CN109608840A - A kind of degradable low temperature polyester alloy 3D printing material and preparation method thereof - Google Patents
A kind of degradable low temperature polyester alloy 3D printing material and preparation method thereof Download PDFInfo
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- 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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- 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
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- C08K5/00—Use of organic ingredients
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- C08K5/098—Metal salts of carboxylic acids
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Abstract
The present invention relates to 3D printing field of material technology, and in particular to a kind of degradable low temperature polyester alloy 3D printing material and preparation method thereof, raw material includes PCL, PBAT, micron order mineral powder, nanoscale mineral powder, biodegradation promotor, lubricant and nucleating agent.Degradable low temperature polyester alloy 3D printing material provided by the invention has good low temperature properties, and the wire rod prepared can print within the scope of 65~80 DEG C, and cooling velocity is fast.It neither scalds, and the speed of finished product can be accelerated.In addition, joined micron order mineral powder in PCL and nanoscale mineral powder carries out compounding enhancing, the intensity for being made material is high, hardness is high, it is ensured that outlet velocity uniformity and stability in print procedure.
Description
Technical field
The present invention relates to 3D printing field of material technology, and in particular to a kind of degradable low temperature polyester alloy 3D printing material
And preparation method thereof.
Background technique
3D printing technique is a kind of special printing technique, it is based on the spatial data of model, with metal or powder
Etc. adhesive materials, be stacked up by printing layer by layer, final " printing " out as model in computer ratio three-dimensional model.
3D printing technique comes across the end of the eighties in last century earliest, starts to gradually mature simultaneously the fashionable whole world rapidly after 2010, and
After into Chinese market also due to it facilitates the characteristic of trend rapidly by the welcome of the majority of consumers.From common cartoon character
The models such as object, sand table or the art work print normally to vehicles such as printing automobile, aircrafts even with human body cell
Liver organization, the figure of 3D printing appear in any place that we are envisioned that.
Existing 3D printing consumptive material mainly has polylactic acid, ABS, PA, PVA etc., since there is offices for above-mentioned a variety of materials
Sex-limited, poly-lactic acid material is at high cost, material is easily deformed at 55 DEG C or more；ABS (acrylate/butadiene/styrene ternary polymerization
Object), a kind of common engineering plastics, processing smell weight is easily deformed in squeezing out processing；PA is a kind of nylon material, price
Valuableness, processing difficulties, processing smell people, processing environment are severe；PVA water-soluble material is mainly used for printing support material dosage
It is few, and process since PVA decomposition is easy to produce toxic gas.
Polycaprolactone (Polycaprolactone, PCL, No. CAS: 24980-41-4) is also known as poly-epsilon-caprolactone, is to pass through
6-caprolactone monomer macromolecule organic polymer made of ring-opening polymerisation under the catalysis of anionic metal complex catalyst, passes through control
Polymerizing condition processed can obtain different molecular weight.Its appearance is white solid powder, nontoxic, not soluble in water, is soluble in a variety of
Polar organic solvent.PCL has good biocompatibility, good organic polymer compatibility and good biology drop
Xie Xing can be used as cell growth support material, can be compatible with a variety of common plastics, 6-12 months under natural environment can be complete
Degradable.In addition, PCL also has good shape memory temperature control property, it is widely used in pharmaceutical carrier, plasticizer, can drops
Solve plastics, nanofiber spinning, the production of moulding material and manufacture field.PCL had into very big answer in 3D printing material
Use prospect.
The patent of invention of ZL201810562955.4 discloses a kind of antibacterial PCL plant fiber recombination line for 3D printing
Material and preparation method thereof is made of the raw material of following parts by weight meter: 60~95 parts of PCL raw material, 1~20 part of plant fiber, being received
1~15 part of filler, 0.1~3 part of chain extender, 0.2~2 part of antibacterial agent of rice.The PCL wire rod although preferable mechanical property, still
The promotion of mechanical property is derived mainly from the addition of the chain extender and plant fiber of particular vendors, and plant fiber itself also needs idol
Join agent processing, higher cost, and the limitation for raw material does not have wide usage yet.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of at low cost, power
Learn that performance is good, degradable, 3D printing temperature is lower and the preferable polyester alloy 3D printing material of effect, another mesh of the invention
Be the preparation method of the polyester alloy 3D printing material is provided, the evenly dispersed of each material may be implemented, avoid stress collection
Middle phenomenon occurs, therefore 3D printing Mechanical Properties of Materials obtained and printing effect are preferable.
The purpose of the invention is achieved by the following technical solution:
A kind of degradable low temperature polyester alloy 3D printing material, the raw material including following parts by weight:
Degradable low temperature polyester alloy 3D printing material provided by the invention has good low temperature properties, the line prepared
Material can print within the scope of 65~80 DEG C, and cooling velocity is fast.It neither scalds, and the speed of finished product can be accelerated.In addition, in PCL
In joined micron order mineral powder and nanoscale mineral powder carries out compounding enhancing, the intensity for being made material is high, hardness is high, Ke Yibao
Card outlet velocity uniformity and stability in print procedure.
Preferably, the raw material including following parts by weight:
PBAT belongs to thermoplastic biodegradable plastics, is tetramethylene adipate and the copolymerization of mutual-phenenyl two acid bromide two alcohol ester
Object has both the characteristic of PBA and PBT, existing preferable ductility and elongation at break, also there is preferable heat resistance and impact
Energy；In addition, also having excellent biological degradability, the present invention joined PBAT in PCL and be modified, and improve 3D printing material
After expecting mechanical property and degradation property, moreover it is possible to enhance the mobility of 3D printing material, to improve the effect of 3D printing.
Wherein, the melt index of the PCL is 5.4-5.8g/10min, and test condition is 160 DEG C/2.16kg, is divided equally again
Son amount is 50000-90000, and melting temperature is 58-60 DEG C.The melt index for the PCL that the present invention selects 5.4g/10min with
On, there is good processing fluidity during 3D printing, thus 3D printing effect is preferable, and weight average molecular weight is 50000
More than, the mechanical properties such as tensile strength, bending strength, elongation at break of PCL have preferable performance.
Wherein, the melt index of the PBAT is 3-6g/10min, and test condition is 190 DEG C/2.16kg, weight average molecular weight
For 12000-15000, Vicat softening point is 75-85 DEG C, and heat distortion temperature is 40-50 DEG C.The melting for the PBAT that the present invention selects
Index has good processing fluidity in 3g/min or more during 3D printing, thus 3D printing effect is preferable, and weight is equal
Molecular weight has preferable performance in mechanical properties such as the tensile strengths, bending strength, elongation at break of 12000 or more, PBAT,
It is more significant to the modifying function of PCL.
Wherein, the micron order mineral powder be one of talcum powder, calcium carbonate, kaolin, glass microballoon or it is a kind of with
On, the mesh number of the micron order mineral powder is 5000-8000 mesh.The micron order ore of present invention addition 5000-8000 mesh partial size
Powder can be effectively improved the mechanical property of printed material, and guarantee it still and have preferable processing fluidity, be conducive to carry out 3D
Printing.Preferably, the micron order mineral powder is calcium carbonate and/or glass microballoon, and calcium carbonate dispersibility in resin is preferably, right
The improvement result of mechanical property is more significant；Glass microballoon is spherical, and can preferably improve the processing flowing of printed material
Property.It is further preferred that the micron order mineral powder is made of calcium carbonate and glass microballoon by weight the ratio of 1-2:1-2.
Wherein, the nanoscale mineral powder be one of talcum powder, calcium carbonate, glass microballoon or more than one, it is described
The partial size of nanoscale mineral powder is 2-10nm.The nanoscale mineral powder of 2-10nm of the present invention can be effectively improved the power of printed material
Performance is learned, and guarantee it still there is preferable processing fluidity, is conducive to carry out 3D printing.Preferably, the nanoscale ore
Powder is talcum powder and/or glass microballoon, and nano talc plays the role of part nucleating agent, and the effective partial size for refining crystal is mended
Fill the intensity of material；Nano-glass microballon is spherical, and material flowability can be improved, and increases the glossiness of product.It is further excellent
Selection of land, the nanoscale mineral powder are made of talcum powder and glass microballoon by weight the ratio of 1-2:1-2.
Wherein, the biodegradation promotor is one of di(2-ethylhexyl)phosphate light calcium, phosphoric acid the second light industry bureau potassium, N- lauroyl glutamate
Or more than one.The effect of biodegradation promotor is to be rapidly decomposed into free radical in the soil, and free radical goes to promote PCL molecule
Chain fracture, to reach the degradation time for shortening PCL.
Wherein, the lubricant is pentaerythritol stearate, in zinc stearate, calcium stearate, silicone oil, polyethylene wax
It is one or more kinds of.The processing fluidity of each material can be enhanced in lubricant, conducive to the uniform mixed of material each in melting process
Conjunction and extruding pelletization.Preferably, the lubricant is silicone oil and/or calcium stearate, silicone oil PCL, PBAT and mineral powder it
Between play the role of bridge formation, can effectively improve mixing dispersibility；And the heatproof of material can be improved in calcium stearate, on the other hand
Outer lubrication can be played, material flowability is improved.
Wherein, the nucleating agent is montanic acid sodium, inorganic laminated silicate, nano silica, 1,3,5- benzene tricarboxylic acyls
One of amine, nano rare earth or more than one.Nucleating agent is accelerated crystalline rate, is increased by the crystallization behavior of change resin
Crystal density and promote fine grain size, reaches and shorten that molding cycle, to improve the product transparency, lustrous surface, tension strong
The physical mechanical properties such as degree, rigidity, heat distortion temperature, impact resistance, creep resistance.Preferably, the nucleating agent is montanic acid
Sodium and/or nano silica, montanic acid sodium not only acts as lubricating action, and can reduce the partial size of crystal, improves intensity；
And nano silica can coat and disperse well with PCL, PBAT, accelerate molding period and cooling time.
A kind of preparation method of degradable low temperature polyester alloy 3D printing material as described above, includes the following steps:
(1) mixing 2-4min will be carried out with the revolving speed of 200-400r/min after PCL and PBAT drying, obtains the first mixing
Material；
(2) micron order mineral powder, nanoscale mineral powder is added, into first mixture with turning for 400-600r/min
Speed carries out mixing 4-8min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, 30-40 DEG C is heated to, with the revolving speed of 600-800r/min
Mixing 6-10min is carried out, third mixture is obtained；
(4) by the third mixture 75-95 DEG C at a temperature of carry out melting extrusion, pelletizing is to get to described complete
Degradation low temperature polyester alloy 3D printing material.
The evenly dispersed of each material may be implemented by batch mixed in preparation method of the invention, avoids stress from concentrating existing
As occurring, therefore 3D printing Mechanical Properties of Materials obtained and printing effect are preferable.
The beneficial effects of the present invention are: degradable low temperature polyester alloy 3D printing material provided by the invention has good
Good low temperature properties, the wire rod prepared can print within the scope of 65~80 DEG C, and cooling velocity is fast.It neither scalds, and can accelerate
The speed of finished product.In addition, joined micron order mineral powder in PCL and nanoscale mineral powder carries out compounding enhancing, material is made
Intensity is high, hardness is high, it is ensured that outlet velocity uniformity and stability in print procedure.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of degradable low temperature polyester alloy 3D printing material, the raw material including following parts by weight:
The micron order mineral powder and nanoscale mineral powder are talcum powder, and the partial size of the nanoscale mineral powder is 2nm,
The mesh number of the micron order mineral powder is 6000 mesh, and the biodegradation promotor is calcium dihydrogen phosphate, and the lubricant is season
Penta tetrol stearate, the nucleating agent are montanic acid sodium.
Wherein, the melt index of the PCL is 5.6g/10min, and test condition is 160 DEG C/2.16kg, weight average molecular weight
It is 70000, melting temperature is 59 DEG C.
Wherein, the melt index of the PBAT is 4.5g/10min, and test condition is 190 DEG C/2.16kg, weight average molecular weight
It is 13000, Vicat softening point is 80 DEG C, and heat distortion temperature is 45 DEG C.
A kind of preparation method of degradable low temperature polyester alloy 3D printing material as described above, includes the following steps:
(1) mixing 3min will be carried out with the revolving speed of 300r/min after PCL and PBAT drying, obtains the first mixture；
(2) into first mixture be added micron order mineral powder, nanoscale mineral powder, with the revolving speed of 500r/min into
Row mixing 6min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, is heated to 35 DEG C, is mixed with the revolving speed of 700r/min
8min obtains third mixture；
(4) by the third mixture 85 DEG C at a temperature of carry out melting extrusion, pelletizing is to get arriving the degradable
Low temperature polyester alloy 3D printing material.
Embodiment 2
A kind of degradable low temperature polyester alloy 3D printing material, the raw material including following parts by weight:
The micron order mineral powder and nanoscale mineral powder are calcium carbonate, and the partial size of the nanoscale mineral powder is 4nm,
The mesh number of the micron order mineral powder is 5000 mesh, and the biodegradation promotor is potassium dihydrogen phosphate, and the lubricant is hard
Resin acid zinc, the nucleating agent are inorganic laminated silicate.
Wherein, the melt index of the PCL is 5.6g/10min, and test condition is 160 DEG C/2.16kg, weight average molecular weight
It is 70000, melting temperature is 59 DEG C.
Wherein, the melt index of the PBAT is 4.5g/10min, and test condition is 190 DEG C/2.16kg, weight average molecular weight
It is 13000, Vicat softening point is 80 DEG C, and heat distortion temperature is 45 DEG C.
A kind of preparation method of degradable low temperature polyester alloy 3D printing material as described above, includes the following steps:
(1) mixing 3min will be carried out with the revolving speed of 300r/min after PCL and PBAT drying, obtains the first mixture；
(2) into first mixture be added micron order mineral powder, nanoscale mineral powder, with the revolving speed of 500r/min into
Row mixing 6min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, is heated to 35 DEG C, is mixed with the revolving speed of 700r/min
8min obtains third mixture；
(4) by the third mixture 85 DEG C at a temperature of carry out melting extrusion, pelletizing is to get arriving the degradable
Low temperature polyester alloy 3D printing material.
Embodiment 3
A kind of degradable low temperature polyester alloy 3D printing material, the raw material including following parts by weight:
The micron order mineral powder is kaolin, and the mesh number of the micron order mineral powder is 8000 mesh, the nanoscale mine
Mountain flour be 6nm calcium carbonate, the biodegradation promotor be potassium dihydrogen phosphate, the lubricant be calcium stearate, it is described at
Core agent is nano silica.
Wherein, the melt index of the PCL is 5.4g/10min, and test condition is 160 DEG C/2.16kg, weight average molecular weight
It is 90000, melting temperature is 60 DEG C.
Wherein, the melt index of the PBAT is 3g/10min, and test condition is 190 DEG C/2.16kg, and weight average molecular weight is
5000, Vicat softening point is 85 DEG C, and heat distortion temperature is 50 DEG C.
A kind of preparation method of degradable low temperature polyester alloy 3D printing material as described above, includes the following steps:
(1) mixing 3min will be carried out with the revolving speed of 300r/min after PCL drying, obtains the first mixture；
(2) into first mixture be added micron order mineral powder, nanoscale mineral powder, with the revolving speed of 500r/min into
Row mixing 6min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, is heated to 35 DEG C, is mixed with the revolving speed of 700r/min
8min obtains third mixture；
(4) by the third mixture 85 DEG C at a temperature of carry out melting extrusion, pelletizing is to get arriving the degradable
Low temperature polyester alloy 3D printing material.
Embodiment 4
A kind of degradable low temperature polyester alloy 3D printing material, the raw material including following parts by weight:
The micron order mineral powder and nanoscale mineral powder are glass microballoon, and the mesh number of the micron order mineral powder is
7000 mesh, the partial size of the nanoscale mineral powder are 6nm, and the biodegradation promotor is N- lauroyl glutamate, the profit
Lubrication prescription is polyethylene wax, and the nucleating agent is 1,3,5- benzene tri carboxylic acid amides.
Wherein, the melt index of the PCL is 5.6g/10min, and test condition is 160 DEG C/2.16kg, weight average molecular weight
It is 70000, melting temperature is 59 DEG C.
Wherein, the melt index of the PBAT is 4.5g/10min, and test condition is 190 DEG C/2.16kg, weight average molecular weight
It is 13000, Vicat softening point is 80 DEG C, and heat distortion temperature is 45 DEG C.
A kind of preparation method of degradable low temperature polyester alloy 3D printing material as described above, includes the following steps:
(1) mixing 3min will be carried out with the revolving speed of 300r/min after PCL and PBAT drying, obtains the first mixture；
(2) into first mixture be added micron order mineral powder, nanoscale mineral powder, with the revolving speed of 500r/min into
Row mixing 6min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, is heated to 35 DEG C, is mixed with the revolving speed of 700r/min
8min obtains third mixture；
(4) by the third mixture 85 DEG C at a temperature of carry out melting extrusion, pelletizing is to get arriving the degradable
Low temperature polyester alloy 3D printing material.
Embodiment 5
A kind of degradable low temperature polyester alloy 3D printing material, the raw material including following parts by weight:
The micron order mineral powder and nanoscale mineral powder are glass microballoon, and the mesh number of the micron order mineral powder is
6000 mesh, the partial size of the nanoscale mineral powder are 10nm, and the biodegradation promotor is N- lauroyl glutamate, the profit
Lubrication prescription is polyethylene wax, and the nucleating agent is nano rare earth.
Wherein, the melt index of the PCL is 5.8g/10min, and test condition is 160 DEG C/2.16kg, weight average molecular weight
It is 50000, melting temperature is 58 DEG C.
Wherein, the melt index of the PBAT is 6g/10min, and test condition is 190 DEG C/2.16kg, and weight average molecular weight is
12000, Vicat softening point is 75 DEG C, and heat distortion temperature is 40 DEG C.
A kind of preparation method of degradable low temperature polyester alloy 3D printing material as described above, includes the following steps:
A kind of preparation method of degradable low temperature polyester alloy 3D printing material as described above, includes the following steps:
(1) mixing 3min will be carried out with the revolving speed of 300r/min after PCL and PBAT drying, obtains the first mixture；
(2) into first mixture be added micron order mineral powder, nanoscale mineral powder, with the revolving speed of 500r/min into
Row mixing 6min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, is heated to 35 DEG C, is mixed with the revolving speed of 700r/min
8min obtains third mixture；
(4) by the third mixture 85 DEG C at a temperature of carry out melting extrusion, pelletizing is to get arriving the degradable
Low temperature polyester alloy 3D printing material.
Embodiment 6
A kind of degradable low temperature polyester alloy 3D printing material, the raw material including following parts by weight:
The micron order mineral powder is made of calcium carbonate and glass microballoon by weight the ratio of 1:1, the micron order mine
The mesh number of object powder is 7000 mesh, and the nanoscale mineral powder is made of talcum powder and glass microballoon by weight the ratio of 1:1, institute
The partial size for stating nanoscale mineral powder is 6nm, and the biodegradation promotor is N- lauroyl glutamate, and the lubricant is poly- second
Alkene wax, the nucleating agent are 1,3,5- benzene tri carboxylic acid amides.
Wherein, the melt index of the PCL is 5.6g/10min, and test condition is 160 DEG C/2.16kg, weight average molecular weight
It is 70000, melting temperature is 59 DEG C.
Wherein, the melt index of the PBAT is 4.5g/10min, and test condition is 190 DEG C/2.16kg, weight average molecular weight
It is 13000, Vicat softening point is 80 DEG C, and heat distortion temperature is 45 DEG C.
A kind of preparation method of degradable low temperature polyester alloy 3D printing material as described above, includes the following steps:
(1) mixing 3min will be carried out with the revolving speed of 300r/min after PCL and PBAT drying, obtains the first mixture；
(2) into first mixture be added micron order mineral powder, nanoscale mineral powder, with the revolving speed of 500r/min into
Row mixing 6min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, is heated to 35 DEG C, is mixed with the revolving speed of 700r/min
8min obtains third mixture；
(4) by the third mixture 85 DEG C at a temperature of carry out melting extrusion, pelletizing is to get arriving the degradable
Low temperature polyester alloy 3D printing material.
To the 3D printing material of embodiment 1-5 into performance test, the result is as follows:
As seen from the above table, 3D printing material of the invention has excellent mechanical property, and 3D printing temperature is lower, can
To meet the printing demand of 3D printing pen, printing effect also highly significant.And embodiment 6 selects the appropriate particle size calcium carbonate of compounding
Tensile property, bending property and hardness can be being promoted with glass microballoon, and still possess preferable 3D printing effect.
Embodiment 7
The present embodiment the difference from embodiment 1 is that:
A kind of preparation method of degradable low temperature polyester alloy 3D printing material, includes the following steps:
(1) mixing 4min will be carried out with the revolving speed of 200r/min after PCL and PBAT drying, obtains the first mixture；
(2) into first mixture be added micron order mineral powder, nanoscale mineral powder, with the revolving speed of 400r/min into
Row mixing 8min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, is heated to 30 DEG C, is mixed with the revolving speed of 600r/min
10min obtains third mixture；
(4) by the third mixture 75 DEG C at a temperature of carry out melting extrusion, pelletizing is to get arriving the degradable
Low temperature polyester alloy 3D printing material.
Embodiment 8
The present embodiment the difference from embodiment 1 is that:
A kind of preparation method of degradable low temperature polyester alloy 3D printing material, includes the following steps:
(1) mixing 2min will be carried out with the revolving speed of 400r/min after PCL and PBAT drying, obtains the first mixture；
(2) into first mixture be added micron order mineral powder, nanoscale mineral powder, with the revolving speed of 600r/min into
Row mixing 4min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, is heated to 40 DEG C, is mixed with the revolving speed of 800r/min
6min obtains third mixture；
(4) by the third mixture 95 DEG C at a temperature of carry out melting extrusion, pelletizing is to get arriving the degradable
Low temperature polyester alloy 3D printing material.
Embodiment 9
The present embodiment the difference from embodiment 1 is that:
A kind of degradable low temperature polyester alloy 3D printing material, the raw material including following parts by weight:
Comparative example 1
A kind of degradable low temperature polyester alloy 3D printing material, the raw material including following parts by weight:
The micron order mineral powder is the glass microballoon of 7000 mesh, and the biodegradation promotor is N- lauroyl paddy ammonia
Acid, the lubricant are polyethylene wax, and the nucleating agent is 1,3,5- benzene tri carboxylic acid amides.
Wherein, the melt index of the PCL is 5.6g/10min, and test condition is 160 DEG C/2.16kg, weight average molecular weight
It is 70000, melting temperature is 59 DEG C.
Wherein, the melt index of the PBAT is 4.5g/10min, and test condition is 190 DEG C/2.16kg, weight average molecular weight
It is 13000, Vicat softening point is 80 DEG C, and heat distortion temperature is 45 DEG C.
A kind of preparation method of degradable low temperature polyester alloy 3D printing material as described above, includes the following steps:
(1) mixing 3min will be carried out with the revolving speed of 300r/min after PCL and PBAT drying, obtains the first mixture；
(2) into first mixture be added micron order mineral powder, nanoscale mineral powder, with the revolving speed of 500r/min into
Row mixing 6min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, is heated to 35 DEG C, is mixed with the revolving speed of 700r/min
8min obtains third mixture；
(4) by the third mixture 85 DEG C at a temperature of carry out melting extrusion, pelletizing is to get arriving the degradable
Low temperature polyester alloy 3D printing material.
Comparative example 2
A kind of degradable low temperature polyester alloy 3D printing material, the raw material including following parts by weight:
The nanoscale mineral powder is the glass microballoon of 6nm, and the biodegradation promotor is N- lauroyl glutamate, institute
Stating lubricant is polyethylene wax, and the nucleating agent is 1,3,5- benzene tri carboxylic acid amides.
Wherein, the melt index of the PCL is 5.6g/10min, and test condition is 160 DEG C/2.16kg, weight average molecular weight
It is 70000, melting temperature is 59 DEG C.
Wherein, the melt index of the PBAT is 4.5g/10min, and test condition is 190 DEG C/2.16kg, weight average molecular weight
It is 13000, Vicat softening point is 80 DEG C, and heat distortion temperature is 45 DEG C.
A kind of preparation method of degradable low temperature polyester alloy 3D printing material as described above, includes the following steps:
(1) mixing 3min will be carried out with the revolving speed of 300r/min after PCL and PBAT drying, obtains the first mixture；
(2) into first mixture be added micron order mineral powder, nanoscale mineral powder, with the revolving speed of 500r/min into
Row mixing 6min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, is heated to 35 DEG C, is mixed with the revolving speed of 700r/min
8min obtains third mixture；
(4) by the third mixture 85 DEG C at a temperature of carry out melting extrusion, pelletizing is to get arriving the degradable
Low temperature polyester alloy 3D printing material.
To the 3D printing material of comparative example 1 and comparative example 2 into performance test, the result is as follows:
By comparative example as above it is found that will cause using single micron order mineral powder or single nanoscale mineral powder
The reduction of mechanical property, and processing fluidity is also poor, and there is also larger problems for printing effect.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of degradable low temperature polyester alloy 3D printing material, it is characterised in that: the raw material including following parts by weight:
2. a kind of degradable low temperature polyester alloy 3D printing material according to claim 1, it is characterised in that: including as follows
The raw material of parts by weight:
3. a kind of degradable low temperature polyester alloy 3D printing material according to claim 1, it is characterised in that: the PCL
Melt index be 5.4-5.8g/10min, test condition be 160 DEG C/2.16kg, weight average molecular weight 50000-90000, melt
Melting temperature is 58-60 DEG C.
4. a kind of degradable low temperature polyester alloy 3D printing material according to claim 1, it is characterised in that: the PBAT
Melt index be 3-6g/10min, test condition be 190 DEG C/2.16kg, weight average molecular weight 12000-15000, dimension card it is soft
Changing point is 75-85 DEG C, and heat distortion temperature is 40-50 DEG C.
5. a kind of degradable low temperature polyester alloy 3D printing material according to claim 1, it is characterised in that: the micron
Grade mineral powder be one of talcum powder, calcium carbonate, kaolin, glass microballoon or more than one, the micron order mineral powder
Mesh number is 5000-8000 mesh.
6. a kind of degradable low temperature polyester alloy 3D printing material according to claim 1, it is characterised in that: the nanometer
Grade mineral powder be one of talcum powder, calcium carbonate, glass microballoon or more than one, the partial size of the nanoscale mineral powder is 2-
10nm。
7. a kind of degradable low temperature polyester alloy 3D printing material according to claim 1, it is characterised in that: the biology
Degradation of promoter be one of di(2-ethylhexyl)phosphate light calcium, phosphoric acid the second light industry bureau potassium, N- lauroyl glutamate or more than one.
8. a kind of degradable low temperature polyester alloy 3D printing material according to claim 1, it is characterised in that: the lubrication
Agent be one of pentaerythritol stearate, zinc stearate, calcium stearate, silicone oil, polyethylene wax or more than one.
9. a kind of degradable low temperature polyester alloy 3D printing material according to claim 1, it is characterised in that: the nucleation
Agent be one of montanic acid sodium, inorganic laminated silicate, nano silica, 1,3,5- benzene tri carboxylic acid amide, nano rare earth or
More than one.
10. a kind of preparation method of degradable low temperature polyester alloy 3D printing material described in any one of claim 1-9,
It is characterized in that: including the following steps:
(1) mixing 2-4min will be carried out with the revolving speed of 200-400r/min after PCL and PBAT drying, obtains the first mixture；
(2) into first mixture be added micron order mineral powder, nanoscale mineral powder, with the revolving speed of 400-600r/min into
Row mixing 4-8min, obtains the second mixture；
(3) biodegradation promotor is added toward the second mixture, is heated to 30-40 DEG C, carried out with the revolving speed of 600-800r/min
6-10min is mixed, third mixture is obtained；
(4) by the third mixture 75-95 DEG C at a temperature of carry out melting extrusion, pelletizing is to get arriving the degradable
Low temperature polyester alloy 3D printing material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110204873A (en) * | 2019-04-17 | 2019-09-06 | 广东波斯科技股份有限公司 | For the shape memory PCL composite material of 3D printing and its application |
| CN110615979A (en) * | 2019-10-31 | 2019-12-27 | 孝感市易生新材料有限公司 | 3D printing material capable of being cooled and solidified quickly and preparation method thereof |
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| CN105524399A (en) * | 2015-12-29 | 2016-04-27 | 银禧工程塑料（东莞）有限公司 | A 3D printing polymer material and a preparing method thereof |
| CN106349661A (en) * | 2015-07-20 | 2017-01-25 | 黑龙江鑫达企业集团有限公司 | Polycaprolactone (PCL) material for 3D printing |
| CN106832838A (en) * | 2017-03-17 | 2017-06-13 | 金旸（厦门）新材料科技有限公司 | It is a kind of to polish in the 3D printing material and methods for making and using same of metal appearance |
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| CN106349661A (en) * | 2015-07-20 | 2017-01-25 | 黑龙江鑫达企业集团有限公司 | Polycaprolactone (PCL) material for 3D printing |
| CN105524399A (en) * | 2015-12-29 | 2016-04-27 | 银禧工程塑料（东莞）有限公司 | A 3D printing polymer material and a preparing method thereof |
| CN106832838A (en) * | 2017-03-17 | 2017-06-13 | 金旸（厦门）新材料科技有限公司 | It is a kind of to polish in the 3D printing material and methods for making and using same of metal appearance |
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| CN110204873A (en) * | 2019-04-17 | 2019-09-06 | 广东波斯科技股份有限公司 | For the shape memory PCL composite material of 3D printing and its application |
| CN110204873B (en) * | 2019-04-17 | 2021-10-29 | 广东波斯科技股份有限公司 | Shape memory PCL composite material for 3D printing and application thereof |
| CN110615979A (en) * | 2019-10-31 | 2019-12-27 | 孝感市易生新材料有限公司 | 3D printing material capable of being cooled and solidified quickly and preparation method thereof |
| CN110615979B (en) * | 2019-10-31 | 2022-02-08 | 孝感市易生新材料有限公司 | 3D printing material capable of being cooled and solidified quickly and preparation method thereof |
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