CN102886069B - 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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- CN102886069B CN102886069B CN201210358478.2A CN201210358478A CN102886069B CN 102886069 B CN102886069 B CN 102886069B CN 201210358478 A CN201210358478 A CN 201210358478A CN 102886069 B CN102886069 B CN 102886069B
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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 inorganic-organic hybridization technical field of composite materials, be specifically related to the preparation method of sol gel bioactive glass-polymer hybridisation material.
Background technology
Osseous tissue is the histoorgan that body weight for humans is wanted, and its major function is motion, supports and protection health, is also the hemopoietic organ that body weight for humans is wanted simultaneously, and the vitals of storage calcium Phosphate minerals.The defect of osseous tissue produces great impact by health and daily life.
But due to congenital and traumatic reason, orthopaedics, dentistry, decorative sursery, plastic surgery etc. clinically, the Cranial defect case causing resected bone to cause by the reason such as bone tumor, bone cyst is very many.After osseous tissue excision, not only cause the disappearance of correlation function, simultaneously due to the excision of osseous tissue, change with the anatomical structure of surrounding tissue, mechanical structure relation, also easily cause the corresponding complication of surrounding tissue to occur.As the hearing disability caused after maxillectomy; Impact of resection of radial head is postoperative there is osteoarthritis of elbow, the involutory exception in joint etc.; After thoracic vertebra tumor resection, may there is flexion deformity, dislocation etc. in vertebra, again cause paraplegia.Therefore, in sacrectomy, usually need corresponding filling material of bone to substitute the osseous tissue of excision, to ensure that the partial function of corresponding defective tissue is still preserved after surgery.
Current clinical conventional bone filling renovation material mainly contains the osseous tissue of biogenic as autologous bone, homogeneous allogenic bone or bone-xenograft; Natural material is as the Corallium Japonicum Kishinouye etc. of modification; And synthetic inorganic material, as calcium sulfate, calcium carbonate, hydroxyapatite, tricalcium phosphate and bio-vitric etc.In general, autologous filler repair materials repairing effect is best, but there is the limited problem of supply.Allogeneic and foreign material also have good repairing effect, but owing to there is the problem of immunity and pathology, are not also widely used clinically.The calcium phosphate material of natural origin, and the inorganic material wide material sources of synthesis class, steady chemical structure, is widely used at present clinically.But also find in application process, inorganic material is due to the characteristic of its own molecular structure, and repair materials exists the shortcomings such as fragility is large, difficult processing, power applications are inconvenient, bone renovating material that neither be best.Bioactivity glass a kind ofly has excellent biocompatibility and bioactive mineral-type bioactive materials, a series of surface reaction can be there is rapidly in it at implant site, form the hydroxyapatite layer that can produce good combination with bone and soft tissue, promote the regeneration of osseous tissue, receive the attention of related researcher.But bio-vitric belongs to inorganic material, still there is the problems such as fragility is large, difficult processing, power applications are inconvenient.
Organic/inorganic composite material can improve the mouldability of material to a certain extent, the mechanical property of controlled material and biology performance.But the composite of research is at present all large-sized hybrid material, as studied the composite that the inorganic material such as more degradable polyester family macromolecule and hydroxyapatite, tricalcium phosphate, bio-vitric are formed at present.The hydridization only rested in large scale still cannot meet must possess biologic activity, degradability, mechanics Adapter Property requirement to bone filling renovation material simultaneously.The hydridization of small scale, the hydridization namely on nanoscale and molecular level, is only the method finally solved the biological degradable composite of above-mentioned multi-functional demand.
Although the material of large scale hydridization and small scale hydridization is the same in the arrangement of composition and atom or molecule, but the hybrid material that organic polymer and inorganic material are formed on a molecular scale, due to the molecular structure feature that it is special, coexisting and combination of dissimilar chemical bond can be realized at material internal simultaneously, as the chemical bond of the ionic bond of high molecular covalent bond and inorganic material, and this combination is at molecular level, combination on nanoscale, make material both can have the characteristic of inorganic material, also can have organic macromolecule feature simultaneously, organic as component state of aggregation, the nanostructured of inorganic phase small scale hydridization shows distinctive nanometer cooperative effect, the new material formed can also have macromolecule independent than ever, the performance that inorganic material is more excellent, thus obtain the new material of unique properties, show the required excellent performance of many people.
The preparation of sol-gel bioglass is hydrolyzed into silicone hydroxyl by alcoxyl key in siloxane precursors, then dewatered by the condensation of silicone hydroxyl, forms the macromole silica network complex of bio-vitric.Based on the composition principle of above-mentioned sol-gel bioglass, the group of macromolecule end group containing silicon alkoxyl is carried out end group modification, silicone hydroxyl is formed by the hydrolysis of silicon alkoxyl, and carry out cocondensation with the silicone hydroxyl group in 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, preparation has the molecular hybrid inorganic-organic bioactivity glass composite of clinical practice meaning.
Summary of the invention
The object of the invention is to the deficiency that fragility is large, power applications is inconvenient overcoming existing sol gel bioactive glass, the preparation method of sol gel bioactive glass-polymer hybridisation composite is provided.
Object of the present invention is achieved through the following technical solutions:
The preparation method of sol gel bioactive glass-polymer hybridisation material, comprises the steps:
(1) macromolecule and isocyanatoalkyl alkoxy silane are reacted, obtain the macromolecule of oxyalkylsiloxane base end-blocking;
(2) macromolecule of oxyalkylsiloxane base end-blocking step (1) obtained and the aqueous solution of the precursor of bioactivity glass are uniformly mixed, and carry out cohydrolysis and dehydration polymerization reaction;
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 obtained step (2) carries out dried after carrying out ripening;
(4) product that step (3) obtains is heat-treated, obtain bio-vitric-polymer hybridisation material.
The reaction temperature of step (2) described cohydrolysis and dehydration polymerization reaction is 4 DEG C ~ 40 DEG C, and pH value range 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 step (3) described ripening is 4 DEG C ~ 100 DEG C.
The described heat treated temperature of step (4) is 100 DEG C ~ 800 DEG C.
Step (1) described macromolecule is two hydroxyl, aminoterminal based high molecular or polyhydroxy, aminoterminal based high molecular, and number-average molecular weight is 100 ~ 20000.
Step (2) also adds the medicative medicine of tool, bioactive molecule solution, slow releasing preparation, genophore or elecrtonegativity macromolecule.
The described isocyanatoalkyl alkoxy silane of step (1) is monoalkoxy, bis-alkoxy or tri-alkoxy.
The precursor of bioactivity glass comprises the SiO that mass percent is 30% ~ 80%
2, mass percent is the CaO of 10% ~ 40%, and mass percent is the P of 1% ~ 10%
2o
5, mass percent is the NaO of 0 ~ 20%.
Step (3) described drying is lyophilization or supercritical drying.
Compared with current material, tool of the present invention has the following advantages and effect:
(1) conventional sol gel biological glass is in ageing drainage procedure, easy cracking, be difficult to prepare massive material, and after adopting organic molecule to carry out hydridization, fractionated polymer subchain can in ageing process stable silicon oxygen network structure, reduce and avoid subsiding and ftractureing of material, being beneficial to the material of preparation bulk.Secondly, owing to there is high molecular structure in system, the fragility of material reduces greatly, and toughness and processing characteristics improve.
(2) sol gel bioactive glass-polymer hybridisation composite that prepared by the present invention remains the excellent properties (external mineralization experiments result shows that this repair materials can form calcium phosphorus precipitation on surface in simulated body fluid) of sol-gel bioglass, a series of surface reaction can be there is in expection at implant site, form the class bone calcium phosphorus precipitation producing good combination with bone, promote the regeneration of osseous tissue.
Accompanying drawing explanation
Fig. 1 is the infared spectrum of sol-gel bioglass-polymer hybridisation material of preparing of the present embodiment and Polyethylene Glycol (PEG).
Fig. 2 is PEG mineralising 7 days surperficial SEM figure in simulated body fluid.
Fig. 3 is glue gel bio-vitric-polymer hybridisation material mineralising 7 days surperficial SEM pictures in simulated body fluid prepared by the present embodiment.
Fig. 4 is the energy spectrogram of the surface deposits of glue gel bio-vitric-polymer hybridisation material prepared by the present embodiment.
Detailed description of the invention
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 thereto.
Embodiment 1
Be that the Polyethylene Glycol (PEG) 200 of hydroxyl reacts with 37.2g isocyanate group triethoxysilane by the both-end base of 16g, obtain the Polyethylene Glycol that 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, 15 DEG C time, stirs 3h with magnetic stirring apparatus 800 revs/min, carry out cohydrolysis reaction.Get cohydrolysis product 10ml, add 0.2g hyaluronic acid, 100ng bone morphogenic protein BMP-2 in solution, mix homogeneously.4 DEG C of ageings, after 10 days, are placed in-20 DEG C of refrigerator 7d, then lyophilization process 48 hours, then after 3 hours, obtain end product in 800 DEG C of heat treatments.
Fig. 1 is sol-gel bioglass-polymer hybridisation material of preparing of the present embodiment and the infared spectrum (sol-gel bioglass that in figure prepared by the corresponding the present embodiment of the curve A-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 bio-vitric hybridisation process, the characteristic absorption peak of its chemical bond amide group.
Fig. 2 is PEG mineralising 7 days surperficial SEM figure in simulated body fluid.Fig. 3 is glue gel bio-vitric-polymer hybridisation material mineralising 7 days surperficial SEM pictures in simulated body fluid prepared by the present embodiment, and as shown in Figure 3, glue gel bio-vitric-polymer hybridisation material surface prepared by the present embodiment has obvious mineral deposition.Fig. 4 is the surface mineral of glue gel bio-vitric-polymer hybridisation material prepared by the present embodiment sedimental energy spectrogram, and energy spectrum analysis shows, in this deposit, main component is calcium P elements.Show that glue gel bio-vitric-polymer hybridisation material prepared by the present embodiment at implant site, a series of surface reaction can occur, form the calcium phosphorus precipitation thing that can produce good combination with bone and soft tissue, promote the regeneration of osseous tissue.
Embodiment 2
By 12g molecular weight be 400 both-end base be that Polyethylene Glycol (PEG) and the 14g isocyanate group triethoxysilane of hydroxyl reacts, obtain the Polyethylene Glycol that 26g end group contains ethyl-silicone.By this molecule of 25g and 16.6g tetraethoxysilane, 1.8g triethyl phosphate, 15g four water-calcium nitrate, 3g sodium oxide together puts into 70 ml waters, with the dilute hydrochloric acid adjust pH to 4 of 1M, 15 DEG C time, stir 5h with magnetic stirring apparatus 600 revs/min, 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 DEG C of ageings 7 days, then through dehydrate step by step, then 100 DEG C of heat treatments 24 hours, obtain end product.
Embodiment 3
By 20g molecular weight be 1000 both-end base be that polycaprolactone (PCL) and the 9.3g isocyanate group triethoxysilane of hydroxyl reacts, obtain the polycaprolactone that 29.3g end group contains ethyl-silicone.Solution and 16.6g tetraethoxysilane, 2g triethyl phosphate, the 14g lime nitrate of this molecule of 25g will be contained, 1g sodium oxide together puts into 60 ml waters, with the dilute hydrochloric acid adjust pH to 4 of 1M, 15 DEG C time, stir 8 hours with magnetic stirring apparatus 800 revs/min, carry out cohydrolysis reaction.Get the cohydrolysis product of 10ml, add a certain amount of elecrtonegativity polymer hyaluronic acid and stir 0.5h again, then 15 DEG C of ageings 14 days, then 200 DEG C of heat treatments 24 hours, obtain end product.
Embodiment 4
By 18g molecular weight be 600 both-end base be that Polyethylene Glycol (PEG) and the 13.5g isocyanate group triethoxysilane of hydroxyl reacts, obtain the Polyethylene Glycol that 31.5g end group contains ethyl-silicone.By this molecule of 20g and 16.6g tetraethoxysilane, 1g triethyl phosphate, 10g lime nitrate, 0.5g sodium oxide together puts into 100 ml waters, with the ammonia adjust pH to 8 of 4M, 15 DEG C time, stir 4 hours with magnetic stirring apparatus 800 revs/min, carry out cohydrolysis reaction.Get cohydrolysis product 10ml, add a certain amount of elecrtonegativity polymeric hydantoin sodium alginate, gentamycin sustained-release micro-spheres, mix homogeneously, then product was 50 DEG C of ageings 2 days, lyophilization process 48h, then 150 DEG C of heat treatments 24 hours, obtained hybrid material.
Embodiment 5
By 16g molecular weight be 8000 both-end base be the PLA-PGA(PLGA of hydroxyl) react with 1g isocyanate group triethoxysilane, obtain the PLGA that 17g end group contains ethyl-silicone.The solution and 16.6g tetraethoxysilane, 0.9g triethyl phosphate, 15g lime nitrate that contain this molecule of 15g are together put into 50 ml waters, with the sodium hydroxide adjust pH to 9 of 1M, 15 DEG C time, stir 4 hours with magnetic stirring apparatus 1200 revs/min, carry out cohydrolysis reaction.Get cohydrolysis product 10ml, add minute quantity and facilitate bone protein, macromolecule 1g chitosan, 0.5g hyaluronic acid, mix homogeneously.By product 45 DEG C of ageings 3 days, lyophilization 48h, then 200 DEG C of heat treatments 48 hours, obtain end product.
Embodiment 6
By 15g molecular weight be 3000 both-end base be that the PEG-PCL copolymer of hydroxyl and 2.4g isocyanate group triethoxysilane react, obtain the PEG-PCL that 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, with the dilute hydrochloric acid adjust pH to 5 of 1M, 15 DEG C time, stir 6 hours with magnetic stirring apparatus 1200 revs/min, carry out cohydrolysis reaction, then pH is adjusted to neutrality (about 7).Get cohydrolysis product 10ml, add and facilitate bone protein BMP, 0.5g collagen protein, be uniformly mixed.At above-mentioned product is placed on 100 DEG C, ageing 1 day, dewaters, then normal temperature drying step by step, then 100 DEG C of heat treatments 24 hours, obtains object product.
Embodiment 7
By 12g molecular weight be 4000 both-end base be that the PLA-PEG-PLA triblock copolymer of hydroxyl and 1.4g isocyanate group triethoxysilane react, obtain the macromolecule that 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, 15 DEG C time, stirs 4 hours with magnetic stirring apparatus 800 revs/min, carry out cohydrolysis reaction.Add buffer, regulate pH to 6.8.Get 10ml and adjust the cohydrolysis product after pH, add medicament slow-release microsphere, chitosan that RGD modifies, hyaluronic acid remix and stir.Ageing 5 days at the product of preparation is placed on 35 DEG C, then 200 DEG C of heat treatments 24 hours, obtain end product.
Embodiment 8
By 20g molecular weight be 2000 both-end base be that the PCL-PEG-PCL triblock copolymer of hydroxyl and 4.7g isocyanate group triethoxysilane react, obtain the macromolecule that 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, with the dilute hydrochloric acid adjust pH to 6 of 1M, 15 DEG C time, stir 2 hours with magnetic stirring apparatus 800 revs/min, carry out cohydrolysis reaction, add ofloxacin slow-release microsphere and 5g collagen stirs 0.5h again.After stirring, above-mentioned reactant is placed in 100 milliliters of plastic beakers, 15 DEG C of ageings 20 days, and supercritical drying 48h, then 200 DEG C of heat treatments 24 hours, obtain product.
Embodiment 9
By 20g molecular weight be 10000 polyurethane and 0.5g isocyanate group triethoxysilane react, obtain the polyurethane that 20.5g end group contains ethyl-silicone.3 grams of these molecules 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, 15 DEG C time, stirs 4 hours with magnetic stirring apparatus 1200 revs/min, 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.By above-mentioned reactant 4 DEG C of ageings 14 days, lyophilization process 48h, then 200 DEG C of heat treatments 24 hours, obtain end product.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; as the medicative medicine of other tools, bioactive molecule solution, slow releasing preparation, genophore or elecrtonegativity macromolecule etc. also can be added in cohydrolysis and dehydration polymerization reaction; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. the preparation method of sol gel bioactive glass-polymer hybridisation material, is characterized in that, comprise the steps:
(1) macromolecule and isocyanatoalkyl alkoxy silane are reacted, obtain the macromolecule of oxyalkylsiloxane base end-blocking; The Polyethylene Glycol of described macromolecule to be both-end base be hydroxyl, molecular weight is 200,400 or 600;
(2) macromolecule of oxyalkylsiloxane base end-blocking step (1) obtained and the aqueous solution of the precursor of bioactivity glass are uniformly mixed, and carry out cohydrolysis and dehydration polymerization reaction;
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 obtained step (2) carries out dried after carrying out ripening;
(4) product that step (3) obtains is heat-treated, obtain sol gel bioactive glass-polymer hybridisation material.
2. the preparation method of sol gel bioactive glass-polymer hybridisation material according to claim 1, it is characterized in that, the reaction temperature of step (2) described cohydrolysis and dehydration polymerization reaction is 4 DEG C ~ 40 DEG C, and pH value range is 4 ~ 9, and the response time is no less than 2 hours.
3. the preparation method of sol gel bioactive glass-polymer hybridisation material according to claim 2, is characterized in that, described pH value adopts hydrochloric acid, ammonia or sodium hydroxide to regulate.
4. the preparation method of sol gel bioactive glass-polymer hybridisation material according to claim 1, is characterized in that, the reaction temperature of step (3) described ripening is 4 DEG C ~ 100 DEG C.
5. the preparation method of sol gel bioactive glass-polymer hybridisation material according to claim 1, is characterized in that, the described heat treated temperature of step (4) is 100 DEG C ~ 800 DEG C.
6. the preparation method of sol gel bioactive glass-polymer hybridisation material according to claim 1, it is characterized in that, step (2) also adds the medicative medicine of tool, bioactive molecule solution, slow releasing preparation, genophore or elecrtonegativity macromolecule.
7. the preparation method of sol gel bioactive glass-polymer hybridisation material according to claim 1, is characterized in that, the described isocyanatoalkyl alkoxy silane of step (1) is monoalkoxy, bis-alkoxy or tri-alkoxy.
8. the preparation method of sol gel bioactive glass-polymer hybridisation material according to claim 1, is characterized in that, the precursor of bioactivity glass comprises the SiO that mass percent is 30% ~ 80%
2, mass percent is the CaO of 10% ~ 40%, and mass percent is the P of 1% ~ 10%
2o
5, mass percent is the Na of 0 ~ 20%
2o.
9. the preparation method of sol gel bioactive glass-polymer hybridisation material according to claim 1, is characterized in that, step (3) described drying is lyophilization or supercritical drying.
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| WO2014124496A1 (en) * | 2013-02-14 | 2014-08-21 | The University Of Sydney | Biocompatible material and uses thereof |
| CN103656755A (en) * | 2013-12-12 | 2014-03-26 | 华南理工大学 | Preparation method of polymer-bioglass hybrid material for bone repair |
| CN108653821B (en) * | 2017-03-27 | 2020-01-07 | 南方医科大学第三附属医院 | Citric acid-bioactive glass organic-inorganic hybrid material and preparation method and application thereof |
| CN108578785B (en) * | 2018-04-26 | 2020-11-27 | 福州大学 | Preparation method of magnetic self-healing bioglass/hydrogel composite material |
| CN109734914B (en) * | 2019-01-15 | 2021-06-22 | 苏州世华新材料科技股份有限公司 | Phosphorus-containing organic silicon resin and preparation method thereof |
| CN111001035A (en) * | 2019-12-25 | 2020-04-14 | 玉子涛 | Preparation method of bioactive glass composite wound gel |
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Granted publication date: 20141231 Termination date: 20200924 |