CN106046726B - A kind of 3D printing composite polylactic acid material and preparation method thereof - Google Patents
A kind of 3D printing composite polylactic acid material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L2205/24—Crystallisation aids
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Abstract
It is the high heat-resisting stereocomplex PLA composition material of the high-ductility suitable for 3D printing being made with PLLA and 58~85wt% of PDLA mixtures, 0.2~2wt% of uracil derivative class nucleator, 5~10wt% of polyethylene glycol, hydroxyl alkane acid lipin polymer 10~30wt% melt blendings the present invention relates to a kind of 3D printing composite polylactic acid material.Material of the present invention can effectively improve the crystallization rate and heat resistance of polylactic acid stereoscopic composite, meet 3D printing forming requirements, and significantly improve the impact strength and elongation at break of stereocomplex PLA, effectively solve the problem of 3D printing polylactic acid article is hard and crisp.
Description
Technical field
The invention belongs to field of high polymer material modification, it is related to a kind of poly-lactic acid material, it is more particularly to a kind of suitable
Composite polylactic acid material with the high heat-resisting vertical structure performance of high-ductility for 3D printing and preparation method thereof.
Background technology
3D printing is to rise a kind of fast free forming technique in 1990s mid-term, and its principle is with computer
Based on the digital model that modeling or scanning prototype are obtained, according to the two-dimensional section data after layering, software and numerical control are utilized
System, by powdery metal, ceramics or polymer etc. can jointing material by the increasing material manufacturing mode successively printed be built into three
Tie up entity.Compared with traditional molding methods, the maximum advantage of 3D printing, just can be directly without machining or mould
The object of any shape is generated from computer graphics data, so as to highly shortened the production cycle of product.3D printing is
Gradually it is applied to education, medical treatment, industrial modeling, scientific research archaeology, architectural design, food industries, clothing component, culture and arts, friendship
The logical field such as instrument and Aero-Space.
3D printing mainly with technology have following four：Selective laser sintering (Selective Laser
Sintering, SLA), fusion sediment moulding (Fused Deposition Modeling, FDM), stereolithography apparatus
(Stereo Lithography Appearance, SLA) and layer separated growth (Laminated Object
Manufacturing, LOM).Wherein, fusion sediment moulding (FDM) is most simple to equipment requirement, and printing cost is also minimum, is mesh
Before the printing type that is most widely used, especially for personal desktop's level 3D printer.
FDM not against laser as shaping the energy, but by thermoplastic silk material heat melt, it is successively accumulated simultaneously
Cooling and solidifying constitutes three-dimensional objects.Conventional FDM printed materials mainly have PLA (PLA), acrylonitrile-butadiene-styrene (ABS)
Copolymer (ABS), nylon (PA) and makrolon (PC) etc..ABS can produce penetrating odor in print procedure, nylon and poly-
The melting temperature of carbonic ester is high, and printing difficulty is big, is also easy to produce buckling deformation.Comparatively, PLA is used as a kind of biological source
Degradable high polymer material, have the advantages that nonhazardous, environmentally safe, melting temperature are low and cooling meat rate is small, make
It turns into most popular 3D printing material.But the crystalline rate of polylactic resin is slow, resistance to heat distorsion and impact resistance
Can be poor, limit the application of its printed product.Therefore, PLA is overcome by improving crystallizing power and toughening modifying
Applied defect in 3D printing material then seems very necessary.
Alpha-carbon atom in PLA monomeric unit is an asymmetric carbon atom, with optical activity, thus PLA have it is left-handed
And two kinds of isotactic spatial configurations of dextrorotation (PDLA) (PLLA).Stereocomplex crystallization can occur between PLLA and PDLA, than respective
The fusing point of homogeneity crystallization is high about 50 DEG C, and this provides possibility to prepare the poly-lactic acid material with high-fire resistance.But Stereocomplex
Crystallization is largely affected by molecular weight, (divides equally again for commonly used in practice HMW PLLA and PDLA
Son amount is more than 40,000 g/mol), due to being limited by intermolecular crystal nucleation, growth and strand transfer ability, molten condition
Homogeneity crystal is mainly generated during lower crystallization, only a small amount of Stereocomplex crystal generation.Therefore, the Stereocomplex of high-fire resistance is prepared
The key of poly-lactic acid material is how to promote its Stereocomplex to crystallize.From the point of view of crystallization and raising crystallinity is accelerated,
It is a kind of maximally efficient and simple and feasible method to add nucleator, and the addition of nucleator can reduce the free energy of nucleating surface
Build, substantial amounts of activation nucleus is provided initial stage in crystallization.
Current research emphasis is concentrated mainly on the crystalline modified of PLLA, and few on induction PLLA and PDLA blendings
The report of thing Stereocomplex crystallization.CN104059343A and CN104804388A utilizes aromatic amides class nucleator (N, N '-two
Cyclohexyl terephthalamide and N, N ', the equal benzene trimethamide of N ' '-thricyclohexyl) improve the vertical of PLLA and PDLA blends
Structure compound crystal speed and crystallinity, so that the poly-lactic acid material of high stereoscopic composite content is made.But this kind of nucleator synthesis
Cumbersome, building-up process uses the arene compounds containing phenyl ring, and preparation process and application may cause one to human body and environment
Fixed harm.
Additionally it has been disclosed that patent in be related to the toughener that 3D printing used with modified polylactic acid material and have inorganic nanoparticles
Sub (CN103665802B) and traditional non-biodegradation type elastomer such as polyethylene (CN104725802A), esters of acrylic acid polymerize
Thing and acetate ethylene copolymer (CN104725806A), transparent butylbenzene anti-impact resin (CN105111703A) etc., and it is biodegradable
Type toughener is mainly polycarbonate elastomer body (CN104629280A) and aliphatic and introduces aromatic binary acid dihydric alcohol
Copolyesters (CN103467950B, CN104177798A).Up to the present, do not increase on hydroxyl alkane acid lipin polymer also
The relevant report of tough PLA 3D printing material.
The content of the invention
The purpose of the present invention is to overcome the shortcomings of that prior art is present there is provided a kind of 3D printing composite polylactic acid material,
So that the crystalline rate of material, heat distortion temperature, impact strength and elongation at break are increased dramatically.
The present invention also aims to provide a kind of preparation method of the composite polylactic acid material.
Composite polylactic acid material of the present invention is a kind of poly- breast of the high heat-resisting Stereocomplex of high-ductility suitable for 3D printing
Acid composition material, it is made with the raw materials melt blending of following weight/mass percentage compositions：PLLA (PLLA) and poly- dextrorotation
58~85wt% of lactic acid (PDLA) mixture, 0.2~2wt% of uracil derivative class nucleator, 5~10wt% of polyethylene glycol, hydroxyl
10~30wt% of alkanoate analog copolymer.
Wherein, in described PLLA and PDLA mixtures, PLLA and PDLA mass ratio are 1: 0.5~2, preferably 1: 1.
It is highly preferred that PLLA used in the present invention and PDLA optical purity is more than 90%, weight average molecular weight is 100,000~300,000 g/
Mol, melt index is 5~20g/10min (2.16kg, 210 DEG C).
Described uracil derivative class nucleator is dystectic for promoting PLLA and PDLA mixtures to selectively produce
Stereocomplex crystal, improves Stereocomplex crystallization rate and crystallinity, and then improve heat resistance.The uracil that can be used derives
Species nucleator includes uracil, 6- methyluracils, 6- amino-uracils, 6- carboxyuracils (orotic acid), 6- hydroxyls urine
Pyrimidine (barbiturates) or 6- amino -1- methyluracils, its addition for composite polylactic acid material gross mass 0.2~
2wt%。
Addition polyethylene glycol is as plasticizer in the composite polylactic acid material of the present invention, and its one side is by improving PLLA
With the migration of PDLA strands, promotion Stereocomplex crystallization is cooperateed with together with uracil derivative class nucleator；The opposing party
Stereocomplex PLA and the compatibility of hydroxyl alkane acid lipin polymer are improved in face, and adjust the melt flows of 3D printing silk material
Performance.The addition of polyethylene glycol is 5~10wt% of composite polylactic acid material gross mass in composite polylactic acid material of the present invention,
It is preferred to use the polyethylene glycol that weight average molecular weight is 1000~10000g/mol.
The hydroxyl alkane acid lipin polymer added in the present invention is to improve stereocomplex PLA as toughener
Pliability and ductility, its addition accounts for 10~30wt% of composite polylactic acid material gross mass.Described hydroxy alkane acid ester
Analog copolymer be poly- (3-hydroxybutyrate ester-co-4- butyric esters), poly- (3-hydroxybutyrate ester-co-3- hydroxyl valerates) or
Poly- (3-hydroxybutyrate ester-co-3- hydroxycaproic esters).
In the present invention, the weight average molecular weight of the hydroxyl alkane acid lipin polymer is 400,000~1,000,000 g/mol.This hair
In the bright various copolymers used, copolymerization units 4 hydroxybutyric acid ester, 3- hydroxyl valerates or 3- hydroxycaproic esters are each common
Molar content in polymers is 5~30%.
And then, present invention also offers the one of the high heat-resisting stereocomplex PLA material of the above-mentioned high-ductility suitable for 3D printing
Kind of preparation method, is first to granulate PLLA, PDLA and uracil derivative class nucleator melt blending, then by obtained PLA
Particle and polyethylene glycol and hydroxyl alkane acid lipin polymer melt blending, extrusion traction wire drawing, are made 3D printing poly- with being combined
Lactate material silk material.
The a diameter of 1.75mm or 3mm of 3D printing silk material prepared by the present invention, diameter error is within ± 2%, for melting
Deposition 3D printer is used, 200~230 DEG C of print temperature scope.
In the above-mentioned preparation method of the present invention, various raw materials are first carried out after drying process, then carry out melt blending.The present invention
It is preferred to use vacuum drying, general control vacuum drying temperature is 60~80 DEG C, 4~12h of drying time.Various raw materials are through drying
Afterwards, moisture is less than 0.025%.
In order to realize that nucleator is good dispersed in PLLA and PDLA matrixes, and 3D printing silk material regular journey
The homogeneity of degree and diameter, present invention employs first double screw extruder melting mixing, rear single screw extrusion machine blending wire drawing
Process.Wherein, the screw speed of double screw extruder and single screw extrusion machine is disposed as 30~100rpm, head and machine
The heating temperature range of each section of cylinder is 170~230 DEG C.
, can also be it is pointed out that in order to avoid thermal-oxidative degradation and hydrolysis occur during melt blending for material
The antioxidant and hydrolysis inhibitor of a small amount of (0.2~1wt%) are added before extrusion.Wherein, described antioxidant includes hindered phenol
Class and phosphorous acid esters composite antioxidant, hydrolysis inhibitor is carbodiimide compound.
The present invention by using uracil derivative class nucleator and low molecular poly collaboration promote PLLA and
PDLA mixtures selectively produce dystectic Stereocomplex crystal, can effectively improve the crystallization rate of polylactic acid stereoscopic composite
And heat resistance, meet the forming requirements of 3D printing.
The uracil that the present invention is selected is a kind of naturally occurring core base, is ribonucleic acid (RNA) constituent, its
Derivative is commonly used for medicine intermediate and nutritional drugs, the good characteristic with bio-compatible and biological absorbable, and and PLA
Matrix has preferable compatibility, and dispersed, lifting nucleating effect is easily reached in the base.
The hydroxyl alkane acid lipin polymer of high-flexibility is a kind of Biodegradable polyester by Microbe synthesis, in poly- second
Under the plasticization of glycol, it has certain compatibility with PLA matrix, can significantly improve stereocomplex PLA
Impact strength and elongation at break, efficiently solve the problem of 3D printing polylactic acid article is hard and crisp.
Raw material PLLA, PDLA, uracil derivative, low molecular poly and hydroxyl alkane acid used in the present invention
Lipin polymer can biological decomposition, therefore prepared stereocomplex PLA material has environmental protection and can give birth to completely
The good characteristic of thing degraded so that the backing material and printing product produced during 3D printing will not be made after discarded to environment
Into harm.
The present invention prepares 3D printing material using melt-blending process, and equipment requirement is simple, and production cost is low, easily realizes production
Industry.
Embodiment
For a further understanding of the present invention, with reference to specific embodiment and comparative example to the preferred embodiment of the invention
It is described in detail.It is to be understood that, following examples are merely to illustrate the present invention, rather than limitation the scope of the present invention.
Without departing from the spirit and substance of the case in the present invention, the modifications or substitutions made to the inventive method, step or condition, belong to
In the scope of the present invention.
Unless otherwise specified, the technological means employed in embodiment is conventional hand well known to those skilled in the art
Section.
In following embodiment and comparative example, PLLA weight average molecular weight is 210,000 g/mol, optical purity 98%, melting
Index 7g/10min (2.16kg, 210 DEG C)；PDLA weight average molecular weight is 130,000 g/mol, optical purity 99%, melt index
12g/10min (2.16kg, 210 DEG C)；The weight average molecular weight of polyethylene glycol is 4000g/mol.
Mechanical property and heat resistance test：Erichsen test is performed with reference to GB/T 1040-2006 standards, stretching speed
Spend 2mm/min；Izod nick break tests are performed with reference to GB/T 1843-2008 standards；Heat distortion temperature is determined with reference to GB/T
1634-2004 standards are performed, underload 0.45MPa, 120 DEG C/h of heating rate.
Embodiment 1.
In terms of mass parts, weigh and dry 49 parts of PLLA after 10h, 49 parts of PDLA at 70 DEG C in vacuum drying oven, urinate phonetic
2 parts of pyridine, after premixing 6min through high speed mixer with 800rpm rotating speed, uses double screw extruder melting extrusion, after tank cooling
Polylactic acid blend particle is obtained by pelleter pelletizing.Five sections of heating-up temperatures of double screw extruder machine barrel are respectively set as 180,
190th, 200,210,215 DEG C, head temperature is set as 220 DEG C, screw speed 60rpm.
Weigh 80 parts of above-mentioned polylactic acid blend particles, 5 parts of polyethylene glycol and 15 parts of poly- (3-hydroxybutyrate ester-co-4- hydroxyls
Butyrate) (4 hydroxybutyric acid ester content 20mol%, the g/mol of weight average molecular weight 540,000), after being premixed through high speed mixer, use single spiral shell
Bar extruder melt blending, 3D printing silk material of the traction Wire Drawing into diameter 1.75mm.Five sections of extruder cylinder of single screw extruder
Heating-up temperature is respectively set as 175,185,195,200,205 DEG C, head temperature is set as 210 DEG C, screw speed 50rpm.
Above-mentioned 3D printing silk material is printed as mechanical property with desktop level 3D printer and heat resistance tests required mark
Quasi- batten, 210 DEG C of print temperature, 80 DEG C of print job platform temperature, test result is shown in Table 1.
Embodiment 2.
In terms of mass parts, weigh and dry 33 parts of PLLA, 66 parts of PDLA, 6- ammonia after 12h at 60 DEG C in vacuum drying oven
1 part of base uracil, after premixing 10min through high speed mixer with 500rpm rotating speed, uses double screw extruder melting extrusion, tank
Polylactic acid blend particle is obtained by pelleter pelletizing after cooling.Five sections of heating-up temperatures of double screw extruder machine barrel are respectively set as
170th, 180,190,200,205 DEG C, head temperature is set as 210 DEG C, screw speed 100rpm.
Weigh 70 parts of above-mentioned polylactic acid blend particles, 10 parts of polyethylene glycol and 20 parts of poly- (3-hydroxybutyrate ester-co-3- hydroxyls
Base valerate) (3- hydroxypentanoic acid ester content 5mol%, the g/mol of weight average molecular weight 610,000), after being premixed through high speed mixer, with list
Screw extruder melt blending, 3D printing silk material of the traction Wire Drawing into diameter 1.75mm.The five of extruder cylinder of single screw extruder
Section heating-up temperature is respectively set as 170,180,190,195,200 DEG C, head temperature is set as 205 DEG C, screw speed 100rpm.
Above-mentioned 3D printing silk material is printed as mechanical property with desktop level 3D printer and heat resistance tests required mark
Quasi- batten, 230 DEG C of print temperature, 90 DEG C of print job platform temperature, test result is shown in Table 1.
Embodiment 3.
In terms of mass parts, weigh and dry 66 parts of PLLA, 33.5 parts of PDLA, 6- carboxylics after 4h at 80 DEG C in vacuum drying oven
0.5 part of base uracil, after premixing 5min through high speed mixer with 1000rpm rotating speed, uses double screw extruder melting extrusion, water
Polylactic acid blend particle is obtained by pelleter pelletizing after groove cooling.Five sections of heating-up temperatures of double screw extruder machine barrel are set respectively
For 190,200,210,220,225 DEG C, head temperature is set as 230 DEG C, screw speed 30rpm.
Weigh 60 parts of above-mentioned polylactic acid blend particles, 10 parts of polyethylene glycol and 30 parts of poly- (3-hydroxybutyrate ester-co-3- hydroxyls
Base capronate) (3- hydroxycaproic acid ester content 22mol%, the g/mol of weight average molecular weight 620,000), after being premixed through high speed mixer, with list
Screw extruder melt blending, 3D printing silk material of the traction Wire Drawing into diameter 1.75mm.The five of extruder cylinder of single screw extruder
Section heating-up temperature is respectively set as 185,195,205,210,215 DEG C, head temperature is set as 220 DEG C, screw speed 30rpm.
Above-mentioned 3D printing silk material is printed as mechanical property with desktop level 3D printer and heat resistance tests required mark
Quasi- batten, 220 DEG C of print temperature, 100 DEG C of print job platform temperature, test result is shown in Table 1.
Comparative example.
In terms of mass parts, weigh and dry 50 parts of PLLA, 50 parts of PDLA after 10h at 70 DEG C in vacuum drying oven, through height
After fast batch mixer is with 800rpm rotating speed premix 6min, double screw extruder melting extrusion is used, by pelletizing machine-cut after tank cooling
Grain obtains polylactic acid blend particle.Five sections of heating-up temperatures of double screw extruder machine barrel are respectively set as 180,190,200,210,
215 DEG C, head temperature is set as 220 DEG C, screw speed 60rpm.
Again by above-mentioned polylactic acid blend particle single screw extrusion machine melt blending, Wire Drawing is drawn into diameter 1.75mm
3D printing silk material.Five sections of heating-up temperatures of extruder cylinder of single screw extruder are respectively set as 175,185,195,200,205 DEG C, machine
Head temperature is set as 210 DEG C, screw speed 50rpm.
Above-mentioned 3D printing silk material is printed as mechanical property with desktop level 3D printer and heat resistance tests required mark
Quasi- batten, 210 DEG C of print temperature, 80 DEG C of print job platform temperature, test result is shown in Table 1.
As can be seen from Table 1, added in PLLA and PDLA mixtures uracil derivative class nucleator, polyethylene glycol and
After hydroxyl alkane acid lipin polymer, slightly reduced though the tensile strength of composition has, elongation at break, impact strength and heat
Deformation temperature all has greatly improved, and shows the pliability of prepared stereocomplex PLA material, ductility and heat-resisting
Property is obviously improved, and has widened PLA as the application of 3D printing material.
Claims (9)
1. a kind of 3D printing composite polylactic acid material, is made with the raw materials melt blending of following weight/mass percentage compositions：PLLA with
58~78.4wt% of PDLA mixtures, 0.2~2wt% of uracil and its derivative species nucleator, 5~10wt% of polyethylene glycol, hydroxyl
10~30wt% of alkanoate analog copolymer；Wherein, in described PLLA and PDLA mixtures, PLLA and PDLA mass ratio are 1
: 0.5~2.
2. 3D printing according to claim 1 composite polylactic acid material, it is characterized in that PLLA and PDLA mass ratio is 1
∶1。
3. 3D printing according to claim 1 composite polylactic acid material, it is characterized in that described uracil and its derivative
Species nucleator is uracil, 6- methyluracils, 6- amino-uracils, 6- carboxyuracils, 6- hydroxyuracils or 6- ammonia
Base -1- methyluracils.
4. 3D printing according to claim 1 composite polylactic acid material, it is characterized in that the polyethylene glycol is divided equally again
Son amount is 1000~10000g/mol.
5. 3D printing according to claim 1 composite polylactic acid material, it is characterized in that described hydroxyl alkane acid esters
Copolymer is poly- (3-hydroxybutyrate ester-co-4- butyric esters), poly- (3-hydroxybutyrate ester-co-3- hydroxyl valerates) or poly-
(3-hydroxybutyrate ester-co-3- hydroxycaproic esters).
6. 3D printing according to claim 5 composite polylactic acid material, it is characterized in that the hydroxyl alkane acid esters are common
The weight average molecular weight of polymers is 400,000~1,000,000 g/mol.
7. 3D printing according to claim 5 composite polylactic acid material, it is characterized in that the hydroxyl alkane acid esters are common
In polymers, copolymerization units 4 hydroxybutyric acid ester, 3- hydroxyl valerates or 3- hydroxycaproic esters mole containing in respective copolymer
Measure as 5~30%.
8. the preparation method of composite polylactic acid material of 3D printing described in claim 1, be first by PLLA, PDLA and uracil and
Its derivative species nucleator melt blending is granulated, then obtained particles of polylactic acid is total to polyethylene glycol and hydroxyl alkane acid esters
Polymers melt blending, extrusion traction wire drawing, is made 3D printing composite polylactic acid wire materials.
9. the 3D printing according to claim 8 preparation method of composite polylactic acid material, it is characterized in that by various raw materials
Remelted blending after drying process.
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| CN108219407A (en) * | 2017-12-05 | 2018-06-29 | 湖北光合生物科技有限公司 | A kind of poly- 3-hydroxybutyrate ester composite material and preparation method thereof |
| JP2019119840A (en) * | 2018-01-11 | 2019-07-22 | 株式会社カネカ | Aliphatic polyester resin composition |
| CN108285625B (en) * | 2018-01-24 | 2020-09-04 | 长沙新材料产业研究院有限公司 | Method for preparing polylactic acid stereocomplex through 3D printing |
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| CN114290632A (en) * | 2021-12-09 | 2022-04-08 | 江南大学 | Preparation method of fused deposition modeling 3D printing heat-resistant stereo polylactic acid wire rod |
| CN117264394A (en) * | 2023-11-20 | 2023-12-22 | 苏州聚复科技股份有限公司 | 3D printing material, printing method and preparation method |
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| CN104629280A (en) * | 2015-02-04 | 2015-05-20 | 山东科技大学 | High-strength high-toughness polyactic acid composite material suitable for 3D printing molding and preparation method of composite material |
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| GB2488811B (en) * | 2011-03-09 | 2015-02-25 | Floreon Transforming Packaging Ltd | Biodegradable polymer blend |
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| CN1861683A (en) * | 2005-04-28 | 2006-11-15 | 索尼株式会社 | Resin composition and molded product obtained therefrom |
| CN104177798A (en) * | 2014-09-19 | 2014-12-03 | 上海材料研究所 | Modified polylactic acid composite material suitable for 3D printing and preparation method of composite material |
| CN104629280A (en) * | 2015-02-04 | 2015-05-20 | 山东科技大学 | High-strength high-toughness polyactic acid composite material suitable for 3D printing molding and preparation method of composite material |
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