated body fluid of present embodiment preparation, and as shown in Figure 3, the glue gel bio-vitric of present embodiment preparation-polymer hybridisation material surface has obvious mineral deposition.Fig. 4 is that the surface mineral of glue gel bio-vitric-polymer hybridisation material of present embodiment preparation is sedimental can spectrogram, and energy spectrum analysis shows that main component is the calcium P elements in this deposit.Show that the glue gel bio-vitric of present embodiment preparation-polymer hybridisation material can a series of surface reactions occur at implant site, formation and bone and soft tissue can both produce the calcium phosphorus precipitation thing of good combination, the regeneration of promotion osseous tissue.
Be that 400 both-end base is that the Polyethylene Glycol (PEG) of hydroxyl reacts with 14g isocyanate group triethoxysilane with the 12g molecular weight, obtain the Polyethylene Glycol that the 26g end group contains ethyl-silicone.With this molecule of 25g and 16.6g tetraethoxysilane, 1.8g triethyl phosphate, 15g four water-calcium nitrate, the 3g sodium oxide is together put into 70 ml waters, with the dilute hydrochloric acid adjust pH to 4 of 1M, in the time of 15 ℃, stir 5h with 600 rev/mins of magnetic stirring apparatuss, carry out cohydrolysis reaction.Get cohydrolysis product 10ml, add the sustained-release micro-spheres of a certain amount of chitosan and ofloxacin, and mix homogeneously.25 ℃ of ageings 7 days, then through dehydrate step by step, 100 ℃ of heat treatments 24 hours, obtain end product again.
Be that 1000 both-end base is that the polycaprolactone (PCL) of hydroxyl reacts with 9.3g isocyanate group triethoxysilane with the 20g molecular weight, obtain the polycaprolactone that the 29.3g end group contains ethyl-silicone.To contain the solution of this molecule of 25g and 16.6g tetraethoxysilane, 2g triethyl phosphate, 14g lime nitrate, the 1g sodium oxide is together put into 60 ml waters, with the dilute hydrochloric acid adjust pH to 4 of 1M, in the time of 15 ℃, stirred 8 hours with 800 rev/mins of magnetic stirring apparatuss, carry out cohydrolysis reaction.Get the cohydrolysis product of 10ml, add a certain amount of elecrtonegativity polymer hyaluronic acid restir 0.5h, then 15 ℃ of ageings 14 days, 200 ℃ of heat treatments 24 hours, obtain end product again.
Be that 600 both-end base is that the Polyethylene Glycol (PEG) of hydroxyl reacts with 13.5g isocyanate group triethoxysilane with the 18g molecular weight, obtain the Polyethylene Glycol that the 31.5g end group contains ethyl-silicone.With this molecule of 20g and 16.6g tetraethoxysilane, 1g triethyl phosphate, 10g lime nitrate, 0.5g sodium oxide is together put into 100 ml waters, with the ammonia adjust pH to 8 of 4M, in the time of 15 ℃, stirred 4 hours with 800 rev/mins of magnetic stirring apparatuss, carry out cohydrolysis reaction.Get cohydrolysis product 10ml, add a certain amount of elecrtonegativity polymeric hydantoin sodium alginate, the gentamycin sustained-release micro-spheres, mix homogeneously, then product is 50 ℃ of ageings 2 days, and 48h is processed in lyophilization, 150 ℃ of heat treatments 24 hours, obtains hybrid material again.
Be that 8000 both-end base is the PLA-PGA(PLGA of hydroxyl with the 16g molecular weight) react with 1g isocyanate group triethoxysilane, obtain the PLGA that the 17g end group contains ethyl-silicone.Solution and 16.6g tetraethoxysilane, 0.9g triethyl phosphate, the 15g lime nitrate that will contain this molecule of 15g are together put into 50 ml waters, sodium hydroxide adjust pH to 9 with 1M, in the time of 15 ℃, stirred 4 hours with 1200 rev/mins of magnetic stirring apparatuss, carry out cohydrolysis reaction.Get cohydrolysis product 10ml, add minute quantity and facilitate bone protein, macromolecule 1g chitosan, 0.5g hyaluronic acid, mix homogeneously.45 ℃ of ageings 3 days, lyophilization 48h 200 ℃ of heat treatments 48 hours, obtained end product again with product.
Be that 3000 both-end base is that PEG-PCL copolymer and the 2.4g isocyanate group triethoxysilane of hydroxyl reacts with the 15g molecular weight, obtain the PEG-PCL that the 17.4g end group contains ethyl-silicone.This molecule of 10g and 16.6g tetraethoxysilane, 1.2g triethyl phosphate, 12g lime nitrate are together put into 50 ml waters, dilute hydrochloric acid adjust pH to 5 with 1M, in the time of 15 ℃, stirred 6 hours with 1200 rev/mins of magnetic stirring apparatuss, carry out cohydrolysis reaction, then pH is adjusted to neutrality (getting final product about 7).Get cohydrolysis product 10ml, add and facilitate bone protein BMP, 0.5g collagen protein, mix.Above-mentioned product is placed on 100 ℃ of lower ageings 1 day, step by step dehydration, normal temperature drying then 100 ℃ of heat treatments 24 hours, obtains the purpose product again.
Be that 4000 both-end base is that PLA-PEG-PLA triblock copolymer and the 1.4g isocyanate group triethoxysilane of hydroxyl reacts with the 12g molecular weight, obtain the macromolecule that the 13.4g end group contains ethyl-silicone.This molecule of 8g and 16.6g tetraethoxysilane, 0.5g triethyl phosphate, 13g lime nitrate are together put into 60 ml waters, with the dilute hydrochloric acid adjust pH to 3 of 1M, in the time of 15 ℃, stirred 4 hours with 800 rev/mins of magnetic stirring apparatuss, carry out cohydrolysis reaction.Add buffer, regulate pH to 6.8.Get the cohydrolysis product after 10ml transfers pH, the chitosan, the hyaluronic acid that add medicament slow-release microsphere, RGD modification remix and stir.The product of preparation is placed on 35 ℃ of lower ageings 5 days, 200 ℃ of heat treatments 24 hours, obtains end product again.
Be that 2000 both-end base is that PCL-PEG-PCL triblock copolymer and the 4.7g isocyanate group triethoxysilane of hydroxyl reacts with the 20g molecular weight, obtain the macromolecule that the 24.7g end group contains ethyl-silicone.This molecule of 10g and 16.6g tetraethoxysilane, 0.4g triethyl phosphate, 6g lime nitrate are together put into 70 ml waters, dilute hydrochloric acid adjust pH to 6 with 1M, in the time of 15 ℃, stirred 2 hours with 800 rev/mins of magnetic stirring apparatuss, carry out cohydrolysis reaction, add ofloxacin slow-release microsphere and 5g collagen restir 0.5h.After stirring, above-mentioned reactant places 100 milliliters of plastic beakers, and 15 ℃ of ageings 20 days, supercritical drying 48h 200 ℃ of heat treatments 24 hours, namely got product again.
Embodiment 9
Be that 10000 polyurethane and 0.5g isocyanate group triethoxysilane react with the 20g molecular weight, obtain the polyurethane that the 20.5g end group contains ethyl-silicone.3 these molecules of gram and 16.6g tetraethoxysilane, 0.8g triethyl phosphate, 8g lime nitrate are together put into 60 ml waters, with the dilute hydrochloric acid adjust pH to 4 of 1M, in the time of 15 ℃, stirred 4 hours with 1200 rev/mins of magnetic stirring apparatuss, carry out cohydrolysis reaction.Add buffer, regulate pH to 6.8, get 10ml and add 0.2g elecrtonegativity polymer hyaluronic acid and 0.5g collagen, mixing and stirring.4 ℃ of ageings 14 days, 48h was processed in lyophilization with above-mentioned reactant, 200 ℃ of heat treatments 24 hours, obtained end product again.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not limited by the examples; as also adding other medicines with therapeutical effect, bioactive molecule solution, slow releasing preparation, genophore or elecrtonegativity macromolecule etc. in cohydrolysis and the dehydration polyreaction; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. collosol and gel bioactivity glass-polymer hybridisation material preparation method is characterized in that, comprises the steps:
(1) macromolecule and isocyanate group alkylalkoxy silane are reacted, obtain the macromolecule of oxyalkylsiloxane base end-blocking;
The aqueous solution of the macromolecule of the oxyalkylsiloxane base end-blocking that (2) step (1) is obtained and the precursor of bioactivity glass mixes, and carries out cohydrolysis and dehydration polyreaction;
Wherein the high molecular mass percent of oxyalkylsiloxane base end-blocking is 60% ~ 10%, and the mass percent of the presoma of bio-vitric is 40% ~ 90%;
(3) product that step (2) is obtained carries out carrying out dried behind the ripening;
(4) product that step (3) is obtained is heat-treated, and obtains collosol and gel bioactivity glass-polymer hybridisation material.
2. collosol and gel bioactivity glass according to claim 1-polymer hybridisation material is characterized in that, the reaction temperature of the described cohydrolysis of step (2) and dehydration polyreaction is 4 ℃ ~ 40 ℃, and the pH value scope is 4 ~ 9, and the response time is no less than 2 hours.
3. collosol and gel bioactivity glass according to claim 2-polymer hybridisation material preparation method is characterized in that, described pH value adopts hydrochloric acid, ammonia or sodium hydroxide to regulate.
4. collosol and gel bioactivity glass according to claim 1-polymer hybridisation material preparation method is characterized in that, the reaction temperature of the described ripening of step (3) is 4 ℃ ~ 100 ℃.
5. collosol and gel bioactivity glass according to claim 1-polymer hybridisation material is characterized in that, the described heat treated temperature of step (4) is 100 ℃ ~ 800 ℃.
6. collosol and gel bioactivity glass according to claim 1-polymer hybridisation material preparation method, it is characterized in that, the described macromolecule of step (1) is two hydroxyls, aminoterminal based high molecular or polyhydroxy, aminoterminal based high molecular, and number-average molecular weight is 100 ~ 20000.
7. collosol and gel bioactivity glass according to claim 1-polymer hybridisation material preparation method, it is characterized in that step (2) also adds medicine, bioactive molecule solution, slow releasing preparation, genophore or the elecrtonegativity macromolecule with therapeutical effect.
8. collosol and gel bioactivity glass according to claim 1-polymer hybridisation material preparation method is characterized in that, the described isocyanate group alkylalkoxy silane of step (1) is monoalkoxy, bis-alkoxy or tri-alkoxy.
9. collosol and gel bioactivity glass according to claim 1-polymer hybridisation material preparation method is characterized in that, it is 30% ~ 80% SiO that the precursor of bioactivity glass comprises mass percent
2, mass percent is 10% ~ 40% CaO, mass percent is 1% ~ 10% P
2O
5, mass percent is 0 ~ 20% NaO.
10. collosol and gel bioactivity glass according to claim 1-polymer hybridisation material preparation method is characterized in that, the described drying of step (3) is lyophilization or supercritical drying.
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| CN104307041A (en) * | 2014-09-22 | 2015-01-28 | 中国人民解放军第四军医大学 | Applications of bionic silicon-calcium hybrid collagen scaffold material within fiber |
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| CN111001035A (en) * | 2019-12-25 | 2020-04-14 | 玉子涛 | Preparation method of bioactive glass composite wound gel |
| CN118126267A (en) * | 2024-03-25 | 2024-06-04 | 江苏海洋大学 | Application of modified bioactive glass in preparation of multifunctional hydrogel |
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