CN100420489C - Controllable cured calcium sulfate bone-cementing agent and its preparation method - Google Patents
Controllable cured calcium sulfate bone-cementing agent and its preparation method Download PDFInfo
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- CN100420489C CN100420489C CNB2006100147336A CN200610014733A CN100420489C CN 100420489 C CN100420489 C CN 100420489C CN B2006100147336 A CNB2006100147336 A CN B2006100147336A CN 200610014733 A CN200610014733 A CN 200610014733A CN 100420489 C CN100420489 C CN 100420489C
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Abstract
The present invention relates to a controllable solidifying calcium sulphate bone adhesive and a preparation method thereof, which has the technical scheme that dewatering calcium sulphate and an accessory ingredient are uniformly mixed and are aged for 1 to 48h for standby; the dewatering calcium sulphate and a solidifying solution are mixed after 2 to 5 min, adhesive slurry is obtained through hydration reaction. The present invention is characterized in that the controllable solidifying calcium sulphate bone adhesive is prepared from the components of the proportion by weight: 40 to 80% of dewatering calcium sulphate, 10 to 50% of solidifying solution and 1 to 20% of accessory ingredient. The produced calcium sulphate bone adhesive has the characteristics of adjustable curing time m high material strength after solidification, less heat discharge in the solidifying process, etc. The present invention can be used for fields of medical bone repairing materials of human body bone defect repair, percutaneous vertebroplasty, etc., and can satisfy the requirements of bone repairing materials for bone tissue engineering.
Description
Technical field
The present invention relates to medical material tech field, particularly a kind of controllable cured calcium sulfate bone-cementing agent.
Background technology
In clinical treatment, when serious comminuted fracture, fracture region bone loss or osteoporosis, it is fixing to use Gypsum Fibrosum to be difficult to merely, and the risk of displacement of fracture secondary and malunion is very high, often needs the internal fixation technology; In addition, spinal column gryposis, vertebra wound, spinal column infect or tumor all will cause vertebral disease, common clinicals such as lumbar spondylolisthesis and lumbar vertebra disintegrate further take place, but in the treatment of cone, adopt external metal implant to fix clinically at present mostly, from the method solution of body or allogenic bone transplantation reparation; Though from the body bone is optimal bone-grafting material, but because that it is originated on the one hand is limited, can not satisfy the case that needs a large amount of bone graftings, can cause on the other hand and get the various complication in bone district, not only bring extra misery, and influence patient's postoperative functional rehabilitation timely to the patient; Allograph bone is mainly derived from corpse, animal and family numbers of patients, though the source is sufficient relatively, allograph bone easily produces immunological rejection, infects hepatitis, HIV (human immunodeficiency virus) (Human Immunodeficiency Virus) etc., and the graft failure rate is also high; And allograph bone is substituted slowly, and the area of new bone volume is less than normal.For the reparation that solves these bone defect area and fixing, the big quantity research of the new material of various synthetic, polymethyl methacrylate (PMMA) bone cement at present commonly used, though it has cohesive and mechanical property preferably preferably, but because it can not be degraded, exist second operation to take out the problem of implant, and the bio-compatible sexual deviation, can cause the fiberization of implant site.Though poly-lactic acid material has excellent biological compatibility and mechanical property,, limited its application at aspects such as bone binding material, minimizing operation wounds owing to can only implant then and carry out the bone reparation in external molding.Calcium phosphate bone cement material research recently is more, some launch are also arranged, but it exists intensity on the low side both at home and abroad, and because its curing rate is very fast, can not satisfy operating requirement, cause operating time short partially, can not be well as a kind of use of bone cementum.Domestic patent CN1446588 synthetic bone binding agents such as (glass-base nanometer hydroxylapatite biology cement and preparation method thereof), its operable time is all short partially, and because the variation of pH value in the solidification process, can cause some inflammatory reactions of human body, and curing rate can bring bigger heat release faster, increases patient's discomfort.The history of the research of the existing last 100 years of calcium sulfate material, as far back as nineteen twenty-eight, just there is the scholar to utilize calcium sulfate to carry out the infection of bone treatment of Canis familiaris L., use calcium sulfate to carry out the research that bone is repaired and just studied at LEONARD F. in 1964 etc., after the eighties, the product of various calcium sulfate emerges in large numbers one after another, but the controllability of material cured time and the mechanical property after the material cured are all not ideal.
Summary of the invention
It is controlled that the present invention aims to provide a kind of hardening time, has better biocompatibility and mechanical strength, and degradation time adjustable bone cement material, and the growth that it can induce bone in vivo helps the healing of bone defect area.
Bone cementum provided by the invention is several and the preparation method technology is as follows:
Controllable cured calcium sulfate bone-cementing agent of the present invention is characterized in that component and weight percent content are as follows:
Dehydrated calcium sulfate material 40-80%
Consolidation liquid 10-50%
Adjuvant 1-20%.
The composition and the mass ratio of described dehydrated calcium sulfate material are as follows:
CaO 20-60％
SO
3 20-50％
H
2O 0-30％。
Described dehydrated calcium sulfate preparation methods is as follows:
Calcium sulphate dihydrate is calcined or calcined in 120-300 ℃ of following saturated steam at 100-400 ℃ of following atmospheric pressure, make the sulfate hemihydrate calcium material; The sulfate dihydrate calcium material is dewatered under 800-1200 ℃, make the anhydrous slufuric acid calcium material, with one or several mix homogeneously in calcium sulphate dihydrate, half-H 2 O calcium sulphate, the anhydrous slufuric acid calcium material, its quality proportioning is as follows:
Calcium sulphate dihydrate 0-100%
Half-H 2 O calcium sulphate 0-100%
Dead plaster 0-100%
With this different materials mix homogeneously, at grinding in ball grinder 4-12h, the control material powder diameter is below 100 microns.
Described consolidation liquid is autoclaved distilled water, wherein contains one or more the combination in NaCl, KCl, type i collagen, the polyvinyl alcohol, and its quality proportioning is as follows:
NaCl 0-1％
KCl 0-1％
Type i collagen 0-1%
Polyvinyl alcohol 0-1%
Water 96-100%
In these several materials one or several are dissolved in the water, make consolidation liquid.
Described adjuvant is natural polymer type i collagen, chitosan, sodium alginate, polyhydric alcohol, hyaluronic acid, fibrin and synthetic high polymer Polyethylene Glycol, polylactone, poly-in dioxanone, poly-anhydride or the polyphosphazene one or several.The preparation method of controllable cured calcium sulfate bone-cementing agent of the present invention is with dehydrated calcium sulfate material and adjuvant mix homogeneously, and is standby behind the ageing 1-48h; Behind dehydrated calcium sulfate material and the consolidation liquid mixing 2-5min,, obtain having close-burning slurry through hydration reaction.
Between the preferred 20-45min of described material cured time.Binding agent is after solidifying 1-3 days, and its compressive resistance is 50-110MPa.
The total quality of various components satisfies 100%, difference hardening time of different proportioning materials, and with this different materials mix homogeneously, at grinding in ball grinder 4-12h, the control material powder diameter is below 100 microns.
Calcium sulfate material itself has the favorable tissue compatibility and bone conductibility, and under the combined effect of the good adjuvant of biocompatibility, and the growth of bone is had good facilitation.Material is behind external curing 24h, and its compressive resistance is 50-110MPa; Material is injected the buffer solution of simulated body fluid environment, and material still can be realized solidifying, and solidifies the back material and have mechanical strength preferably.Material after the curing is 4-6 week degraded in the environment of hydrochloric acid-Tris simulated body fluid, and in the degradation process, the mechanical property of material still has reservation significantly; In the simulated body fluid environment of PBS, degrade, because ion and phosphatic effect, so the degraded of material is slack-off, degradation time is 4-8 week; Therefore in vivo, can predict, the degradation speed of material can be slack-off.
In a word, compare with existing material, the up time that the bone cementum that the present invention relates to has higher mechanical strength, grows, and can be implemented in the rigorous environment and solidify, prepared dehydrated calcium sulfate has scalable hardening time under the firming agent effect, solidify back strength of materials height, characteristics such as heat release is little in the solidification process can be applicable to medical bone renovating material fields such as defect of human body bone reparation, vertebroplasty, satisfy the requirement of bone tissue engineer to bone renovating material.
Specific implementation method
Provide embodiments of the invention below, be to further specify, rather than limit the scope of the invention of the present invention.
Embodiment 1:
In chamber type electric resistance furnace, 100 ℃ of insulation 5h generate half-H 2 O calcium sulphate with calcium sulphate dihydrate; 90g half-H 2 O calcium sulphate and 10g calcium sulphate dihydrate are mixed the back at grinding in ball grinder 4h, make its particle diameter less than 100 microns; After getting the powder of 40g porphyrize and 5g type i collagen, 4g chitosan, 5g sodium alginate, 6g polyhydric alcohol mixed grinding then, ageing 24h.Consolidation liquid forms serosity for containing the 0.9%NaCl aqueous solution behind the adding 40ml consolidation liquid mixing 2min.Serosity begins initial set behind 5min, final set behind 25min, and best service time, the compressive strength behind the material cured 48h was 50MPa between the 10-20min behind the formation serosity, material is degraded in 56 days in PBS simulated body fluid environment.
Embodiment 2:
Calcium sulphate dihydrate in chamber type electric resistance furnace, behind 400 ℃ of insulation 5h, is generated half-H 2 O calcium sulphate; 80g half-H 2 O calcium sulphate and 20g calcium sulphate dihydrate are mixed the back at grinding in ball grinder 12h, make its particle diameter less than 50 microns; After getting the powder of 40g porphyrize and 5g hyaluronic acid, 5g fibrin, 5g Polyethylene Glycol mixed grinding then, ageing 24h.Consolidation liquid is the aqueous solution that contains 0.2%NaCl, 0.6%KCl, forms serosity behind the adding 45ml consolidation liquid mixing 5min.Serosity begins initial set behind 10min, final set behind 45min, best service time is between the 10-20min behind the formation serosity, compressive strength behind the material cured 24h is 65MPa, degraded in 30 days was degraded after 7 days in the environment of hydrochloric acid-Tris simulated body fluid, and intensity keeps 30%, after 20 days, material still has＞intensity of 2MPa.
Embodiment 3:
In the high steam still, behind 120 ℃ of insulation 8h, generate half-H 2 O calcium sulphate this moment with calcium sulphate dihydrate, and calcium sulphate dihydrate at chamber type electric resistance furnace, behind 1200 ℃ of insulation 2h, is generated dead plaster this moment; 30g calcium sulphate dihydrate, 10g half-H 2 O calcium sulphate and 60g dead plaster are mixed the back at grinding in ball grinder 8h, make its particle diameter less than 100 microns; After getting the powder of 60g porphyrize and 5g type i collagen, 5g hyaluronic acid mixed grinding then, ageing 24h.Consolidation liquid is the aqueous solution that contains 0.2%NaCl, 0.6%KCl, 0.5%I Collagen Type VI, 0.5% polyvinyl alcohol, forms serosity behind the adding 30ml consolidation liquid mixing 5min.Serosity begins initial set behind 15min, final set behind 40min, and best service time, the compressive strength behind the material cured 24h was 94MPa, degraded in 40 days in the environment of hydrochloric acid-Tris simulated body fluid in order to form between the 20-30min behind the serosity.
Embodiment 4:
Calcium sulphate dihydrate in the high steam still, behind 300 ℃ of insulation 2h, is generated half-H 2 O calcium sulphate; At grinding in ball grinder 8h, make its particle diameter the 100g half-H 2 O calcium sulphate less than 100 microns; After getting the powder of 60g porphyrize and 5g type i collagen, 5g polylactone mixed grinding then, ageing 48h.Consolidation liquid is the aqueous solution that contains 0.2%NaCl, 0.6%KCl, 0.5%I Collagen Type VI, 0.5% polyvinyl alcohol, forms serosity behind the adding 30ml consolidation liquid mixing 3min.Serosity begins initial set behind 15min, final set behind 45min, and best service time, the compressive strength behind the material cured 72h was 110MPa in order to form between the 20-30min behind the serosity, material is degraded in 53 days in PBS simulated body fluid environment.
Embodiment 5:
Calcium sulphate dihydrate in chamber type electric resistance furnace, behind 1000 ℃ of insulation 4h, is generated dead plaster; 50g calcium sulphate dihydrate, 50g dead plaster are mixed the back at grinding in ball grinder 8h, make its particle diameter less than 100 microns; After getting the powder of 70g porphyrize and 5g type i collagen, 5g hyaluronic acid mixed grinding then, ageing 24h.Consolidation liquid is the aqueous solution that contains 0.1%NaCl, 0.1%KCl, 1%I Collagen Type VI, 1% polyvinyl alcohol, forms serosity behind the adding 20ml consolidation liquid mixing 5min.Serosity begins initial set behind 15min, final set behind 40min, and best service time, the compressive strength behind the material cured 24h was 89MPa, degraded in 35 days in the environment of hydrochloric acid-Tris simulated body fluid in order to form between the 20-30min behind the serosity.
Embodiment 6:
Calcium sulphate dihydrate in chamber type electric resistance furnace, behind 800 ℃ of insulation 10h, is generated dead plaster; The 100g dead plaster is mixed the back at grinding in ball grinder 5h, make its particle diameter less than 50 microns; After getting the powder of 40g porphyrize and 5g type i collagen, the poly-anhydride mixed grinding of 5g then, ageing 24h.Consolidation liquid is the aqueous solution that contains 0.2%NaCl, 0.2%KCl, forms serosity behind the adding 50ml consolidation liquid mixing 2min.Serosity begins initial set behind 15min, final set behind 45min, and best service time, the compressive strength behind the material cured 24h was 70MPa, degraded in 35 days in the environment of hydrochloric acid-Tris simulated body fluid in order to form between the 20-30min behind the serosity.
Embodiment 7:
Calcium sulphate dihydrate in the high steam still, behind 200 ℃ of insulation 2h, is generated half-H 2 O calcium sulphate; At grinding in ball grinder 12h, make its particle diameter the 100g half-H 2 O calcium sulphate less than 100 microns; The powder and the 1g that get the 80g porphyrize then gather behind the dioxanone mixed grinding, and ageing 1h, consolidation liquid are the aqueous solution that contains 0.9%NaCl, 0.9%KCl, form serosity behind the adding 20ml consolidation liquid mixing 2min.Serosity begins initial set behind 5min, final set behind 20min, and best service time, the compressive strength behind the material cured 48h was 110MPa between the 10-15min behind the formation serosity, degraded in 45 days in the environment of hydrochloric acid-Tris simulated body fluid.
Embodiment 8:
Calcium sulphate dihydrate in chamber type electric resistance furnace, behind 1200 ℃ of insulation 4h, is taken out and quenches in ice-water bath, and form the dead plaster of amorphous state this moment, at grinding in ball grinder 12h, makes its particle diameter less than 100 microns the 100g dead plaster; After getting the powder of 80g porphyrize and 5g sodium alginate, 5g polyhydric alcohol mixed grinding then, ageing 24h.Consolidation liquid is the aqueous solution that contains 0.4%NaCl, 0.4%KCl, forms serosity behind the adding 20ml consolidation liquid mixing 5min.Serosity begins initial set behind 15min, final set behind 45min, and best service time, the compressive strength behind the material cured 24h was 92MPa between the 20-35min behind the formation serosity, degraded in 40 days in the environment of hydrochloric acid-Tris simulated body fluid.
Embodiment 9:
In chamber type electric resistance furnace, 120 ℃ of insulation 12h generate half-H 2 O calcium sulphate with calcium sulphate dihydrate, and calcium sulphate dihydrate in the high steam still, behind 200 ℃ of insulation 2h, is generated half-H 2 O calcium sulphate; After getting each 50g of half-H 2 O calcium sulphate that two kinds of distinct methods make respectively and mixing,, make its particle diameter less than 100 microns at grinding in ball grinder 8h; After getting the powder and 5g type i collagen and 5g polyphosphazene mixed grinding of 60g porphyrize then, ageing 24h.Consolidation liquid is the aqueous solution that contains 0.9%NaCl, 0.9%KCl, forms serosity behind the adding 35ml consolidation liquid mixing 2min.Serosity begins initial set behind 5min, final set behind 30min, and best service time, the compressive strength behind the material cured 24h was 98MPa between the 10-20min behind the formation serosity, degraded in 35 days in the environment of hydrochloric acid-Tris simulated body fluid.
Controllable cured calcium sulfate bone-cementing agent that the present invention discloses and discloses and preparation method thereof can be by using for reference this paper disclosure.Although controllable cured calcium sulfate bone-cementing agent of the present invention and preparation method thereof is described by preferred embodiment, but those skilled in the art obviously can change method as herein described in not breaking away from content of the present invention, spirit and scope, more particularly, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (8)
1. controllable cured calcium sulfate bone-cementing agent is characterized in that component and weight percent content are as follows:
Dehydrated calcium sulfate material 40-80%
Consolidation liquid 10-50%
Adjuvant 1-20%;
The composition and the mass ratio of described dehydrated calcium sulfate material are as follows:
CaO 20-60％
SO
3 20-50％
H
2O 0-30％；
Described dehydrated calcium sulfate preparation methods is as follows:
Calcium sulphate dihydrate is calcined or calcined in 120-300 ℃ of following saturated steam at 100-400 ℃ of following atmospheric pressure, make the sulfate hemihydrate calcium material; The sulfate dihydrate calcium material is dewatered under 800-1200 ℃, make the anhydrous slufuric acid calcium material, with one or several mix homogeneously in calcium sulphate dihydrate, half-H 2 O calcium sulphate, the anhydrous slufuric acid calcium material, its quality proportioning is as follows:
Calcium sulphate dihydrate 0-100%
Half-H 2 O calcium sulphate 0-100%
Dead plaster 0-100%,
At grinding in ball grinder 4-12h, the control material powder diameter is below 100 microns.
2. controllable cured calcium sulfate bone-cementing agent as claimed in claim 1 is characterized in that described consolidation liquid is autoclaved distilled water, wherein contains one or more the combination in NaCl, KCl, type i collagen, the polyvinyl alcohol, and its quality proportioning is as follows:
NaCl 0-1％
KCl 0-1％
Type i collagen 0-1%
Polyvinyl alcohol 0-1%
Water 96-100%.
3. controllable cured calcium sulfate bone-cementing agent as claimed in claim 1 is characterized in that described adjuvant is natural polymer type i collagen, chitosan, sodium alginate, polyhydric alcohol, hyaluronic acid, fibrin and synthetic high polymer Polyethylene Glycol, polylactone, poly-in dioxanone, poly-anhydride or the polyphosphazene one or several.
4. controllable cured calcium sulfate bone-cementing agent as claimed in claim 1 is characterized in that dehydrated calcium sulfate material and adjuvant mix homogeneously, and is standby behind the ageing 1-48h; Behind dehydrated calcium sulfate material and the consolidation liquid mixing 2-5min,, obtain having close-burning slurry through hydration reaction.
5. controllable cured calcium sulfate bone-cementing agent as claimed in claim 4 is characterized in that the described material cured time is between 20-45min.
6. controllable cured calcium sulfate bone-cementing agent as claimed in claim 1 is characterized in that described binding agent after solidifying 24h, and its compressive resistance is 50-110MPa.
7. controllable cured calcium sulfate bone-cementing agent as claimed in claim 1 is characterized in that described binding agent in hydrochloric acid-Tris simulated body fluid, and its degradation time is in 4-6 week.
8. controllable cured calcium sulfate bone-cementing agent as claimed in claim 1 is characterized in that described binding agent in the PBS simulated body fluid, and its degradation time is in 4-8 week.
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| CN101843918A (en) * | 2010-05-27 | 2010-09-29 | 甘少磊 | Composite bone repairing material based on nano-hydroxyapatite and hemihydrate calcium sulfate and preparation method thereof |
| CN108187144A (en) * | 2018-01-16 | 2018-06-22 | 北京科技大学 | A kind of injectable expansion composite bone cement of imitative trabecular bone structure and preparation method thereof |
| CN110755680B (en) * | 2019-11-25 | 2022-05-17 | 中鼎凯瑞科技成都有限公司 | Vitamin D-loaded calcium citrate/calcium sulfate composite bone cement and preparation method thereof |
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| CN1754519A (en) * | 2004-09-28 | 2006-04-05 | 中央医疗器材股份有限公司 | Method for controlling orthopaedic gypsum constituent operation time and its constituent |
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