CN108187134A - A kind of preparation method of the in-situ modified calcium phosphate bone cement 3D printing material of medical polylactic acid - Google Patents
A kind of preparation method of the in-situ modified calcium phosphate bone cement 3D printing material of medical polylactic acid Download PDFInfo
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- CN108187134A CN108187134A CN201810054143.9A CN201810054143A CN108187134A CN 108187134 A CN108187134 A CN 108187134A CN 201810054143 A CN201810054143 A CN 201810054143A CN 108187134 A CN108187134 A CN 108187134A
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- Prior art keywords
- calcium phosphate
- printing material
- parts
- polylactic acid
- medical
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000010146 3D printing Methods 0.000 title claims abstract description 57
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 51
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 50
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 42
- 239000002639 bone cement Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000001506 calcium phosphate Substances 0.000 claims description 41
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 35
- 235000011010 calcium phosphates Nutrition 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000010792 warming Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 17
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 6
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 6
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 claims description 4
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- JBPBWEKERUNUQY-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)Cl(C)(C)C Chemical compound C(CCCCCCCCCCCCCCCCC)Cl(C)(C)C JBPBWEKERUNUQY-UHFFFAOYSA-N 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract 1
- 239000000341 volatile oil Substances 0.000 abstract 1
- 210000000988 bone and bone Anatomy 0.000 description 18
- -1 isooctyl Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical group [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 230000000278 osteoconductive effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 208000020084 Bone disease Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000033115 angiogenesis Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001900 immune effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000014786 phosphorus Nutrition 0.000 description 1
- 230000002980 postoperative effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical class 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Veterinary Medicine (AREA)
- Dermatology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Medical Uses (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to 3D printing field of material technology, and in particular to a kind of preparation method of the medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid.The preparation method of the medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid includes：Step 1: prepare organic lithium soapstone；Step 2: prepare organic lithium soapstone modified phosphate calcium powder；Step 3: prepare 3D printing material.This method is not only of low cost, but also simple for process, while purification efficiency and agilawood essential oil purity are high.The medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid made from the preparation method of the medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid has the advantages that excellent mechanical strength, mechanical property and flexible.Moreover, the preparation method of the application has very strong practicability, industrial prospect is extremely bright.
Description
Technical field
The present invention relates to 3D printing field of material technology, and in particular to a kind of medical in-situ modified calcium phosphate bone water of polylactic acid
The preparation method of mud 3D printing material.
Background technology
In the world, bone defect patient is caused to increase year by year due to astogeny, wound, bone disease etc. are numerous.
Therefore, the demand of bone impairment renovation material is increasingly increased.Traditional Bone Defect Repari mode is mainly the shifting of autologous bone and allograph bone
It plants, but because there are problems that immunological rejection, supply source are limited and need second operation etc. is many to be difficult to overcome, traditional bone moves
Plant method gradually decreases, and is at the same time increased sharply using artificial bone renovating material.In artificial medical bone organization material field
In, the calcium phosphate of active component based on calcium phosphate material (mainly indefiniteness calcium phosphate, tricalcium phosphate, tetracalcium phosphate etc.)
Bone cement (Calcium phosphate cement, CPC) is due to good biocompatibility, osteoconductive and skeletonization
The active degrading activity mutually coordinated the superior functions such as can voluntarily cure and be widely used in numerous clinical applications.
The major advantage of Medical C PC：(1) CPC microballoons not only can arbitrarily fill at irregular bone defect, but also accumulate
Interconnected three dimensional pore structures can be formed in filling process, be conducive to bone tissue grow into and angiogenesis.(2) CPC has
There are good biocompatibility and osteoconductive, therefore the postoperative probability that ancillary drug is needed to be treated subtracts significantly
It is few.Just because of this, using CPC as 3D printing material, bone tissue material is prepared by 3D printing technique, by flourishing state
Family is widely used in the fields industry such as clinical bone replacement and reparation.
But CPC consolidates at present there is also many clinical practice problems wherein most basic key technology difficulty is exactly CPC
The mechanical strength and mechanical property of bone tissue after change are simultaneously non-specifically satisfactory.It searches to the bottom reason, is primarily due to CPC and consolidates
The brittleness of bone tissue after change is big, and internal flexibility is poor, and after being acted on by very big external force, the internal stress of generation is difficult to comparatively fast
It guides and dissipates, the bone tissue after CPC curings is caused to be unable to bear very big external force and is acted on and recurring structure destruction.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of in-situ modified calcium phosphate bone of medical polylactic acid
The preparation method of cement 3D printing material, the medical in-situ modified calcium phosphate bone cement 3D printing of polylactic acid made from the preparation method
Material has the advantages that excellent mechanical strength, mechanical property and flexible.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of preparation method of the in-situ modified calcium phosphate bone cement 3D printing material of medical polylactic acid is provided, it includes following
Step：
Step 1: prepare organic lithium soapstone：Hectorite is scattered in the water of certain temperature first, while by quaternary ammonium salt
It is scattered in the water of certain temperature, respectively obtains hot solution；Then two kinds of hot solutions are mixed, and is warming up under certain temperature and stirs
Mix reaction certain time；Then it washed, filtered, and dried under certain temperature to constant weight, obtain organic lithium soapstone；
Step 2: prepare organic lithium soapstone modified phosphate calcium powder：By organic lithium soapstone made from step 1 and calcium phosphate
Powder is added in absolute ethyl alcohol, is warming up to certain temperature and held for some time, is then washed, filtered, and in a constant temperature
Degree is lower dry to constant weight, obtains organic lithium soapstone modified phosphate calcium powder；
Step 3: prepare 3D printing material：By organic lithium soapstone modified phosphate calcium powder, glycolide, lactide, isooctyl acid
Stannous is uniformly mixed in organic solvent, then is passed through in pyroreaction kettle and is warming up to certain temperature again, insulation reaction certain time
Stop reaction and cooling discharge afterwards；Then it filters, obtained filter cake is added in absolute ethyl alcohol and is stirred certain time,
It washed, filtered again, finally dried at a certain temperature to constant weight, and be ground to certain particle size, obtained described medical poly-
The in-situ modified calcium phosphate bone cement 3D printing material of lactic acid.
In above-mentioned technical proposal, in the step 1, the quaternary ammonium salt is Cetyltrimethylammonium bromide, octadecyl
One or both of trimethyl ammonium chloride, cetyl trimethylammonium bromide or hexadecyltrimethylammonium chloride press arbitrary ratio
The composition of example.
In above-mentioned technical proposal, in the step 2, the calcium phosphate powder is indefiniteness calcium phosphate, tricalcium phosphate or phosphorus
One kind or arbitrary two or more compositions in any proportion in sour four calcium.
In above-mentioned technical proposal, in the step 3, the organic solvent is one kind in chloroform, tetrahydrofuran or pyridine
Or two or more combinations in any proportion.
In above-mentioned technical proposal, in the step 1, organic lithium soapstone is prepared：100 parts of hectorites are scattered in 60 first
In~85 DEG C of 300~500 parts of water, while 10~30 parts of quaternary ammonium salts are also scattered in 60~85 DEG C of 300~500 parts of water
In, respectively obtain hot solution；Then two kinds of hot solutions are mixed, and is warming up at 90~95 DEG C and is stirred to react 1~2h；Then into
Row washing, filtering, and dried at 60~105 DEG C to constant weight, obtain organic lithium soapstone.
In above-mentioned technical proposal, in the step 2, organic lithium soapstone modified phosphate calcium powder is prepared：Step 1 is made
5~15 parts of organic lithium soapstones and 40~100 parts of calcium phosphate powders be added in 300~500 parts of absolute ethyl alcohols, be warming up to 50~80
DEG C and keep the temperature 5~8h, then washed, filtered, and at 100~130 DEG C dry to constant weight, obtain organic lithium soapstone and change
Property calcium phosphate powder.
In above-mentioned technical proposal, in the step 3,3D printing material is prepared：100~200 parts of organic lithium soapstones are modified
Calcium phosphate powder, 20~50 parts of glycolides, 20~50 parts of lactides, 1~5 part of stannous iso caprylate are organic molten at 500~1000 parts
It is uniformly mixed in agent, then is passed through in pyroreaction kettle and is warming up to 150~180 DEG C again, stop reaction simultaneously after 10~20h of insulation reaction
Cooling discharge；Then it filters, obtained filter cake is added in 300~500 parts of absolute ethyl alcohols and is stirred 1~3h, then into
Row washing, filtering, are finally dried at 50~80 DEG C to constant weight, and are ground to granularity as 2000~10000 mesh, are obtained described
The medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid.
In above-mentioned technical proposal, the water in the step 1 is pure water.
Compared with prior art, advantageous effect is the present invention：
(1) the preparation side of a kind of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid provided by the invention
Method, the preparation method step 1 are to prepare quaternary ammonium salt-modified organic lithium soapstone.Why organic modification is carried out, be to improve
The compatibility of calcium phosphate material and polylactic acid.Organic lithium soapstone and calcium phosphate carry out back flow reaction, main mesh in absolute ethyl alcohol
Be that organic lithium soapstone platelet is allowed fully to coat calcium phosphate powder particles surface.In absolute ethyl alcohol, organic lithium soapstone stratiform knot
Structure expands, is disintegrated, delaminates, so as to generate countless nano lamellar platelets.Absolute ethyl alcohol after filtering can pass through the side such as rectifying
Formula recycles.By characterization methods such as infrared, XRD, SEM, organic lithium soapstone nano lamellar platelet sub-fraction first is found
In the pore structure on calcium phosphate granules surface, secondly remaining major part is superimposed by modes such as Molecular Adsorption power is deposited in for absorption
Calcium phosphate granules surface, so as to form one layer of layer that organises for having certain hydrophobic performance.Simple unmodified hectorite also may be used
Calcium phosphate powder particles surface is adsorbed and be wrapped up in absolute ethyl alcohol, but calcium phosphate granules and polylactic acid phase at this time
Capacitive is poor, can not equably participate in poly lactic acid polymerized reaction on a molecular scale.Then by organic lithium soapstone modified phosphate calcium
Powder, glycolide, lactide, catalyst stannous iso caprylate are uniformly mixed in the organic solvents such as chloroform, then are passed through pyroreaction
Certain temperature, insulation reaction certain time, generation and the mixed uniformly polylactic acid of calcium phosphate molecular level are warming up in kettle again.But
This when also remains some unreacted monomers and catalyst, therefore adds in the absolute ethyl alcohol of sufficient amount, removes these completely
Impurity.Obviously, organic solvent and absolute ethyl alcohol here can also be recycled by modes such as rectifying.Obtained material
Bulk composition is the CPC of the active constituent based on calcium phosphate, and polylactic acid network reaches polylactic acid and CPC through CPC particles
In molecular level hydridization.Certain particle size is ground to, the as medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid
Material.
(2) the preparation side of a kind of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid provided by the invention
Method, the in-situ modified calcium phosphate bone cement 3D printing material of obtained medical polylactic acid, on the one hand remains CPC and was originally had
Excellent mechanical strength and mechanical property, on the other hand have excellent flexibility by introducing polylactic acid, greatly change
It has been apt to the big essence shortcoming of simple CPC material fragilities.
(3) the preparation side of a kind of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid provided by the invention
Method, the preparation method by organic lithium soapstone package so that polylactic acid is uniformly mixed with CPC on molecular level scale,
Effect the modes such as mixes considerably beyond polylactic acid with the physical mechanical of CPC.
(4) the preparation side of a kind of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid provided by the invention
Method, due to introducing polylactic acid ingredient, the biocompatibility of modified CPC and it is biodegradable the advantages that it is more prominent
Go out.Therefore, the preparation method of the application has very strong practicability, and industrial prospect is extremely bright.
(5) the preparation side of a kind of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid provided by the invention
Method, the preparation method utilize in-situ modified technique, and CPC participates in polylactic acid (PLA) and polymerize preparation reaction process, dividing so as to be made
The PLA modified phosphate calcium bones of hybridization compounding are carried out on sub- horizontal scale, and as medical 3D printing material.
Specific embodiment
In order to which technical problem solved by the invention, technical solution and advantageous effect is more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
Embodiment 1.
A kind of preparation method of the in-situ modified calcium phosphate bone cement 3D printing material of medical polylactic acid, it includes following step
Suddenly：
Step 1: prepare organic lithium soapstone：100 parts of hectorites are scattered in 70 DEG C of 400 parts of water first, while by 20
Part quaternary ammonium salt is also scattered in 70 DEG C of 400 parts of water, respectively obtains hot solution；Then two kinds of hot solutions are mixed, and heated up
1.5h is stirred to react to 93 DEG C；Then it washed, filtered, and dried at 80 DEG C to constant weight, obtain organic lithium soapstone；
In the present embodiment, quaternary ammonium salt is Cetyltrimethylammonium bromide；
Wherein, the water in step 1 is pure water；
Step 2: prepare organic lithium soapstone modified phosphate calcium powder：By 10 parts of organic lithium soapstones and 80 made from step 1
Part calcium phosphate powder is added in 400 parts of absolute ethyl alcohols, is warming up to 65 DEG C and is kept the temperature 7h, is then washed, filtered, and in 125
It is dried at DEG C to constant weight, obtains organic lithium soapstone modified phosphate calcium powder；
In the present embodiment, calcium phosphate powder is indefiniteness calcium phosphate；
Step 3: prepare 3D printing material：By 150 parts of organic lithium soapstone modified phosphate calcium powders, 35 parts of glycolides, 35 parts
Lactide, 3 parts of stannous iso caprylates are uniformly mixed in 800 parts of organic solvents, then are passed through in pyroreaction kettle and are warming up to 160 again
DEG C, stop reaction and cooling discharge after insulation reaction 15h；Then it filters, obtained filter cake is added in 400 parts of absolute ethyl alcohols
And 2h is stirred, then washed, filtered, it finally dries to constant weight, and be ground to granularity as 5000 mesh, that is, makes at 75 DEG C
Obtain the medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid.
In the present embodiment, organic solvent is chloroform.
Embodiment 2.
A kind of preparation method of the in-situ modified calcium phosphate bone cement 3D printing material of medical polylactic acid, it includes following step
Suddenly：
Step 1: prepare organic lithium soapstone：100 parts of hectorites are scattered in 60 DEG C of 300 parts of water first, while by 10
Part quaternary ammonium salt is also scattered in 60 DEG C of 300 parts of water, respectively obtains hot solution；Then two kinds of hot solutions are mixed, and heated up
1h is stirred to react to 90 DEG C；Then it washed, filtered, and dried at 60 DEG C to constant weight, obtain organic lithium soapstone；
In the present embodiment, quaternary ammonium salt is octadecyltrimethylammonium chloride；
Wherein, the water in step 1 is pure water；
Step 2: prepare organic lithium soapstone modified phosphate calcium powder：By 5 parts of organic lithium soapstones made from step 1 and 40 parts
Calcium phosphate powder is added in 300 parts of absolute ethyl alcohols, is warming up to 50 DEG C and is kept the temperature 5h, then washed, filtered, and in 100 DEG C
Lower drying obtains organic lithium soapstone modified phosphate calcium powder to constant weight；
In the present embodiment, calcium phosphate powder is tricalcium phosphate；
Step 3: prepare 3D printing material：By 100 parts of organic lithium soapstone modified phosphate calcium powders, 20 parts of glycolides, 20 parts
Lactide, 1 part of stannous iso caprylate are uniformly mixed in 500 parts of organic solvents, then are passed through in pyroreaction kettle and are warming up to 150 again
DEG C, stop reaction and cooling discharge after insulation reaction 10h；Then it filters, obtained filter cake is added in 300 parts of absolute ethyl alcohols
And 1h is stirred, then washed, filtered, it finally dries to constant weight, and be ground to granularity as 2000 mesh, that is, makes at 50 DEG C
Obtain the medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid.
In the present embodiment, organic solvent is tetrahydrofuran.
Embodiment 3.
A kind of preparation method of the in-situ modified calcium phosphate bone cement 3D printing material of medical polylactic acid, it includes following step
Suddenly：
Step 1: prepare organic lithium soapstone：100 parts of hectorites are scattered in 85 DEG C of 500 parts of water first, while by 30
Part quaternary ammonium salt is also scattered in 85 DEG C of 500 parts of water, respectively obtains hot solution；Then two kinds of hot solutions are mixed, and heated up
2h is stirred to react to 95 DEG C；Then it washed, filtered, and dried at 105 DEG C to constant weight, obtain organic lithium soapstone；
In the present embodiment, quaternary ammonium salt is octadecyltrimethylammonium chloride；
Wherein, the water in step 1 is pure water；
Step 2: prepare organic lithium soapstone modified phosphate calcium powder：By 15 parts of organic lithium soapstones and 100 made from step 1
Part calcium phosphate powder is added in 500 parts of absolute ethyl alcohols, is warming up to 80 DEG C and is kept the temperature 8h, is then washed, filtered, and in 130
It is dried at DEG C to constant weight, obtains organic lithium soapstone modified phosphate calcium powder；
In the present embodiment, calcium phosphate powder is tetracalcium phosphate；
Step 3: prepare 3D printing material：By 200 parts of organic lithium soapstone modified phosphate calcium powders, 50 parts of glycolides, 50 parts
Lactide, 5 parts of stannous iso caprylates are uniformly mixed in 1000 parts of organic solvents, then are passed through in pyroreaction kettle and are warming up to 180 again
DEG C, stop reaction and cooling discharge after insulation reaction 20h；Then it filters, obtained filter cake is added in 500 parts of absolute ethyl alcohols
And 3h is stirred, then washed, filtered, it is finally dried at 80 DEG C to constant weight, and be ground to granularity as 10000 mesh, i.e.,
The medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid is made.
In the present embodiment, organic solvent is pyridine.
Embodiment 4.
A kind of preparation method of the in-situ modified calcium phosphate bone cement 3D printing material of medical polylactic acid, it includes following step
Suddenly：
Step 1: prepare organic lithium soapstone：100 parts of hectorites are scattered in 65 DEG C of 350 parts of water first, while by 15
Part quaternary ammonium salt is also scattered in 65 DEG C of 350 parts of water, respectively obtains hot solution；Then two kinds of hot solutions are mixed, and heated up
1.8h is stirred to react to 91 DEG C；Then it washed, filtered, and dried at 70 DEG C to constant weight, obtain organic lithium soapstone；
In the present embodiment, quaternary ammonium salt presses arbitrary ratio for cetyl trimethylammonium bromide and hexadecyltrimethylammonium chloride
The composition of example；
Wherein, the water in step 1 is pure water；
Step 2: prepare organic lithium soapstone modified phosphate calcium powder：By 7 parts of organic lithium soapstones made from step 1 and 50 parts
Calcium phosphate powder is added in 350 parts of absolute ethyl alcohols, is warming up to 60 DEG C and is kept the temperature 7h, then washed, filtered, and in 110 DEG C
Lower drying obtains organic lithium soapstone modified phosphate calcium powder to constant weight；
In the present embodiment, calcium phosphate powder is the composition of indefiniteness calcium phosphate and tricalcium phosphate in any proportion；
Step 3: prepare 3D printing material：By 180 parts of organic lithium soapstone modified phosphate calcium powders, 40 parts of glycolides, 40 parts
Lactide, 4 parts of stannous iso caprylates are uniformly mixed in 600 parts of organic solvents, then are passed through in pyroreaction kettle and are warming up to 160 again
DEG C, stop reaction and cooling discharge after insulation reaction 12h；Then it filters, obtained filter cake is added in 350 parts of absolute ethyl alcohols
And 1.5h is stirred, then washed, filtered, it is finally dried at 60 DEG C to constant weight, and be ground to granularity as 3000 mesh, i.e.,
The medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid is made.
In the present embodiment, organic solvent is the combination of chloroform and tetrahydrofuran in any proportion.
Embodiment 5.
A kind of preparation method of the in-situ modified calcium phosphate bone cement 3D printing material of medical polylactic acid, it includes following step
Suddenly：
Step 1: prepare organic lithium soapstone：100 parts of hectorites are scattered in 80 DEG C of 450 parts of water first, while by 25
Part quaternary ammonium salt is also scattered in 80 DEG C of 450 parts of water, respectively obtains hot solution；Then two kinds of hot solutions are mixed, and heated up
1.8h is stirred to react to 94 DEG C；Then it washed, filtered, and dried at 90 DEG C to constant weight, obtain organic lithium soapstone；
In the present embodiment, quaternary ammonium salt is octadecyltrimethylammonium chloride, cetyl trimethylammonium bromide and hexadecane
The composition of base trimethyl ammonium chloride in any proportion；
Wherein, the water in step 1 is pure water；
Step 2: prepare organic lithium soapstone modified phosphate calcium powder：By 12 parts of organic lithium soapstones and 90 made from step 1
Part calcium phosphate powder is added in 450 parts of absolute ethyl alcohols, is warming up to 70 DEG C and is kept the temperature 7h, is then washed, filtered, and in 120
It is dried at DEG C to constant weight, obtains organic lithium soapstone modified phosphate calcium powder；
In the present embodiment, calcium phosphate powder is the group of indefiniteness calcium phosphate, tricalcium phosphate and tetracalcium phosphate in any proportion
Close object；
Step 3: prepare 3D printing material：By 180 parts of organic lithium soapstone modified phosphate calcium powders, 40 parts of glycolides, 45 parts
Lactide, 2 parts of stannous iso caprylates are uniformly mixed in 900 parts of organic solvents, then are passed through in pyroreaction kettle and are warming up to 170 again
DEG C, stop reaction and cooling discharge after insulation reaction 18h；Then it filters, obtained filter cake is added in 450 parts of absolute ethyl alcohols
And 2.5h is stirred, then washed, filtered, it is finally dried at 70 DEG C to constant weight, and be ground to granularity as 9000 mesh, i.e.,
The medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid is made.
In the present embodiment, organic solvent is the combination of chloroform, tetrahydrofuran and pyridine in any proportion.
Experiment：
By the in-situ modified calcium phosphate bone cement 3D printing materials A~D of polylactic acid medical made from embodiment 1 to 4, it is external into
Similar commodity (the model of mouth：Jet-2A, Israel CollPlant biology 3D printing company produce) carry out various contrast tests, knot
Fruit is as shown in table 1 below.
Table 13D printed material performance comparison test results
| Test index | A | B | C | D | Jet-2A |
| Bending strength (MPa) | 1.2 | 1.5 | 1.5 | 1.6 | 0.9 |
| Compression strength (MPa) | 8.3 | 8.5 | 8.1 | 8.0 | 7.7 |
| Flexibility (mm) | 0.5 | 0.5 | 0.5 | 0.5 | 2 |
| Printing precision (mm) | 0.2 | 0.1 | 0.2 | 0.2 | 0.4 |
As shown in Table 1, the in-situ modified calcium phosphate bone cement 3D printing material of medical polylactic acid that prepared by the application has machine
The advantages of performance indicators such as tool intensity, mechanical property, flexibility are excellent, hence it is evident that be better than the property of the similar commodity of external import at present
Energy.Therefore, the preparation process industrial prospect of the application is bright, can create huge economic benefit.
The above embodiments are merely illustrative of the technical solutions of the present invention rather than limiting the scope of the invention, although
The present invention is explained in detail with reference to preferred embodiment, it will be understood by those of ordinary skill in the art that, it can be to this hair
Bright technical solution is modified or replaced equivalently, without departing from the spirit and scope of technical solution of the present invention.
Claims (8)
1. a kind of preparation method of the in-situ modified calcium phosphate bone cement 3D printing material of medical polylactic acid, it is characterised in that：It is wrapped
Include following steps：
Step 1: prepare organic lithium soapstone：Hectorite is scattered in the water of certain temperature first, while quaternary ammonium salt is also disperseed
In the water of certain temperature, hot solution is respectively obtained；Then two kinds of hot solutions are mixed, and is warming up under certain temperature and stirs instead
Answer certain time；Then it washed, filtered, and dried under certain temperature to constant weight, obtain organic lithium soapstone；
Step 2: prepare organic lithium soapstone modified phosphate calcium powder：By organic lithium soapstone made from step 1 and calcium phosphate powder
It is added in absolute ethyl alcohol, is warming up to certain temperature and held for some time, is then washed, filtered, and under certain temperature
Drying obtains organic lithium soapstone modified phosphate calcium powder to constant weight；
Step 3: prepare 3D printing material：By organic lithium soapstone modified phosphate calcium powder, glycolide, lactide, stannous iso caprylate
It is uniformly mixed in organic solvent, then is passed through in pyroreaction kettle and is warming up to certain temperature again, insulation reaction is stopped after a certain period of time
Only reaction and cooling discharge；Then it filters, obtained filter cake is added in absolute ethyl alcohol and is stirred certain time, then into
Row washing, filtering, finally dry to constant weight, and be ground to certain particle size, obtain the medical polylactic acid at a certain temperature
In-situ modified calcium phosphate bone cement 3D printing material.
2. a kind of preparation side of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid according to claim 1
Method, it is characterised in that：In the step 1, the quaternary ammonium salt is Cetyltrimethylammonium bromide, octadecyl trimethyl chlorine
Change the combination of one or both of ammonium, cetyl trimethylammonium bromide or hexadecyltrimethylammonium chloride in any proportion
Object.
3. a kind of preparation side of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid according to claim 1
Method, it is characterised in that：In the step 2, the calcium phosphate powder is in indefiniteness calcium phosphate, tricalcium phosphate or tetracalcium phosphate
One kind or arbitrary two or more compositions in any proportion.
4. a kind of preparation side of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid according to claim 1
Method, it is characterised in that：In the step 3, the organic solvent for one or both of chloroform, tetrahydrofuran or pyridine with
On combination in any proportion.
5. a kind of preparation side of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid according to claim 1
Method, it is characterised in that：In the step 1, organic lithium soapstone is prepared：100 parts of hectorites are scattered in 60~85 DEG C first
In 300~500 parts of water, while 10~30 parts of quaternary ammonium salts are also scattered in 60~85 DEG C of 300~500 parts of water, respectively
To hot solution；Then two kinds of hot solutions are mixed, and is warming up at 90~95 DEG C and is stirred to react 1~2h；Then it is washed, mistake
Filter, and dried at 60~105 DEG C to constant weight, obtain organic lithium soapstone.
6. a kind of preparation side of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid according to claim 1
Method, it is characterised in that：In the step 2, organic lithium soapstone modified phosphate calcium powder is prepared：By 5~15 parts made from step 1
Organic lithium soapstone and 40~100 parts of calcium phosphate powders are added in 300~500 parts of absolute ethyl alcohols, are warming up to 50~80 DEG C and heat preservation 5
Then~8h is washed, is filtered, and dried at 100~130 DEG C to constant weight, obtains organic lithium soapstone modified phosphate calcium
Powder.
7. a kind of preparation side of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid according to claim 1
Method, it is characterised in that：In the step 3,3D printing material is prepared：By 100~200 parts of organic lithium soapstone modified phosphate calcium powders
End, 20~50 parts of glycolides, 20~50 parts of lactides, 1~5 part of stannous iso caprylate mix in 500~1000 parts of organic solvents
Uniformly, it then is passed through in pyroreaction kettle and is warming up to 150~180 DEG C again, stop reacting after 10~20h of insulation reaction and cool down
Material；Then it filters, obtained filter cake is added in 300~500 parts of absolute ethyl alcohols and is stirred 1~3h, then washed,
Filtering is finally dried at 50~80 DEG C to constant weight, and is ground to granularity as 2000~10000 mesh, is obtained described medical poly-
The in-situ modified calcium phosphate bone cement 3D printing material of lactic acid.
8. a kind of preparation side of medical in-situ modified calcium phosphate bone cement 3D printing material of polylactic acid according to claim 1
Method, it is characterised in that：Water in the step 1 is pure water.
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| CN109721040A (en) * | 2019-03-07 | 2019-05-07 | 中山职业技术学院 | A kind of preparation method of high-performance biomedicine type alpha tricalcium phosphate |
| CN110075359A (en) * | 2019-03-26 | 2019-08-02 | 华南理工大学 | A kind of ultrasonic wave added prepares porous bone cement bracket and preparation method thereof |
| CN110368524A (en) * | 2019-07-30 | 2019-10-25 | 东南大学 | A kind of bioactivity bone repairing support and preparation method thereof |
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