CN102390941A - Medical alpha-hemihydrate calcium sulfate artificial bone repairing material and preparation method thereof - Google Patents
Medical alpha-hemihydrate calcium sulfate artificial bone repairing material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a medical alpha-hemihydrate calcium sulfate artificial bone repairing material and a preparation method thereof. The material has uniform particle size distribution, regular shape, favorable biocompatibility and wide market application prospect in the field such as a bone transplanting material and the like. In addition, the invention relates to the application of the bone repairing material and the like.
Description
Technical field
The invention belongs to the medical product field, particularly, the present invention relates to medical α-calcium sulphate hemihydrate artificial bone repair materials and preparation method thereof.In addition, the invention still further relates to the application of this bone renovating material.
Background technology
Along with Increase of population and aging, be one of modal disease clinically because of the bone that causes behind wound, infection and the tumor resection is damaged.According to the recent statistics of the U.S., the surgical operation that relates to the bone defect repair its every year is above 1,000,000 person-times.And China, existing limbs the disabled is about 7,550,000 people, and the accidental injury that causes because of traffic, industrial injury and sports etc. is with annual 7.3% speed increase, and the active demand of a large amount of clinical applications has driven growing continuously and fast of bone renovating material.
Clinical various bone renovating materials are mainly titanium metal, alumina-ceramic, bio-vitric, tricalcium phosphate (TCP), polymethylmethacrylate (PMMA), bone cement, the various biomaterial that is the basis with Win 40350 (HAP) at present.Above-mentioned these materials are owing to defectives such as biocompatibility, osteoinductive limit its application.
The nineties in 20th century, U.S. Wright medical skill ltd went out bone transplantation substitute product OsteoSet of new generation, the calcium sulphate hemihydrate (CaSO that is to use special method to process with calcium sulfate for the matrix development and production
41/2H2O).Have excellent biological compatibility and bone inductive effect,, get permission a kind of bone graft substitute in clinical use through the authentication of U.S. FDA (U.S. food and FAD).
Correspondingly, Chinese patent 00100673 discloses the Osteological material of calcium sulphate hemihydrate, but does not study particle diameter character, does not also contain the calcium succinate composition; Chinese patent 0180866 discloses the setting particle of sulfur acid calcium, the complicated means preparation but it need pressurize etc., nor contain the calcium succinate composition; Chinese patent 02125346 discloses the composite biological material of sulfur acid calcium, but does not study particle diameter character, does not also contain the calcium succinate composition; Chinese patent 02809194 discloses a kind of bone transplantation group compound based on calcium phosphate/calcium sulfate, phosphoric acid calcium wherein, but do not contain calcium succinate; Chinese patent 02817063 discloses the implant compositions that contains calcium sulfate compound and polymkeric substance, but does not study particle diameter character, does not also contain the calcium succinate composition; Chinese patent 200480009791 discloses and has contained the Injectable composition of particle diameter less than 0.1 micron granular hardened calcium sulfate material, is used for the bone salts equivalent material, but does not wherein have the calcium succinate composition; Chinese patent 200510103264 discloses citric acid half-H 2 O calcium sulphate bone substitute, but does not study particle diameter character, does not also contain the calcium succinate composition; Chinese patent 200510131093 has mentioned that bone substitute can comprise terra alba small-particle and at least a lime carbonate, bata-tricalcium phosphate, secondary calcium phosphate, dicalcium phosphate dihydrate, magnesiumcarbonate, tricresyl phosphate magnesium, Marinco H or the magnesian small-particle of being selected from, but does not point out the use of calcium succinate all the time; Chinese patent 200610014733 discloses controllable cured calcium sulfate bone-cementing agent and preparation method thereof, but its controllable be not the size of particle diameter, nor contain calcium succinate; Chinese patent 200610029066 and 200610029067 discloses the compound self-curing material of biological activity tricalcium silicate/calcium sulphate hemihydrate, but does not study particle diameter character, does not also contain the calcium succinate composition; Chinese patent 200810301291 discloses calcium sulfate composite material, and it is made up of compound that contains strontium and calcium sulfate, but does not study particle diameter character, does not also contain calcium succinate.
The inventor is through long-term and arduous research; Find unexpectedly, in the process of preparation α-calcium sulphate hemihydrate, add the composition that forms calcium succinate; Not only can make the crystal grain that finally obtains not receive the influence of mixing element; And pattern is more regular, and size distribution is homogeneous comparatively, can directly be pressed into the paddy repair materials fully; More unexpected is; The preparation method that the inventor studied; Can be through regulating the size that these simple means of amount of alcohol added are regulated the crystal grain particle diameter; And in the preparation process, avoided pressure process and too high temperature (as, 140 ℃), make preparation operation more easily, cost lower.
Summary of the invention
Technical problem to be solved by this invention just provides the regular α of pattern-calcium sulphate hemihydrate artificial bone repair materials and preparation method thereof, remedying the defective of prior art, and the deficiency of additional prior art.
Particularly, in first aspect, the invention provides the preparation method of artificial bone repair materials, it comprises:
(1) in the solution that mixes succsinic acid, calcium hydroxide and water, add ethanol, add sulfuric acid reaction then, filtering also more successively, drying obtains powder; With
(2) heating mixes the solution of succsinic acid, calcium chloride and water, adds resulting powder of step (1) and insulation reaction then, filters successively, dries and obtain powder, and this powder compression is become artificial bone renovating material.
Stirring is for disperseing solute, and effects such as accelerated reaction are known in those skilled in the art.Therefore preferred in the preparation method of first aspect present invention, all can stir in the process of mixing, adding and/or reacting, like magnetic agitation.The speed that stirs can be 100-400rpm, as 200-400rpm (as, in step (1)) or 100-300rpm (as, in step (2)).
Because the succsinic acid indissoluble is separated, therefore in the process of mixing succsinic acid, can mix with water earlier, ultra-sonic dispersion 5-60min extremely dissolves fully, and then adds other materials.
Dry use usually heat up dry (that is, oven dry), this knows to those skilled in the art.Drying temperature can be 30-120 ℃, is dried to no longer loss of weight of powder usually.For example, drying temperature can be 30-50 ℃, is generally 2-6 hour time of drying, and and for example, drying temperature is 100-120 ℃, is generally 0.5-3 hour time of drying.
In the preparation method of first aspect present invention; The powder that step (2) obtains can directly be pressed into the artificial bone repair materials; Also can with other materials (as, polymkeric substance, tackiness agent, microbiotic, Delicious peptide and/or chemotherapeutics) mix the back compacting, preferably directly suppress.The form that is pressed into can be general lamellar morphology (that is, tablet), so that cut and correction of the flank shape when using, also can directly be pressed into the form of use.
Preferably in the preparation method of first aspect present invention,
Ethanol in the step (1) is absolute ethyl alcohol;
Solution and ethanol volume ratio in the step (1) are 1:0.5-5, are preferably 1:0.7-3.5, most preferably are 1:0.75-3, like 1:3, and 1:1.5,1:1, or 1:0.75;
Step (2) is carried out under normal pressure; And/or
The particle diameter of the resulting powder of step (2) preferably less than 80 microns, is more preferably less than 50 microns less than 100 microns, as between the 25-55 micron, and 20-35,17-25, perhaps 14-18 micron.
It is also preferred in the preparation method of first aspect present invention,
The succsinic acid in the step (1) and the mol ratio of calcium hydroxide are 1:0.5-2, are preferably 1:0.85-1.25, most preferably are 1:1;
Calcium hydroxide and vitriolic mol ratio in the step (1) are 1:1-3, and preferably 1:1.5-2.5 most preferably is 1:2;
The succsinic acid in the step (1) and the weight ratio of water are 0.25-0.6:150, are preferably 0.3-0.45:150, most preferably are 0.3872:150;
Solution in the step (2) contains the calcium chloride of 20-40% (w/w), preferably contains the calcium chloride of 25-35% (w/w), most preferably contains 30% calcium chloride; And/or
The succsinic acid in the step (2) and the weight ratio of water are 0.5-0.8:35, are preferably 0.6-0.75:35, most preferably are 0.686:35.
It is also preferred in the preparation method of first aspect present invention,
Other processes in the step (1) except the exsiccant process are carried out at 0-50 ℃, preferably carry out at 10-40 ℃, are more preferably at 20-30 ℃ to carry out, and most preferably carry out in room temperature (25 ℃);
The temperature of heating is 90-100 ℃ in the step (2), is preferably 95-100 ℃, most preferably is 100 ℃; And/or
The temperature of insulation is 100-130 ℃ in the step (2), is preferably 105-125 ℃, most preferably is 110-120 ℃.
It is preferred in addition in the preparation method of first aspect present invention,
The time of reaction is 1-4 hour in the step (1), is preferably 1.5-2.5 hour, most preferably is 2 hours; And/or
The time of reaction is 2-6 hour in the step (2), is preferably 3-5 hour, most preferably is 4 hours;
Can also be preferred in the preparation method of first aspect present invention,
Sulfuric acid in the step (1) is that the form with sulphuric acid soln provides, and the concentration of preferably sulfuric acid solution is 0.5-2mol/L, is preferably 0.8-1.5mol/L, most preferably is 1.2mol/L; And/or
Slowly add sulfuric acid in the step (1), preferably adding vitriolic speed is 10-50mmol/ hour, preferably 20-30mmol/ hour, most preferably is 24mmol/ hour.
Among the preparation method in the specific embodiment of the invention,
Solution in the step (1) and ethanol volume ratio are 1:3, and the particle diameter of the resulting powder of step (2) is between the 29.9-52.1 micron thus;
Solution in the step (1) and ethanol volume ratio are 1:1.5, and the particle diameter of the resulting powder of step (2) is between the 23.6-33.2 micron thus;
Solution in the step (1) and ethanol volume ratio are 1:1, and the particle diameter of the resulting powder of step (2) is between the 17.8-23.6 micron thus; And/or
Solution in the step (1) and ethanol volume ratio are 1:0.75, and the particle diameter of the resulting powder of step (2) is between the 14.2-17.5 micron thus.
In second aspect, the invention provides the artificial bone repair materials of preparing method's preparation of first aspect present invention, wherein contain calcium sulfate and calcium succinate.
In the third aspect; The artificial bone repair materials that the invention provides second aspect present invention is used for the application of the medical product of bone repair in preparation, and preferred wherein artificial bone repair materials and a surname are from one or more the compound use of material of microbiotic, Delicious peptide and chemotherapeutics.
In yet another aspect, the invention provides the method for regulating powder diameter size in the artificial bone renovating material, it comprises solution and alcoholic acid volume ratio in the preparing method's who regulates first aspect present invention the step (1).That is, the invention provides the method for regulating powder diameter size in the artificial bone renovating material, it comprises:
(1) solution of mixing succsinic acid, calcium hydroxide and water, regulator solution and alcoholic acid volume ratio add the ethanol through the adjusted volume ratio, add sulfuric acid reaction then, and filtering also more successively, drying obtains powder; With
(2) heating mixes the solution of succsinic acid, calcium chloride and water, adds resulting powder of step (1) and insulation reaction then, filters successively, dries and obtain powder, and this powder compression is become artificial bone renovating material.Identical described in the preparation method of each preferred aspect and first aspect present invention wherein.
The present invention has obtained following beneficial effect:
1, preparation method of the present invention need not to carry out compressive reaction, can prepare.
2, powder diameter is more regular in the artificial bone repair materials of preparation method of the present invention preparation, makes constant product quality, and clinical use has no side effect, and more can replace other repair materials clinically.
3, under preparing method's framework of the present invention, according to the different volumes of being found than the influence rule of ethanol/solution to grain-size, pattern, can active adjustment artificial bone repair materials in the size of powder.Along with improving constantly of absolute ethyl alcohol/solution proportion in the reaction soln; To reduce grain-size, length is narrowed down to about 17um by 50um, and width is narrowed down to about 7um by 13um; Length-to-diameter ratio narrows down to 2.4 by 3.1, make crystal formation by needle-like, thin wall shape to bar-shaped, heavy wall shape transition.
For the ease of understanding, below will describe in detail the present invention through concrete accompanying drawing and embodiment.What need particularly point out is that specific examples and accompanying drawing only are in order to explain, not constitute limitation of the scope of the invention.Obviously those of ordinary skill in the art can explain according to this paper, within the scope of the invention the present invention is made various corrections and change, and these corrections and change are also included in the scope of the present invention.In addition, the present invention has quoted open source literature, and these documents also are in order more clearly to describe the present invention, and their full text content is all included the present invention in and carried out reference, just look like they full text in specification sheets of the present invention repeated description the same excessively.
Description of drawings:
The artificial bone repair materials finished product that Fig. 1 prepares for preparation technology according to the present invention;
Fig. 2 is for going out the SEM photo of the powder of step (1) with different ratios ethanol/formulations prepared from solutions, (a)-(d) corresponding successively embodiment 1-4 wherein, and wherein crystal habit, size are comparatively mixed and disorderly;
Fig. 3 is for going out the SEM photo of the powder of step (2) with different ratios ethanol/formulations prepared from solutions, (a)-(d) corresponding successively embodiment 1-4 wherein, and wherein crystal habit is regular;
Fig. 4 has wherein measured crystalline long (length), wide (width) and long-width ratio (ratio) respectively for prepare the measuring result of the crystalline size (Crain size) of the powder of step (2) with different ratios ethanol (Ethanol amount).
Concrete embodiment:
Below in conjunction with concrete embodiment, further illustrate the present invention.Should be understood that these embodiment only are used to explain the present invention, and be not used in restriction scope of the present invention.
Embodiment 1 is with ethanol preparation bone renovating material at high proportion
(1) preparation of amorphous powder:
Under the room temperature (25 ℃), take by weighing succsinic acid 0.3872g, ultra-sonic dispersion is 5 minutes in 150ml zero(ppm) water; Adding is the calcium hydroxide 0.24g of 1:1 with the succsinic acid mol ratio, ultrasonic once more 5 minutes, above-mentioned solution is pressed the 1:3 volume ratio add absolute ethyl alcohol; When utilizing magnetic stirrer, in solution, drip the dilute sulphuric acid 5.4ml of 1.2mol/L, rate of addition is 20mL/h; Then, the reaction 2h, filter, dry amorphous powder.
(2) preparation of micron order crystal powder:
Take by weighing succsinic acid 0.6860g, ultra-sonic dispersion is 3 minutes in 35ml zero(ppm) water, adds calcium chloride, (making it become massfraction is 30% calcium chloride solution); Above-mentioned solution is poured in the there-necked flask, placed oil bath pan, the top is equipped with recirculated water, magnetic agitation; Rotating speed is 200 rev/mins, is preheated to the powder that adds step (1) preparation gained after 100 ℃, and control reaction temperature is 110 ℃, reaction 4h; Filter, oven dry obtains crystalline powder (powder detects through ESEM and is micron powder, and powder diameter is between the 29.9-52.1 micron); Carry out compressing tablet, make the bone renovating material tablet, sterilization, envelope.
Embodiment 2 is with middle ratio ethanol preparation bone renovating material
(1) preparation of amorphous powder:
Under the room temperature (25 ℃), take by weighing succsinic acid 0.3872g, ultra-sonic dispersion is 5 minutes in 150ml zero(ppm) water; Adding is the calcium hydroxide 0.24g of 1:1 with the succsinic acid mol ratio, ultrasonic once more 5 minutes, above-mentioned solution is pressed the 2:3 volume ratio add absolute ethyl alcohol; When utilizing magnetic stirrer, in solution, drip the dilute sulphuric acid 5.4ml of 1.2mol/L, rate of addition is 20mL/h; The reaction 2h, filter, dry amorphous powder.
(2) preparation of micron order crystal powder:
Take by weighing succsinic acid 0.6860g, ultra-sonic dispersion is 3 minutes in 35ml zero(ppm) water, adds calcium chloride, (making it become massfraction is 30% calcium chloride solution); Above-mentioned solution is poured in the there-necked flask, placed oil bath pan, the top is equipped with recirculated water, magnetic agitation; Rotating speed is 200 rev/mins, is preheated to the powder that adds step (1) preparation gained after 100 ℃, and control reaction temperature is 120 ℃, reaction 4h; Filter, oven dry obtains crystalline powder (powder detects through ESEM and is micron powder, and powder diameter is between the 23.6-33.2 micron) and carries out compressing tablet; Make the bone renovating material tablet, sterilization, envelope.
Embodiment 3 is with equal proportion ethanol preparation bone renovating material
(1) preparation of amorphous powder:
Under the room temperature (25 ℃), take by weighing succsinic acid 0.3872g, ultra-sonic dispersion is 5 minutes in 150ml zero(ppm) water; Adding is the calcium hydroxide 0.24g of 1:1 with the succsinic acid mol ratio, ultrasonic once more 5 minutes, above-mentioned solution is pressed the 1:1 volume ratio add absolute ethyl alcohol; When utilizing magnetic stirrer, in solution, drip the dilute sulphuric acid 5.4ml of 1.2mol/L, rate of addition is 20mL/h; The reaction 2h, filter, dry amorphous powder.
(2) preparation of micron order crystal powder:
Take by weighing succsinic acid 0.6860g, ultra-sonic dispersion is 3 minutes in 35ml zero(ppm) water, adds calcium chloride, (making it become massfraction is 30% calcium chloride solution); Above-mentioned solution is poured in the there-necked flask, placed oil bath pan, the top is equipped with recirculated water, magnetic agitation; Rotating speed is 200 rev/mins, is preheated to the powder that adds step (1) preparation gained after 100 ℃, and control reaction temperature is 118 ℃, reaction 4h; Filter, oven dry obtains crystalline powder (powder detects through ESEM and is micron powder, and powder diameter is between the 17.8-23.6 micron) and carries out compressing tablet; Make the bone renovating material tablet, sterilization, envelope.
Embodiment 4 is with low ratio ethanol preparation bone renovating material
(1) preparation of amorphous powder:
Under the room temperature (25 ℃), take by weighing succsinic acid 0.3872g, ultra-sonic dispersion is 5 minutes in 150ml zero(ppm) water; Adding is the calcium hydroxide 0.24g of 1:1 with the succsinic acid mol ratio, ultrasonic once more 5 minutes, above-mentioned solution is pressed the 4:3 volume ratio add absolute ethyl alcohol; When utilizing magnetic stirrer, in solution, drip the dilute sulphuric acid 5.4ml of 1.2mol/L, rate of addition is 20mL/h; The reaction 2h, filter, dry amorphous powder.
(2) preparation of micron order crystal powder:
Take by weighing succsinic acid 0.6860g, ultra-sonic dispersion is 3 minutes in 150ml zero(ppm) water, adds calcium chloride, (making it become massfraction is 30% calcium chloride solution); Above-mentioned solution is poured in the there-necked flask, placed oil bath pan, the top is equipped with recirculated water, magnetic agitation; Rotating speed is 200 rev/mins, is preheated to the powder that adds step (1) preparation gained after 100 ℃, and control reaction temperature is 112 ℃, reaction 4h; Filter, oven dry obtains crystalline powder (powder detects through ESEM and is micron powder, and powder diameter is between the 14.2-17.5 micron) and carries out compressing tablet; Make the bone renovating material tablet, sterilization, envelope.
The clinical efficacy of embodiment 5 bone renovating materials of the present invention
Zhao so-and-so (numbering 0079XX), man, 23 years old; Left side ilium pain appearred under no obvious inducement before January; Limitation of activity, the X sheet shows: left ilium bone cyst, about 3cm * 3cm size; Row left ilium tumour excision bone grafting operation, wherein used artificial bone is to prepare according to the embodiment of the invention 4 methods.The postoperative wound healing is good, the not swollen inflammation of show.In 1 week of patient's postoperative, left lower extremity can carry out simple telescopic movable in bed, and 2 weeks can be leant on with turning down and walked.Allergy and general toxic reaction are not found in postoperative check in January, and the X sheet shows: the artificial bone of implantation has small amount of degradation, have very thin trabecular bone structure to form on every side, and bone density increases; Postoperative 3 months, the most of degraded of artificial bone, cavity area is substituted by freshman bone tissue; Postoperative June, artificial bone is absorbed fully, and bone cavity has formed good trabecular bone structure, and new bone is connected patient's freedom of movement through reinventing deformation with normal bone on every side naturally.
Claims (10)
1. the preparation method of artificial bone repair materials, it comprises:
(1) in the solution that mixes succsinic acid, calcium hydroxide and water, add ethanol, add sulfuric acid reaction then, filtering also more successively, drying obtains powder; With
(2) heating mixes the solution of succsinic acid, calcium chloride and water, adds resulting powder of step (1) and insulation reaction then, filters successively, dries and obtain powder, and this powder compression is become artificial bone renovating material.
2. the described preparation method of claim 1, wherein,
Ethanol in the step (1) is absolute ethyl alcohol;
Solution and ethanol volume ratio in the step (1) are 1:0.5-5, are preferably 1:0.7-3.5, most preferably are 1:0.75-3, like 1:3, and 1:1.5,1:1, or 1:0.75;
Step (2) is carried out under normal pressure; And/or
The particle diameter of the resulting powder of step (2) preferably less than 80 microns, is more preferably less than 50 microns less than 100 microns, as between the 25-55 micron, and 20-35,17-25, perhaps 14-18 micron.
3. the described preparation method of claim 1, wherein,
The succsinic acid in the step (1) and the mol ratio of calcium hydroxide are 1:0.5-2, are preferably 1:0.85-1.25, most preferably are 1:1;
Calcium hydroxide and vitriolic mol ratio in the step (1) are 1:1-3, and preferably 1:1.5-2.5 most preferably is 1:2;
The succsinic acid in the step (1) and the weight ratio of water are 0.25-0.6:150, are preferably 0.3-0.45:150, most preferably are 0.3872:150;
Solution in the step (2) contains the calcium chloride of 20-40% (w/w), preferably contains the calcium chloride of 25-35% (w/w), most preferably contains 30% calcium chloride; And/or
The succsinic acid in the step (2) and the weight ratio of water are 0.5-0.8:35, are preferably 0.6-0.75:35, most preferably are 0.686:35.
4. the described preparation method of claim 1, wherein,
Other processes in the step (1) except the exsiccant process are carried out at 0-50 ℃, preferably carry out at 10-40 ℃, are more preferably at 20-30 ℃ to carry out, and most preferably carry out in room temperature (25 ℃);
The temperature of heating is 90-100 ℃ in the step (2), is preferably 95-100 ℃, most preferably is 100 ℃; And/or
The temperature of insulation is 100-130 ℃ in the step (2), is preferably 105-125 ℃, most preferably is 110-120 ℃.
5. the described preparation method of claim 1, wherein,
The time of reaction is 1-4 hour in the step (1), is preferably 1.5-2.5 hour, most preferably is 2 hours; And/or
The time of reaction is 2-6 hour in the step (2), is preferably 3-5 hour, most preferably is 4 hours.
6. the described preparation method of claim 1, wherein,
Sulfuric acid in the step (1) is that the form with sulphuric acid soln provides, and the concentration of preferably sulfuric acid solution is 0.5-2mol/L, is preferably 0.8-1.5mol/L, most preferably is 1.2mol/L; And/or
Adding vitriolic speed in the step (1) is 10-50mmol/ hour, preferably 20-30mmol/ hour, most preferably is 24mmol/ hour.
7. the artificial bone repair materials of arbitrary described preparing method's preparation of claim 1-6 wherein contains calcium sulfate and calcium succinate.
8. the described artificial bone repair materials of claim 7 is used for the application of the medical product of bone repair in preparation.
9. the described application of claim 9, wherein artificial bone repair materials and one or more the compound use of material that is selected from microbiotic, Delicious peptide and chemotherapeutics.
10. regulate the method for the size of powder diameter in the artificial bone renovating material, it comprises solution and alcoholic acid volume ratio in the arbitrary described preparing method's who regulates claim 1-6 the step (1).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633287A (en) * | 2012-04-05 | 2012-08-15 | 中国科学院宁波材料技术与工程研究所 | Preparation methods of medical alpha-calcium sulfate hemihydrate powder and calcium sulfate artificial bone material |
| CN105169470A (en) * | 2015-09-02 | 2015-12-23 | 北京益而康生物工程开发中心 | Method for preparing injectable bone repair material by virtue of ultra-gravity process |
| CN108187133A (en) * | 2018-01-09 | 2018-06-22 | 楼毅 | A kind of preparation method of medical composite type α-half-H 2 O calcium sulphate artificial bone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996039203A1 (en) * | 1995-06-06 | 1996-12-12 | Gensci Regeneration Laboratories, Inc. | Modified osteogenic materials |
| CN1470247A (en) * | 2002-07-24 | 2004-01-28 | 清华大学 | Bone repairing material |
| US20050208094A1 (en) * | 2003-09-05 | 2005-09-22 | Armitage Bryan M | Bone cement compositions having fiber-reinforcement and/or increased flowability |
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2011
- 2011-08-10 CN CN 201110227747 patent/CN102390941B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996039203A1 (en) * | 1995-06-06 | 1996-12-12 | Gensci Regeneration Laboratories, Inc. | Modified osteogenic materials |
| CN1470247A (en) * | 2002-07-24 | 2004-01-28 | 清华大学 | Bone repairing material |
| US20050208094A1 (en) * | 2003-09-05 | 2005-09-22 | Armitage Bryan M | Bone cement compositions having fiber-reinforcement and/or increased flowability |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633287A (en) * | 2012-04-05 | 2012-08-15 | 中国科学院宁波材料技术与工程研究所 | Preparation methods of medical alpha-calcium sulfate hemihydrate powder and calcium sulfate artificial bone material |
| CN102633287B (en) * | 2012-04-05 | 2014-05-07 | 中国科学院宁波材料技术与工程研究所 | Preparation methods of medical alpha-calcium sulfate hemihydrate powder and calcium sulfate artificial bone material |
| CN105169470A (en) * | 2015-09-02 | 2015-12-23 | 北京益而康生物工程开发中心 | Method for preparing injectable bone repair material by virtue of ultra-gravity process |
| CN108187133A (en) * | 2018-01-09 | 2018-06-22 | 楼毅 | A kind of preparation method of medical composite type α-half-H 2 O calcium sulphate artificial bone |
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| CN102390941B (en) | 2013-01-23 |
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