CN101974212B - Polycaprolactone/calcium sulfate composite material and preparation method thereof - Google Patents
Polycaprolactone/calcium sulfate composite material and preparation method thereof Download PDFInfo
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- CN101974212B CN101974212B CN2010105225681A CN201010522568A CN101974212B CN 101974212 B CN101974212 B CN 101974212B CN 2010105225681 A CN2010105225681 A CN 2010105225681A CN 201010522568 A CN201010522568 A CN 201010522568A CN 101974212 B CN101974212 B CN 101974212B
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 171
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 73
- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000000975 co-precipitation Methods 0.000 claims abstract description 15
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 235000011132 calcium sulphate Nutrition 0.000 claims description 78
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- 238000005303 weighing Methods 0.000 claims description 21
- 239000001175 calcium sulphate Substances 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 238000000748 compression moulding Methods 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 230000004927 fusion Effects 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000003643 water by type Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 claims description 3
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 229940095672 calcium sulfate Drugs 0.000 abstract 3
- 229940095564 anhydrous calcium sulfate Drugs 0.000 abstract 2
- 239000003876 biosurfactant Substances 0.000 abstract 1
- 230000018729 macromolecule modification Effects 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The invention discloses a polycaprolactone/calcium sulfate composite material and a preparation method thereof, belonging to the field of macromolecule modification. The method comprises the following steps: utilizing biosurfactant to carry out surface modification on anhydrous calcium sulfate or calcium sulfate whiskers; and adopting a coprecipitation and mould pressing method to prepare anhydrous calcium sulfate or calcium sulfate whiskers reinforced polycaprolactone composite material. The composite material prepared by the method in the invention has the advantages of high mechanical strength and adjustable performance, thereby laying a foundation for the application thereof.
Description
Technical field
The invention belongs to macromolecule modified field, be specifically related to polycaprolactone/calcium sulfate composite material and preparation method thereof.
Background technology
Polycaprolactone has water-fast, oil resistant, and anti-muriatic performance, and have lower fusing point (about 60 ℃) and melt viscosity, this makes its easy machine-shaping.Polycaprolactone is applied to fields such as bone tissue engineer, medicament slow release because of having biocompatibility, biological degradability and hypotoxicity.Though above-mentioned all advantages are arranged, in practical application, the mechanical strength of polycaprolactone is low can not to meet the demands, and need carry out enhancing modified to it.
Domestic be used for strengthening polycaprolactone mainly contain calcium phosphate salt and Win 40350, but the degradation speed of calcium phosphate salt is slow, Win 40350 can not be absorbed in vivo basically.And therefore polycaprolactone, needs to add the enhancement component faster of degrading because the high-crystallinity degraded is very slow.Domestic less about the patent of invention that strengthens polycaprolactone, Chinese invention patent CN101693773A adopts the acorn nut powder that polycaprolactone is carried out enhancing modified, but the adding of acorn nut powder has influenced the biocompatibility and the degradation property of polycaprolactone, limits its Application Areas.Chinese invention patent CN1593673A adopts melt blending or mould pressing method to strengthen polycaprolactone with chitin fiber; But traditional melt blending technology needs to carry out being higher than under the temperature of melting point polymer; Shearing force that screw rod is stronger and high temperature can make the part poly-caprolactone degradation, thereby influence the mechanical property of material.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, a kind of polycaprolactone/calcium sulfate composite material and preparation method thereof is provided, the bar-shaped and whisker structure of calcium sulfate is not destroyed in the course of processing; The intensity of polycaprolactone is improved significantly.
The object of the invention is realized through following proposal:
Polycaprolactone/calcium sulfate composite material, the composition of this material is mainly: polycaprolactone 5g～19g, calcium sulfate 1g～15g.
Said calcium sulfate is anhydrous calciumsulphate or calcium sulfate crystal whiskers through surface-treated; Properties-correcting agent adopts a kind of in Yelkin TTS, rhamnolipid, the lipopeptid or more than one.
The preparation method of above-mentioned polycaprolactone/calcium sulfate composite material, following steps:
(1) coprecipitation method prepares polycaprolactone and calcium sulfate composite material
Taking by weighing the 16g polycaprolactone stirs in 50～60 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing 2.4g calcium sulfate, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of calcium sulfate and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Pour into fast in the beaker that fills the 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 35～50 ℃ of vacuum drying ovens, obtains the blend of powdered polycaprolactone and calcium sulfate;
(2) compression molding of polycaprolactone and anhydrous calciumsulphate matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 70～75 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, the die sinking sampling.
In the aforesaid method, said calcium sulfate is anhydrous calciumsulphate or calcium sulfate crystal whiskers through surface-treated,
(1) surface-treated of anhydrous calciumsulphate: take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 30～35 ℃, suction filtration is removed until impurity for 5 times.Add 15g calcium sulfate then, stirred restir 30 minutes 30 minutes ultrasonic 10 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of anhydrous calciumsulphates that obtain surface-treated down after dry 20 hours in vacuum drying oven.
(2) surface-treated of calcium sulfate crystal whiskers: take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 30～35 ℃, suction filtration is removed until impurity for 5 times.Add the 15g calcium sulfate crystal whiskers then, stirred restir 30 minutes 30 minutes ultrasonic 10 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of calcium sulfate crystal whiskers that obtain surface-treated down after dry 20 hours in vacuum drying oven.
The properties-correcting agent that said anhydrous calciumsulphate or calcium sulfate crystal whiskers surface-treated are adopted also comprises a kind of in rhamnolipid or the lipopeptid or more than one.
Polycaprolactone/calcium sulfate composite material of the present invention can be applicable to the bone reparation.
The present invention compared with prior art, advantage and effect be, adopts the preparation method of polycaprolactone/calcium sulfate composite material of the present invention, and the bar-shaped and whisker structure of calcium sulfate is not destroyed in the course of processing, the intensity of polycaprolactone is improved significantly; In whole technological process, can not make poly-caprolactone degradation; Technology of the present invention is simple, and is extensive in the clinical application field for it.
Calcium sulfate has HS, hypotoxicity, and advantages such as good biocompatibility adopt calcium sulfate powder and whisker modified polycaprolactone, can improve the strength and toughness of polycaprolactone simultaneously.The degradation speed of calcium sulfate is very fast, after the adding, can improve the slower deficiency of poly-caprolactone degradation.In addition; General industry is compared with tensio-active agent; Advantages such as that the bioactivity surface promoting agent has is nontoxic, biocompatibility adopt bioactivity surface promoting agent such as Yelkin TTS to calcium sulfate powder and the whisker modified powder oleophylic value surperficial with whisker that improve, and make the interfacial adhesion increase of calcium sulfate powder and whisker and polycaprolactone; Improve the mechanical property of matrix material, but matrix material can not receive application limitations because of having toxicity.
Adopt that calcium sulfate crystal whiskers and polycaprolactone are compound then to show tangible advantage.Itself has excellent biological compatibility calcium sulfate crystal whiskers, can degradation in vivo absorb.And the calcium sulfate crystal whiskers similar joins in the polycaprolactone in the structure of short glass fiber, can effectively improve the modulus and the shock strength of material, and improves material stiffness simultaneously and toughness is that most of powder body material reinforced effects is unapproachable.Therefore, this patent has adopted the enhancing matrix of calcium sulfate crystal whiskers as polycaprolactone.
Description of drawings
Fig. 1 is the electron scanning micrograph that the anhydrous calciumsulphate of the embodiment of the invention 1 strengthens polycaprolactone composite material.
Fig. 2 is the electron scanning micrograph that the calcium sulfate crystal whiskers of the embodiment of the invention 2 strengthens polycaprolactone composite material.
Fig. 3 is the electron scanning micrograph that the modification anhydrous calciumsulphate of the embodiment of the invention 3 strengthens polycaprolactone composite material.
Fig. 4 is the electron scanning micrograph that the wastewaters with modified calcium sulfate whiskers of the embodiment of the invention 4 strengthens polycaprolactone composite material.
Fig. 5 is the electron scanning micrograph that the wastewaters with modified calcium sulfate whiskers of the embodiment of the invention 5 strengthens polycaprolactone composite material.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further explain, but embodiment of the present invention is not limited thereto.
Embodiment 1
(1) coprecipitation method prepares polycaprolactone and anhydrous calciumsulphate matrix material
Taking by weighing the 16g polycaprolactone stirs in 58 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing 2.4g anhydrous slufuric acid calcium powder, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of anhydrous calciumsulphate and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Just pour into fast in ultrasonic, fill in the beaker of 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 45 ℃ of vacuum drying ovens, obtains the mixture of powdered polycaprolactone and anhydrous calciumsulphate.
(2) compression molding of polycaprolactone and anhydrous calciumsulphate matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 75 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, die sinking sampling (160 * 10 * 4mm
3).
Embodiment 2
(1) coprecipitation method prepares polycaprolactone and calcium sulfate crystal whiskers matrix material
Taking by weighing the 16g polycaprolactone stirs in 50 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing the modification anhydrous slufuric acid calcium powder of 2.4g, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of calcium sulfate crystal whiskers and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Just pour into fast in ultrasonic, fill in the beaker of 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 35 ℃ of vacuum drying ovens, obtains the mixture of powdered polycaprolactone and calcium sulfate crystal whiskers.
(2) compression molding of polycaprolactone and wastewaters with modified calcium sulfate whiskers matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 70 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, die sinking sampling (160 * 10 * 4mm
3).
Embodiment 3
(1) surface-treated of anhydrous calciumsulphate
Take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 35 ℃, suction filtration is removed until impurity for 5 times.Add 15g calcium sulfate then, stirred 30 minutes, ultrasonic 10 minutes, restir 30 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 50 ℃ of anhydrous calciumsulphates that obtain surface-treated down after dry 20 hours in vacuum drying oven.
(2) coprecipitation method prepares polycaprolactone and modification anhydrous calciumsulphate matrix material
Taking by weighing the 16g polycaprolactone stirs in 60 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing the modification anhydrous slufuric acid calcium powder of 2.4g, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of anhydrous calciumsulphate and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Just pour into fast in ultrasonic, fill in the beaker of 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 30 ℃ of vacuum drying ovens, obtains the mixture of powdered polycaprolactone and modification anhydrous calciumsulphate.
(3) compression molding of polycaprolactone and modification anhydrous calciumsulphate matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 71 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, die sinking sampling (160 * 10 * 4mm
3).
Embodiment 4
(1) surface-treated of calcium sulfate crystal whiskers
Take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 35 ℃, suction filtration is removed until impurity for 5 times.Add the 15g calcium sulfate crystal whiskers then, stirred 30 minutes, ultrasonic 10 minutes, restir 30 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of calcium sulfate crystal whiskers that obtain surface-treated down after dry 20 hours in vacuum drying oven.
(2) coprecipitation method prepares polycaprolactone and wastewaters with modified calcium sulfate whiskers matrix material
Taking by weighing the 16g polycaprolactone stirs in 55 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing the wastewaters with modified calcium sulfate whiskers of 2.4g, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of wastewaters with modified calcium sulfate whiskers and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Just pour into fast in ultrasonic, fill in the beaker of 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 45 ℃ of vacuum drying ovens, obtains the mixture of powdered polycaprolactone and wastewaters with modified calcium sulfate whiskers.
(3) compression molding of polycaprolactone and wastewaters with modified calcium sulfate whiskers matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 70 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, die sinking sampling (160 * 10 * 4mm
3).
Embodiment 5
(1) surface-treated of calcium sulfate crystal whiskers
Take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 35 ℃, suction filtration is removed until impurity for 5 times.Add the 15g calcium sulfate crystal whiskers then, stirred 30 minutes, ultrasonic 10 minutes, restir 30 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of calcium sulfate crystal whiskers that obtain surface-treated down after dry 20 hours in vacuum drying oven.
(2) coprecipitation method prepares polycaprolactone and wastewaters with modified calcium sulfate whiskers matrix material
Taking by weighing the 16g polycaprolactone stirs in 60 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing the wastewaters with modified calcium sulfate whiskers of 4g, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of wastewaters with modified calcium sulfate whiskers and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Just pour into fast in ultrasonic, fill in the beaker of 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 40 ℃ of vacuum drying ovens, obtains the mixture of powdered polycaprolactone and wastewaters with modified calcium sulfate whiskers.
(3) compression molding of polycaprolactone and wastewaters with modified calcium sulfate whiskers matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 73 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, die sinking sampling (160 * 10 * 4mm
3).
Following table is: embodiment 1～5 pure polycaprolactone and composite materials property
The foregoing description is merely preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other are any not to deviate from change, the modification done under spirit of the present invention and the principle, substitute, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (3)
1. the preparation method of polycaprolactone/calcium sulfate composite material is characterized in that following steps:
(1) coprecipitation method prepares polycaprolactone and calcium sulfate composite material
Taking by weighing the 16g polycaprolactone stirs in 50～60 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing 2.4g calcium sulfate, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of calcium sulfate and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Pour into fast in the beaker that fills the 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 35～50 ℃ of vacuum drying ovens, obtains the blend of powdered polycaprolactone and calcium sulfate;
(2) compression molding of polycaprolactone and anhydrous calciumsulphate matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 70～75 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, the die sinking sampling.
2. preparation method according to claim 1 is characterized in that, said calcium sulfate is anhydrous calciumsulphate or calcium sulfate crystal whiskers through surface-treated;
Said anhydrous calciumsulphate through surface-treated prepares as follows: take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 35 ℃, suction filtration 5 times is removed until impurity; Add 15g calcium sulfate then, stirred restir 30 minutes 30 minutes ultrasonic 10 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of anhydrous calciumsulphates that obtain surface-treated down after dry 20 hours in vacuum drying oven;
Said calcium sulfate crystal whiskers through surface-treated prepares as follows: take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 35 ℃, suction filtration 5 times is removed until impurity; Add the 15g calcium sulfate crystal whiskers then, stirred restir 30 minutes 30 minutes ultrasonic 10 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of calcium sulfate crystal whiskers that obtain surface-treated down after dry 20 hours in vacuum drying oven.
3. preparation method according to claim 2 is characterized in that, the said properties-correcting agent that anhydrous calciumsulphate or calcium sulfate crystal whiskers adopted through surface-treated also comprises a kind of in rhamnolipid or the lipopeptid or more than one.
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| CN102212204B (en) * | 2011-05-16 | 2013-01-16 | 刘立文 | Modified anhydrous calcium sulfate and preparation method thereof |
| CN102634847B (en) * | 2012-04-25 | 2015-04-22 | 昆明理工大学 | Method for surface modification of calcium sulfate crystal whisker |
| CN103352396B (en) * | 2013-06-09 | 2015-10-28 | 华东理工大学 | A kind of method being prepared crystal whisker of gypsum by the modification of organic/inorganic compound coating |
| CN103319866B (en) * | 2013-07-16 | 2015-12-23 | 暨南大学 | Magnesia crystal whisker/biodegradable polyester composite material and its preparation method and application |
| CN105820522B (en) * | 2016-04-01 | 2017-12-26 | 安徽理工大学 | A kind of calcium sulfate crystal whiskers activeness and quietness lactic acid composite material and preparation method thereof |
| CN108373585A (en) * | 2018-03-05 | 2018-08-07 | 湖北民族学院 | α-half-H 2 O calcium sulphate/aliphatic poly resin composite material and preparation method thereof |
| CN108721702B (en) * | 2018-06-29 | 2021-06-29 | 江西理工大学 | A kind of preparation method of magnesium/L-polylactic acid composite bone scaffold |
| CN112675365A (en) * | 2020-11-19 | 2021-04-20 | 宁波宝亭生物科技有限公司 | Preparation method of high-strength absorbable bone nail |
| CN115742478B (en) * | 2022-11-17 | 2025-03-14 | 东华大学 | A rapid prototyping method for fabric-reinforced thermoplastic composite materials |
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