CN106496977A - A kind of 3D printing poly-lactic acid material and preparation method thereof, Method of printing - Google Patents

A kind of 3D printing poly-lactic acid material and preparation method thereof, Method of printing Download PDF

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Publication number
CN106496977A
CN106496977A CN201610910906.6A CN201610910906A CN106496977A CN 106496977 A CN106496977 A CN 106496977A CN 201610910906 A CN201610910906 A CN 201610910906A CN 106496977 A CN106496977 A CN 106496977A
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China
Prior art keywords
poly
hydroxyapatite
printing
preparation
lactic acid
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CN201610910906.6A
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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 CN201610910906.6A priority Critical patent/CN106496977A/en
Publication of CN106496977A publication Critical patent/CN106496977A/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
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

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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

A kind of 3D printing poly-lactic acid material and preparation method thereof, Method of printing.The raw materials by weight for preparing the material mainly contains following components：Hydroxyapatite 35 90%, poly-dl-lactide 10 65%, mass percent sum≤100% of above two raw material.There is the poly-lactic acid material of the present invention room temperature to print, and reduces the probability of spray nozzle clogging, improves print performance so that poly-lactic acid material can carry out the structure of labyrinth, can better adapt to difference and demand.

Description

A kind of 3D printing poly-lactic acid material and preparation method thereof, Method of printing
Technical field
The present invention relates to field of compound material, more particularly to a kind of 3D printing poly-lactic acid material and preparation method thereof, print Method.
Background technology
3D printing technique is a kind of special printing technique, it 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 stereomodel of ratio as model in computer. 3D printing technique comes across the end of the eighties in last century earliest, starts the gradually ripe and fashionable whole world rapidly after 2010, and Also welcome by consumers in general because which facilitates the characteristic of trend rapidly after entering Chinese market.From common cartoon character The models such as thing, sand table or the art work, to the vehicles such as automobile, aircraft are printed, print normally even with human body cell Liver organization, the figure of 3D printing occur in any we be envisioned that where.
Important component part of the 3D printing consumptive material as 3D printing technique, the shaping speed of impact prototype, precision and physics, Chemical property, directly influences the selection of the secondary application and user of prototype to moulding process equipment.Commonly use in the market It is (poly- to benzene that 3D printing consumptive material is mainly PLA (polylactic acid), ABS (one butadiene of acrylonitrile, one styrene copolymer), PETG - 1,4 one cyclohexanedimethanol vinegar of dioctyl phthalate ethylene glycol vinegar) etc..As CN 104987680A disclose a kind of height for 3D printing The high heat-proof polylactic acid material of intensity, including the component of following mass parts：100 parts of Poly-L-lactic acid resin, inorganic filler 1-20 parts, Polybasic carboxylic acid slaine 0.01-5 parts, amides compound 0.1-5 parts, plasticizer 0.1-5 parts, antioxidant 0.1-1 parts and anti- Hydrolytic reagent 0.1-2 parts；The weight average molecular weight of the Poly-L-lactic acid resin is 100000-400000；The hydrolysis-resisting agent is poly- At least one or two in carbodiimide compound, single second carbide imine compound, the compound with active group epoxy radicals Plant use mixed above；The inorganic filler is nano silicon, Pulvis Talci, calcium sulfate crystal whiskers, one kind in Muscovitum or extremely The mixture of few two kinds of formation, a diameter of 0.05-5 μm of the inorganic filler.
But polylactic acid toughness is poor, it is flexible to lack and limits PLA as 3D printing consumptive material the shortcomings of elasticity, poor heat resistance Further use.
Content of the invention
For overcoming defect present in prior art, an object of the present invention to be to provide a kind of 3D printing polylactic acid material Material.The material of the present invention has excellent biocompatibility and degradability, and can carry out 3D printing, structure with smooth Diversified organization bracket, can be advantageously applied in polylactic acid 3D printing.
It is that the present invention is adopted the following technical scheme that up to above-mentioned purpose：
A kind of 3D printing poly-lactic acid material, raw materials by weight mainly contain following components：
Hydroxyapatite (HAp) 35-90%, for example, 37%, 42%, 47%, 51%, 56%, 59%, 63%, 67%, 70%th, 74%, 78%, 81%, 84%, 88% etc., poly-dl-lactide (PDLLA) 10-65%, for example, 12%, 16%, 19%th, 22%, 24%, 29%, 33%, 37%, 42%, 47%, 51%, 56%, 59%, 63% etc., above two raw material Mass percent sum≤100%.
Preferably, raw materials by weight mainly contains following components：Hydroxyapatite (HAp) 45-85%, disappears outward Rotation polylactic acid (PDLLA) 15-55%, mass percent sum≤100% of above two raw material.
The present invention provide material can print in room temperature, for printing environmental requirement not high, while composite has Preferable mechanical property and biocompatibility.The material that the present invention is provided can be used for bone defect healing, pharmaceutical carrier, basis doctor Learn the aspects such as research.
The material that the present invention is provided both had solved the use at normal temperatures of HAp composites, maintained PDLLA again in room temperature Under performance.
An object of the present invention also resides in the preparation method for providing poly-lactic acid material of the present invention, including following step Suddenly：
(1) poly-dl-lactide is added to the CHCl of hydroxyapatite3Mix in suspension；
(2) heating of step (1) gained mixed liquor is made CHCl3Rapid evaporation obtains final product the poly-lactic acid material.
Preferably, hydroxyapatite is 0.5-20 with the mass ratio of poly-dl-lactide in step (1):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.
Preferably, in step (1) hydroxyapatite CHCl3In suspension the mass concentration of hydroxyapatite be 2～ 30%, for example, 4%, 8%, 13%, 16%, 19%, 22%, 24%, 28% etc..
Preferably, in step (1) hydroxyapatite CHCl3The compound method of suspension is：By hydroxyapatite plus 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, the stirring is carried out using constant temperature blender with magnetic force.
Preferably, described stirring mixing time be more than 5min, for example, 8min, 12min, 16min, 20min, 25min, 32min, 38min, 45min etc., preferably 10～30min.
Preferably, the rotating speed during stirring is 300～800rpm.
Preferably, poly-dl-lactide to be added in step (1) CHCl of hydroxyapatite3Mix in suspension logical Crossing stirring is carried 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.
Preferably, continuing stirring in step (2) during heating, the time that preferably stirs 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 the heating be 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.
Preferably, the preparation method of the present invention is comprised the following steps：
(1) mass ratio is weighed respectively for 9:1～6:4 hydroxyapatite and poly-dl-lactide；
(2) hydroxyapatite is added in chloroform, is placed at 18～30 DEG C in constant temperature blender with magnetic force and stirs 10～30min of mixing, speed of agitator are 300～800rpm；
(3) poly-dl-lactide is added to the CHCl of above-mentioned hydroxyapatite3In suspension, continue at 18～30 DEG C 60～180min of magnetic agitation, makes poly-dl-lactide fully dissolve；
(4) by constant temperature blender with magnetic force temperature adjustment be 40-80 DEG C, continue 60～180min of magnetic agitation, make CHCl3Hurry up Speed evaporation obtains final product described poly-lactic acid material.
The HAp/PDLLA composite mortars of gained are put in needle tubing during use, add syringe needle, be placed in 3D printer according to The print routine of setting can be printed.
The process printed using the material of the present invention is as follows：
(1) opening operation software, open printing machine connect computer；
(2) printed material is loaded onto printer, and installs printhead by open printing machine；
(3) printer model is imported on software；
(4) print platform is adjusted, printer is made in printable state；
(5) print parameters are adjusted；
(6) start button is clicked on, starts to print.
Preferably, the printhead bore is 160 μm -600 μm.
Preferably, the parameter during printing is：Speed is 2-15m/min, preferably 3.12-12.96m/min, pressure For 30-95psi.
There is the poly-lactic acid material of the present invention room temperature to print, and reduces the probability of spray nozzle clogging, improves print performance so that poly- Lactate material can carry out the structure of labyrinth, can better adapt to difference and demand.Additionally, the poly- breast that the present invention is provided Sour material has excellent biocompatibility and degradability, and can carry out 3D printing, structure diversification with smooth Organization bracket, can be advantageously applied in 3D printing.
Specific embodiment
For the present invention is better described, technical scheme is readily appreciated, the present invention's is typical but non-limiting Embodiment is as follows：
Embodiment 1
A kind of 3D printing poly-lactic acid material, raw materials by weight contain following components：
Hydroxyapatite 90%
Poly-dl-lactide 10%
It is prepared via a method which：
(1) hydroxyapatite and poly-dl-lactide that quality is 9g, 1g are weighed respectively；
(2) hydroxyapatite is added in the chloroform of 60mL, is placed in constant temperature blender with magnetic force at 30 DEG C and stirs Mixing 10min is mixed, speed of agitator is 300rpm；
(3) poly-dl-lactide is added to the CHCl of above-mentioned hydroxyapatite3In suspension, continue magnetic force at 18 DEG C Stirring 180min, makes poly-dl-lactide fully dissolve；
(4) by constant temperature blender with magnetic force temperature adjustment be 60 DEG C, continue magnetic agitation 180min, make CHCl3Rapid evaporation Obtain final product described poly-lactic acid material.
Embodiment 2
A kind of 3D printing poly-lactic acid material, raw materials by weight contain following components：
Hydroxyapatite 50%
Poly-dl-lactide 50%
It is prepared via a method which：
(1) hydroxyapatite and poly-dl-lactide that quality is 5g, 5g are weighed respectively；
(2) hydroxyapatite is added in the chloroform of 40mL, is placed in constant temperature blender with magnetic force at 18 DEG C and stirs Mixing 30min is mixed, speed of agitator is 800rpm；
(3) poly-dl-lactide is added to the CHCl of above-mentioned hydroxyapatite3In suspension, continue magnetic force at 30 DEG C Stirring 60min, makes poly-dl-lactide fully dissolve；
(4) by constant temperature blender with magnetic force temperature adjustment be 40 DEG C, continue magnetic agitation 40min, make CHCl3Rapid evaporation is Obtain described poly-lactic acid material.
Embodiment 3
A kind of 3D printing poly-lactic acid material, raw materials by weight mainly contain following components：
Hydroxyapatite 40%
Poly-dl-lactide 60%
It is prepared via a method which：
(1) hydroxyapatite and poly-dl-lactide that quality is 4g, 6.0g are weighed respectively；
(2) hydroxyapatite is added in the chloroform of 60mL, is placed in constant temperature blender with magnetic force at 20 DEG C and stirs Mixing 5min is mixed, speed of agitator is 500rpm；
(3) poly-dl-lactide is added to the CHCl of above-mentioned hydroxyapatite3In suspension, continue magnetic force at 25 DEG C Stirring 30min, makes poly-dl-lactide fully dissolve；
(4) by constant temperature blender with magnetic force temperature adjustment be 70 DEG C, continue magnetic agitation 100min, make CHCl3Rapid evaporation Obtain final product described poly-lactic acid material.
Embodiment 4
A kind of 3D printing poly-lactic acid material, raw materials by weight contain following components：
Hydroxyapatite 70%
Poly-dl-lactide 30%
It is prepared via a method which：
(1) hydroxyapatite and poly-dl-lactide that quality is 7g, 3g are weighed respectively；
(2) hydroxyapatite is added in the chloroform of 60mL, is placed in constant temperature blender with magnetic force at 25 DEG C and stirs Mixing 20min is mixed, speed of agitator is 400rpm；
(3) poly-dl-lactide is added to the CHCl of above-mentioned hydroxyapatite3In suspension, continue magnetic force at 25 DEG C Stirring 120min, makes poly-dl-lactide fully dissolve；
(4) by constant temperature blender with magnetic force temperature adjustment be 65 DEG C, continue magnetic agitation 120min, make CHCl3Rapid evaporation Obtain final product described poly-lactic acid material.
Comparative example 1
Hydroxyapatite 1g, poly-dl-lactide 9g is weighed, material is prepared into sample according to the method for embodiment 1, is entered Row performance test.
Following table is 1 resulting materials performance parameter of embodiment 1-4 and comparative example：
From table 1 it follows that material obtained in the embodiment of the present invention is compared to prepared material not within the scope of the present invention More preferably, mechanical property during printing is more excellent for material printing effect.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art Technical staff it will be clearly understood that any improvement in the present invention, to the equivalence replacement of each raw material of product of the present invention and auxiliary element Interpolation, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (10)

1. a kind of 3D printing poly-lactic acid material, it is characterised in that raw materials by weight mainly contains following components：Hydroxyl phosphorus Lime stone 35-90%, poly-dl-lactide 10-65%, mass percent sum≤100% of above two raw material.
2. poly-lactic acid material according to claim 1, it is characterised in that raw materials by weight is mainly contained with the following group Point：Hydroxyapatite 45-85%, poly-dl-lactide 15-55%, state mass percent sum≤100% of two kinds of raw materials.
3. the preparation method of poly-lactic acid material according to claim 1, comprises the steps：
(1) poly-dl-lactide is added in the chloroform suspension of hydroxyapatite and is mixed；
(2) chloroform rapid evaporation is made to obtain final product the poly-lactic acid material heating of step (1) gained mixed liquor.
4. preparation method according to claim 3, it is characterised in that hydroxyapatite and the poly- breast of raceme in step (1) 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 hydroxyapatite in step (1) In suspension, the mass concentration of hydroxyapatite is 2～30%.
6. the preparation method according to any one of claim 3-5, it is characterised in that the three of hydroxyapatite in step (1) The compound method of chloromethanes suspension is：Hydroxyapatite is added in chloroform, stirring mixing at 18～30 DEG C.
7. preparation method according to claim 6, it is characterised in that the stirring is carried out using constant temperature blender with magnetic force；
Preferably, the time of the stirring mixing is more than 5min, preferably 10～30min；
Preferably, the rotating speed during 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) Mixing in the chloroform suspension for being added to hydroxyapatite is carried out by stirring；
Preferably, more than 30min, preferably 60～180min are stirred at 18～30 DEG C.
9. the preparation method according to any one of claim 3-8, it is characterised in that continue stirring during heating in step (2), It is preferred that the time that stirs is more than 30min, more preferably 60～180min；
Preferably, the temperature of the heating is more than 40 DEG C, preferably 60 DEG C.
10. a kind of usage right requires that the process printed by the material described in 1 or 2 is as follows：
(1) opening operation software, open printing machine connect computer；
(2) printed material is loaded onto printer, and installs printhead by open printing machine；
(3) printer model is imported on software；
(4) print platform is adjusted, printer is made in printable state；
(5) print parameters are adjusted；
(6) start button is clicked on, starts to print；
Preferably, the printhead bore is 160 μm -600 μm；
Preferably, the parameter during printing is：Speed is 2-15m/min, preferably 3.12-12.96m/min, and pressure is 30- 95psi.
CN201610910906.6A 2016-10-19 2016-10-19 A kind of 3D printing poly-lactic acid material and preparation method thereof, Method of printing Pending CN106496977A (en)

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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610910906.6A CN106496977A (en) 2016-10-19 2016-10-19 A kind of 3D printing poly-lactic acid material and preparation method thereof, Method of printing

Publications (1)

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CN106496977A true CN106496977A (en) 2017-03-15

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103285428A (en) * 2013-04-26 2013-09-11 中国国旅贸易有限责任公司 Artificial bone material and preparation method thereof
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
CN103285428A (en) * 2013-04-26 2013-09-11 中国国旅贸易有限责任公司 Artificial bone material and preparation method thereof
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: 20170315

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