CN106433056A - 3D printing biological material as well as preparation method and printing method thereof - Google Patents

3D printing biological material as well as preparation method and printing method thereof Download PDF

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Publication number
CN106433056A
CN106433056A CN201610910363.8A CN201610910363A CN106433056A CN 106433056 A CN106433056 A CN 106433056A CN 201610910363 A CN201610910363 A CN 201610910363A CN 106433056 A CN106433056 A CN 106433056A
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China
Prior art keywords
bata
tricalcium phosphate
printing
preparation
poly
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CN201610910363.8A
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Chinese (zh)
Inventor
张东锋
赵小文
赖文
苏冬冬
吴小丽
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Shenzhen Aike Cellon Polytron Technologies Inc
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Shenzhen Aike Cellon Polytron Technologies Inc
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Priority to CN201610910363.8A priority Critical patent/CN106433056A/en
Publication of CN106433056A publication Critical patent/CN106433056A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/325—Calcium, strontium or barium phosphate

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a 3D printing biological material as well as a preparation method and a printing method thereof. Raw materials for preparing the 3D printing biological material mainly comprise the following components in percentage by weight: 45-95% of beta-tricalcium phosphate and 5-55% of ooly-DL-lactide, wherein the sum of mass percentages of the two raw materials is less than or equal to 100%. By adopting the 3D printing biological material disclosed by the invention, normal-temperature printing can be achieved, the probability that a printing nozzle is blocked can be reduced, the defects that a single-beta-tricalcium phosphate material is high in brittleness can be solved, the toughness of the material can be improved, the degradation property of the material is improved due to addition of polylactic acid, a complex three-dimensional structure can be relatively well printed, and the application range of the 3D printing material can be widened.

Description

A kind of 3D prints biomaterial and preparation method thereof, Method of printing
Technical field
The present invention relates to field of compound material, particularly relate to a kind of 3D and print biomaterial and preparation method thereof, printing side Method.
Background technology
3D printing technique is a kind of special printing technique, and it is based on the spatial data of model, with metal or powder Etc. can jointing material, be stacked up by printing layer by layer, final " printing " goes out the three-dimensional model of ratio the same with model in computer. 3D printing technique comes across the end of the eighties in last century the earliest, starts the gradually ripe and rapid fashionable whole world after 2010, and Also because it facilitates the characteristic of trend to be welcome by consumers in general rapidly after entrance Chinese market.From common cartoon character The model such as thing, sand table or the art work, to printing the vehicles such as automobile, aircraft, print even with human body cell normally Liver organization, the figure that 3D prints occurs in our conceivable place any.
3D printing consumables as the important component part of 3D printing technique, affect the shaping speed of prototype, precision and physics, Chemical property, directly influences secondary application and the selection to moulding process equipment for the user of prototype.Commonly use in the market 3D printing consumables is mainly PLA (PLA), ABS (acrylonitrile one butadiene one styrene copolymer), PETG (gather to benzene Dioctyl phthalate ethylene glycol vinegar-1,4 one cyclohexanedimethanol vinegar) etc..As CN 104987680A discloses a kind of height printing for 3D Intensity height heat-proof polylactic acid material, including the component of following mass parts：PLLA resin 100 parts, inorganic filler 1-20 part, Polybasic carboxylic acid slaine 0.01-5 part, amides compound 0.1-5 part, plasticizer 0.1-5 part, antioxidant 0.1-1 part and anti- Hydrolytic reagent 0.1-2 part；The weight average molecular weight of described PLLA resin is 100000-400000；Described hydrolysis-resisting agent is poly- At least one or two in carbodiimide compound, single carbodiimide compound, the compound with active group epoxy radicals Plant use mixed above；Described inorganic filler is nano silicon, talcum powder, calcium sulfate crystal whiskers, the one in mica or extremely Few two kinds of mixtures being formed, a diameter of 0.05-5 μm of described inorganic filler.
But PLA toughness is poor, lack the shortcomings such as flexibility and elasticity, poor heat resistance limits PLA as 3D printing consumables Utilization further.
Content of the invention
For overcoming defect present in prior art, an object of the present invention is to provide a kind of 3D and prints biomaterial. The material of the present invention has excellent biocompatibility and a degradability, and can be smooth carry out 3D printing, structure is many The organization bracket of sample, can be advantageously applied in 3D printing.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of 3D prints biomaterial, and raw materials by weight mainly contains following components：
Bata-tricalcium phosphate (β-TCP) 45-95%, for example, the 47%th, the 51%th, the 56%th, the 59%th, the 63%th, the 67%th, the 70%th, 74%th, the 78%th, the 81%th, the 84%th, the 88%th, 93% etc., poly-dl-lactide (PDLLA) 5-55%, for example, the 8%th, the 12%th, 16%th, the 19%th, the 22%th, the 24%th, the 29%th, the 33%th, the 37%th, the 42%th, the 47%th, the 51%th, 54% etc., the quality hundred of above two raw material Proportion by subtraction sum≤100%.
As preferably, raw materials by weight mainly contains following components：Bata-tricalcium phosphate (β-TCP) 60-90%, outward PDLLA (PDLLA) 15-45%, chloroform (chloroform, CHCl3) 7%-28%, the percent mass of above-mentioned three kinds of raw materials Than sum≤100%.
The material that the present invention provides can print at normal temperature, and not high for the environmental requirement printing, composite has simultaneously Preferable mechanical property and biocompatibility.The material that the present invention provides can be used for bone defect healing, pharmaceutical carrier, basis doctor Learn the aspects such as research.
The material that the present invention provides both had solved the transportation problem of composite, maintained again PDLLA property at normal temperatures Can, expand β-TCP composite and print the range of application of industry at 3D.
An object of the present invention also resides in the preparation method providing biomaterial of the present invention, including walk as follows Suddenly：
(1) poly-dl-lactide is joined the CHCl of bata-tricalcium phosphate3Suspension mixes；
(2) heating of step (1) gained mixed liquor is made CHCl3Rapid evaporation i.e. obtains described biomaterial.
As preferably, in step (1), bata-tricalcium phosphate and the mass ratio of poly-dl-lactide are 0.5-20:1, for example, 0.8:1、1.3:1、1.8:1、2.5:1、4:1、6:1、8:1、11:1、14:1、17:1 etc., preferably 1.5～9:1.
As preferably, the CHCl of bata-tricalcium phosphate in step (1)3In suspension the mass concentration of bata-tricalcium phosphate be 2～ 32%, for example, the 4%th, the 8%th, the 13%th, the 16%th, the 19%th, the 22%th, the 24%th, the 28%th, 31% etc..
As preferably, the CHCl of bata-tricalcium phosphate in step (1)3The compound method of suspension is：Bata-tricalcium phosphate is added Enter in chloroform, at 18～30 DEG C, for example, 20 DEG C, 23 DEG C, 26 DEG C, the lower stirring mixing such as 29 DEG C.
Preferably, described stirring uses constant temperature blender with magnetic force to carry out.
Preferably, described stirring mixing time be more than 5min, for example, 8min, 12min, 16min, 20min, 25min, 32min, 38min, 45min etc., preferably 10～30min.
Preferably, rotating speed during described stirring is 300～800rpm.
As preferably, poly-dl-lactide is joined by step (1) CHCl of bata-tricalcium phosphate3In suspension, mixing is logical Cross stirring to carry out.
Preferably, at 18～30 DEG C, for example, 20 DEG C, 23 DEG C, 26 DEG C, lower stirring more than the 30min such as 29 DEG C, for example, 38min、42min、46min、50min、55min、62min、68min、75min、90min、120min、150min、175min、 200min etc., preferably 60～180min, make poly-dl-lactide fully dissolve.
As preferably, continuing stirring in step (2) during heating, the time preferably stirred is more than 30min, for example, 38min、42min、46min、50min、55min、62min、68min、75min、90min、120min、150min、175min、 200min etc., more preferably 60～180min.
Preferably, the temperature of described heating is more than 40 DEG C, for example, 43 DEG C, 46 DEG C, 49 DEG C, 55 DEG C, 62 DEG C, 70 DEG C, 75 DEG C, 80 DEG C etc., preferably 40-80 DEG C, more preferably 60 DEG C.
As preferably, the preparation method of the present invention comprises the following steps：
(1) weighing mass ratio respectively is 9:1～6:The bata-tricalcium phosphate of 4 and poly-dl-lactide；
(2) join bata-tricalcium phosphate in chloroform, at 18～30 DEG C, be placed in constant temperature blender with magnetic force stirring Mixing 10～30min, speed of agitator is 300～800rpm；
(3) poly-dl-lactide is joined the CHCl of above-mentioned bata-tricalcium phosphate3In suspension, continue at 18～30 DEG C Magnetic agitation 60～180min, makes poly-dl-lactide fully dissolve；
(4) constant temperature blender with magnetic force temperature is adjusted to 40-80 DEG C, continues magnetic agitation 60～180min, make CHCl3Hurry up Speed is evaporated and is i.e. obtained described biomaterial.
During use put into the β-TCP/PLGA composite mortar of gained in needle tubing, add syringe needle, be placed in 3D printer by Can print according to the print routine setting.
The process using the material of the present invention to print is as follows：
(1) opening operation software, open printing machine, connect computer；
(2) printed material is loaded onto printer, and is installed printhead by open printing machine；
(3) on software, printer model is imported；
(4) adjust print platform, make printer be in printable state；
(5) print parameters is adjusted；
(6) click on start button, start to print.
Preferably, described printhead bore is 160 μm-600 μm.
Preferably, parameter during described printing is：Speed is 2-15m/min, preferably 3.36-14.4m/min, and pressure is 30-80psi.
The biomaterial of the present invention has normal temperature and prints, and reduces the blocking probability of printing head, improves single β-phosphoric acid The big shortcoming of the fragility of three calcium materials, improves the toughness of material, and the addition of PLA improves the degradation property of material, can Preferably print the three-dimensional structure of complexity, expand the range of application of 3D printed material.Additionally, the biological material that the present invention provides Material has excellent biocompatibility and a degradability, and can be smooth carry out 3D printing, the diversified tissue of structure Support, can be advantageously applied in 3D printing.
Detailed description of the invention
For the present invention is better described, it is simple to understand technical scheme, the present invention's is typical but non-limiting Embodiment is as follows：
Embodiment 1
A kind of 3D prints biomaterial, and raw materials by weight contains following components：
Bata-tricalcium phosphate 90%
Poly-dl-lactide 10%
It is prepared via a method which：
(1) bata-tricalcium phosphate that quality is 9g, 1g and poly-dl-lactide are weighed respectively；
(2) bata-tricalcium phosphate is joined in the chloroform of 60mL, be placed in constant temperature blender with magnetic force at 30 DEG C and stir Mixing mixing 10min, speed of agitator is 300rpm；
(3) poly-dl-lactide is joined the CHCl of above-mentioned bata-tricalcium phosphate3In suspension, at 18 DEG C, continue magnetic force Stirring 180min, makes poly-dl-lactide fully dissolve；
(4) constant temperature blender with magnetic force temperature is adjusted to 60 DEG C, continues magnetic agitation 180min, make CHCl3Rapid evaporation Obtain described biomaterial.
Embodiment 2
A kind of 3D prints biomaterial, and raw materials by weight contains following components：
Bata-tricalcium phosphate 45%
Poly-dl-lactide 55%
It is prepared via a method which：
(1) bata-tricalcium phosphate that quality is 4.5g, 5.5g and poly-dl-lactide are weighed respectively；
(2) bata-tricalcium phosphate is joined in the chloroform of 40mL, be placed in constant temperature blender with magnetic force at 18 DEG C and stir Mixing mixing 30min, speed of agitator is 800rpm；
(3) poly-dl-lactide is joined the CHCl of above-mentioned bata-tricalcium phosphate3In suspension, at 30 DEG C, continue magnetic force Stirring 60min, makes poly-dl-lactide fully dissolve；
(4) constant temperature blender with magnetic force temperature is adjusted to 40 DEG C, continues magnetic agitation 40min, make CHCl3Rapid evaporation is Biomaterial described in.
Embodiment 3
A kind of 3D prints biomaterial, and raw materials by weight mainly contains following components：
Bata-tricalcium phosphate 40%
Poly-dl-lactide 60%
It is prepared via a method which：
(1) bata-tricalcium phosphate that quality is 4.0g, 6.0g and poly-dl-lactide are weighed respectively；
(2) bata-tricalcium phosphate is joined in the chloroform of 60mL, be placed in constant temperature blender with magnetic force at 20 DEG C and stir Mixing mixing 5min, speed of agitator is 500rpm；
(3) poly-dl-lactide is joined the CHCl of above-mentioned bata-tricalcium phosphate3In suspension, at 25 DEG C, continue magnetic force Stirring 30min, makes poly-dl-lactide fully dissolve；
(4) constant temperature blender with magnetic force temperature is adjusted to 70 DEG C, continues magnetic agitation 100min, make CHCl3Rapid evaporation Obtain described biomaterial.
Embodiment 4
A kind of 3D prints biomaterial, and raw materials by weight contains following components：
Bata-tricalcium phosphate 70%
Poly-dl-lactide 30%
It is prepared via a method which：
(1) bata-tricalcium phosphate that quality is 7g, 3g and poly-dl-lactide are weighed respectively；
(2) bata-tricalcium phosphate is joined in the chloroform of 60mL, be placed in constant temperature blender with magnetic force at 25 DEG C and stir Mixing mixing 20min, speed of agitator is 400rpm；
(3) poly-dl-lactide is joined the CHCl of above-mentioned bata-tricalcium phosphate3In suspension, at 25 DEG C, continue magnetic force Stirring 120min, makes poly-dl-lactide fully dissolve；
(4) constant temperature blender with magnetic force temperature is adjusted to 65 DEG C, continues magnetic agitation 120min, make CHCl3Rapid evaporation Obtain described biomaterial.
Comparative example 1
Weigh bata-tricalcium phosphate 2.5g, poly-dl-lactide 7.5g, material is prepared as sample according to the method for embodiment 1 Product, carry out performance test.
Table 1 below is embodiment 1-4 and comparative example 1 resulting materials performance parameter：
Table 1
From table 1 it follows that the material that the embodiment of the present invention prepares is compared to not prepared material within the scope of the present invention Material printing effect is more preferable, and mechanical property during printing is more excellent.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office It is limited to above-mentioned method detailed, i.e. do not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of each raw material to product of the present invention is replaced and auxiliary element Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (10)

1. a 3D prints biomaterial, it is characterised in that raw materials by weight mainly contains following components：β-tricresyl phosphate Ca45-95%, poly-dl-lactide 5-55%, mass percent sum≤100% of above two raw material.
2. biomaterial according to claim 1, it is characterised in that raw materials by weight mainly contains following group Point：Bata-tricalcium phosphate 60-90%, poly-dl-lactide 10-40%, mass percent sum≤100% of above two raw material.
3. the preparation method of biomaterial according to claim 1, comprises the steps：
(1) poly-dl-lactide is joined in the chloroform suspension of bata-tricalcium phosphate and mix；
(2) chloroform rapid evaporation is made i.e. to obtain described biomaterial the heating of step (1) gained mixed liquor.
4. preparation method according to claim 3, it is characterised in that in step (1), bata-tricalcium phosphate is poly-with racemic newborn The mass ratio of acid is 0.5-20:1, preferably 1.5～9:1.
5. the preparation method according to claim 3 or 4, it is characterised in that the chloroform of bata-tricalcium phosphate in step (1) In suspension, the mass concentration of bata-tricalcium phosphate is 2～32%.
6. the preparation method according to any one of claim 3-5, it is characterised in that in step (1) bata-tricalcium phosphate three The compound method of chloromethanes suspension is：Bata-tricalcium phosphate is joined in chloroform, stirring mixing at 18～30 DEG C.
7. preparation method according to claim 6, it is characterised in that described stirring uses constant temperature blender with magnetic force to carry out；
Preferably, the time of described stirring mixing is more than 5min, preferably 10～30min；
Preferably, rotating speed during described stirring is 300～800rpm.
8. the preparation method according to any one of claim 3-7, it is characterised in that by poly-dl-lactide in step (1) The chloroform suspension joining bata-tricalcium phosphate mixes and is carried out by stirring；
Preferably, at 18～30 DEG C, more than 30min, preferably 60～180min are stirred.
9. the preparation method according to any one of claim 3-8, it is characterised in that continue stirring in step (2) during heating, The time preferably stirred is more than 30min, more preferably 60～180min；
Preferably, the temperature of described heating is more than 40 DEG C, preferably 60 DEG C.
10. the process using the material described in claim 1 or 2 to print is as follows：
(1) opening operation software, open printing machine, connect computer；
(2) printed material is loaded onto printer, and is installed printhead by open printing machine；
(3) on software, printer model is imported；
(4) adjust print platform, make printer be in printable state；
(5) print parameters is adjusted；
(6) click on start button, start to print；
Preferably, described printhead bore is 160 μm-600 μm；
Preferably, parameter during described printing is：Speed is 2-15m/min, preferably 3.36-14.4m/min, and pressure is 30- 80psi.
CN201610910363.8A 2016-10-19 2016-10-19 3D printing biological material as well as preparation method and printing method thereof Pending CN106433056A (en)

Priority Applications (1)

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Application Number Priority Date Filing Date Title
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1546180A (en) * 2003-12-08 2004-11-17 华中科技大学 Degradable composite support frame and its preparing process
CN105770988A (en) * 2016-04-20 2016-07-20 清华大学深圳研究生院 Bone repairing biological ceramic material based on 3D printing and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1546180A (en) * 2003-12-08 2004-11-17 华中科技大学 Degradable composite support frame and its preparing process
CN105770988A (en) * 2016-04-20 2016-07-20 清华大学深圳研究生院 Bone repairing biological ceramic material based on 3D printing and preparation method thereof

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Application publication date: 20170222