CN109135218A - A kind of low temperature 3D printing material and preparation method thereof - Google Patents
A kind of low temperature 3D printing material and preparation method thereof Download PDFInfo
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- CN109135218A CN109135218A CN201810587217.5A CN201810587217A CN109135218A CN 109135218 A CN109135218 A CN 109135218A CN 201810587217 A CN201810587217 A CN 201810587217A CN 109135218 A CN109135218 A CN 109135218A
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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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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Abstract
The invention discloses a kind of low temperature 3D printing materials, according to parts by weight, including following components: 70-85 parts of polycaprolactone, 2-8 parts of composite epoxy resin, 1-3 parts of polypropylene terephthalate, 1-5 parts of diisooctyl phthalate, 1-3 parts of nucleating agent, 1-3 parts of crosslinking agent, 8-23 parts of blanc fixe, 1-3 parts of lubricant, 0.1-0.5 parts of nanoparticle；The composite epoxy resin includes bisphenol A type epoxy resin and bisphenol f type epoxy resin, and the weight ratio of the bisphenol A type epoxy resin and bisphenol f type epoxy resin is 2-5:1.The crystallization hardness and surface gloss of low temperature 3D printing material can be improved in the present invention.
Description
Technical field
The invention belongs to 3D printing field of material technology, and in particular to a kind of low temperature 3D printing material and preparation method thereof.
Background technique
Polycaprolactone (Polycaprolactone, abbreviation PCL) is by 6-caprolactone in metallo-organic compound (such as four
Phenyltin) catalyst is made, ring-opening polymerisation forms under the conditions of dihydroxy or trihydroxy make initiator, belong to aggretion type polyester, point
Son amount is different and different with the type and dosage of starting material from discrimination degree, there is 5 nonpolar methylene-on structural repeat unit
CH2With a polar ester groups-COO-.Polycaprolactone has good flexibility, Memorability and workability, while in nature
Middle ester group structure is easily decomposed by microorganism or enzyme, and in soil and water environment, the 6-12 month can resolve into CO completely2And H2O has life
Biodegradable, good compatibility can be fine with PE, PP, ABS, AS, PC, PVAC, PVB, PVE, PA, PLA natural rubber etc.
Ground mutual tolerance.It is fine with biological cell compatibility in vivo, cell can on its pedestal normal growth, and can be biodegradable into CO2And H2O,
With biocompatibility.Tg is -60 DEG C, very soft, has great extensibility；Its fusing point be 60-63 DEG C, can low temperature at
Type.With high crystalline and low melting point, PCL is a kind of semicrystalline nontoxicity polymer, and crystallinity is about 45% or so, tool
There are ultralow glass transition temperature Tg (about -60 DEG C), polycaprolactone is not hygroscopic, and the methods of extrusion, blow molding, injection molding can be used and be made
Fiber, thin slice, sheet material, wire rod etc.；Polycaprolactone decomposition temperature is about 350 DEG C, and the decomposition temperature of other polyester is generally 250
DEG C or so, therefore it has good thermal stability.
At present in 3D printing industry, there are the following problems as 3D printing material for polycaprolactone material, 1.: polycaprolactone material
Material crystallization hardness partially it is soft cause gear be engaged during transportation do not cause tightly feeding skidding cannot continue feeding, 2.: material table
There are coarse phenomenons for face smoothness, increase motor in turn in the frictional force that feeding process increases wire rod and feeds inside pipe wall
Load, problem above seriously affected that printing is normal to be used.At the same time, the crystallization of existing low temperature 3D printing material is hard
Degree and surface gloss are also unable to satisfy the requirement of existing industry, need to be further increased.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of low temperature 3D printing materials and preparation method thereof.Come
Overcome in the prior art polycaprolactone there are the shortcomings that, and improve the practicability of product.The present invention, which can significantly improve, to be gathered in oneself
Ester crystallizes the glossiness of hardness and surface, and solution gear is engaged during transportation does not cause tightly feeding skidding that cannot continue feeding
The problem of and the problem of increase wire rod in the feeding process and feed the frictional force of inside pipe wall, and then improve polycaprolactone low temperature
Consumptive material while improving the crystallization hardness and surface gloss of low temperature 3D printing material in the practicability in 3D printing field.
The invention adopts the following technical scheme:
A kind of low temperature 3D printing material, according to parts by weight, including following components:
The composite epoxy resin includes bisphenol A type epoxy resin and bisphenol f type epoxy resin, the bisphenol type epoxy
The weight ratio of resin and bisphenol f type epoxy resin is 2-5:1.Bisphenol A type epoxy resin and bisphenol f type epoxy resin are mixed to prepare
The composite epoxy resin.
Further, the molecular weight of the polycaprolactone is 40000-80000.
Further, the epoxide number of the bisphenol A type epoxy resin is 0.23-0.38, the epoxy of bisphenol f type epoxy resin
Value is 0.2-0.5.
Further, the nucleating agent is sorbierite.
Further, the crosslinking agent is vinyl monomer.
Further, the crosslinking agent is acrylic acid, hydroxy-ethyl acrylate, hydroxypropyl acrylate, methacrylic acid, methyl
One of hydroxy-ethyl acrylate, hydroxymethyl acrylamide (or N hydroxymethyl acrylamide) are a variety of.
Further, the blanc fixe is the powder of 5000-8000 mesh number.
Further, the lubricant is that higher aliphatic, fatty acid alcohol, silicone oil are one such or a variety of.
Further, the nanoparticle includes nano-titanium dioxide and nano lanthanum oxide.Optionally, nano-titanium dioxide
Weight ratio with nano lanthanum oxide is 5-10:1.
Further, the partial size of the nano-titanium dioxide is 10-100nm；Optionally, the grain of the nano-titanium dioxide
Diameter is 10-50nm；Optionally, the partial size of the nano-titanium dioxide is 50-100nm.
Further, the partial size of the nano lanthanum oxide is 50-100nm；Optionally, the partial size of the nano lanthanum oxide is
50-80nm；The partial size of the nano lanthanum oxide is 80-100nm.
Further, the nucleating agent is sorbierite.
A kind of preparation method of low temperature 3D printing material, comprising the following steps:
(1) polycaprolactone, lubricant are put into high speed mixer, (temperature is no more than the 38 DEG C) mixing at 2-38 DEG C
Uniformly, incorporation time can be 3-8min, such as 5min；
(2) composite epoxy resin, polypropylene terephthalate, diisooctyl phthalate, nucleation is then added
Agent, crosslinking agent, blanc fixe, nanoparticle stir evenly at 5-38 DEG C, and mixing time can be 3-8min, such as
5min；
(3) double screw extruder will be added through the mixed material of step (2) to be granulated, through screw rod gun barrel blended melting
It squeezes out, water cooling, traction, the air-dried water removal in surface, obtains low temperature 3D printing material granule；
The wherein temperature setting of double screw extruder an are as follows: area: 60-70 DEG C；2nd area: 80-90 DEG C；3rd area: 90-100 DEG C；
4th area: 100-110 DEG C；5th area: 90-110 DEG C；6th area: 80-110 DEG C；Seven 80-100 DEG C of areas；8th area: 90-110 DEG C；9th area:
70-80℃；Screw speed is 300-450 rev/min；The cooling temperature of water is controlled at 0-15 DEG C；
(4) the low temperature 3D printing material granule is put into moisture drying machine and carries out drying and processing, obtain low temperature 3D printing
Material dry particle, moisture drying machine temperature setting are 35-40 DEG C, drying time 2-3h；
(5) the low temperature 3D printing material dry particle after step (4) drying is added in single screw extrusion machine and is processed
Obtain the low temperature 3D printing material.
During 3D printing, the nucleating agent and barium sulfate or other auxiliary agents that are usually added into will affect the processing ruler of material
Very little precision and print temperature, and present invention adds after nucleating agent and blanc fixe powder, find through overtesting, addition its
Its component or auxiliary agent will not influence to material accurate to dimension and print temperature, while the material of polycaprolactone can be improved
Hardness and surface flatness are crystallized, the close transportation problem of polycaprolactone gear is solved and reduces and feeding inside pipe wall frictional force
The problem of.
In engaged gears transmission process, partially soft material resistance during being fed to nozzle can become 3D printing wire rod
Greatly, at this moment gear can wear material line footpath become smaller and cause occlusion not tight and cannot continue feeding, seriously affect normal print, needle
To this problem of the prior art, the present invention can significantly improve the crystallization hardness of material and the surface brightness of product, while not
Influence processing stability, the compatibility of object and the temperature of printing of product.
The crystallization hardness of low temperature 3D printing material of the invention is 95shore A, and roughness grade is 0.05 micron,
Feel and mesh test surfaces are smooth.
Compared with prior art, advantages of the present invention are as follows: formula of the invention as a whole, is mutually assisted by each component
It adjusts, the glossiness of polycaprolactone crystallization hardness and surface can be significantly improved, solution gear is engaged during transportation not to be made tightly
The problem of cannot continuing feeding at feeding skidding, and increase the frictional force of wire rod and charging inside pipe wall in the feeding process and ask
Topic, and then polycaprolactone low temperature consumptive material is improved in the practicability in 3D printing field, while improving low temperature 3D printing material
Crystallize hardness and surface gloss.
Specific embodiment
In order to preferably explain the present invention, it is described further now in conjunction with following specific embodiments, but the present invention is unlimited
In specific embodiment.
Embodiment 1
A kind of low temperature 3D printing material, preparation method the following steps are included:
(1) 83 parts of polycaprolactones (molecular weight 60000) (without being dried in advance), 1.5 parts of white silicone oil are put into height
In fast batch mixer, (temperature is no more than 38 DEG C) are uniformly mixed, incorporation time 5min at 2-38 DEG C；
(2) 2 parts of composite epoxy resins are then added, and (weight ratio of bisphenol A type epoxy resin and bisphenol f type epoxy resin is
2:1), 1 part of polypropylene terephthalate, 1 part of diisooctyl phthalate, 1.5 portions of nucleating agents, 2 parts of methylol propylene
Amide, 12 parts of blanc fixes (6000 mesh), 0.1 part of nanoparticle (nano-titanium dioxide (partial size 10-100nm) and nano oxygen
The weight ratio for changing lanthanum (partial size 50-100nm) is 5:1), it is stirred evenly at 5-38 DEG C, mixing time 5min；
(3) double screw extruder will be added through the mixed material of step (2) to be granulated, through screw rod gun barrel blended melting
It squeezes out, water cooling, traction, the air-dried water removal in surface, obtains low temperature 3D printing material granule；
The wherein temperature setting of double screw extruder an are as follows: area: 60 DEG C；2nd area: 85 DEG C；3rd area: 90 DEG C；4th area: 100
℃；5th area: 90 DEG C；6th area: 90 DEG C；Seven 90 DEG C of areas；8th area: 90 DEG C；9th area: 70 DEG C；Screw speed is 300-450 rpm
Clock；The cooling temperature of water is controlled at 0-15 DEG C；
(4) the low temperature 3D printing material granule is put into moisture drying machine and carries out drying and processing, obtain low temperature 3D printing
Material dry particle, moisture drying machine temperature setting are 35-40 DEG C, drying time 2-3h；
(5) the low temperature 3D printing material dry particle after step (4) drying is added in single screw extrusion machine and is processed
The low temperature 3D printing material is obtained, the wire rod line footpath specification of finished product is 1.5-4.0MM.
Embodiment 2
A kind of low temperature 3D printing material, preparation method the following steps are included:
(1) 73 parts of polycaprolactones (molecular weight 60000) (without being dried in advance), 1.5 parts of white silicone oil are put into height
In fast batch mixer, (temperature is no more than 38 DEG C) are uniformly mixed, incorporation time 5min at 2-38 DEG C；
(2) 5 parts of composite epoxy resins are then added, and (weight ratio of bisphenol A type epoxy resin and bisphenol f type epoxy resin is
5:1), 3 parts of polypropylene terephthalate, 3 parts of diisooctyl phthalates, 1 portion of nucleating agent, 2.5 parts of methylol propylene
Amide, 22 parts of blanc fixes (8000 mesh), 0.5 part of nanoparticle (nano-titanium dioxide (partial size 10-100nm) and nano oxygen
The weight ratio for changing lanthanum (partial size 50-100nm) is 10:1), it is stirred evenly at 5-38 DEG C, mixing time 5min；
(3) double screw extruder will be added through the mixed material of step (2) to be granulated, through screw rod gun barrel blended melting
It squeezes out, water cooling, traction, the air-dried water removal in surface, obtains low temperature 3D printing material granule；
The wherein temperature setting of double screw extruder an are as follows: area: 65 DEG C；2nd area: 85 DEG C；3rd area: 90 DEG C；4th area: 100
℃；5th area: 90 DEG C；6th area: 90 DEG C；Seven 90 DEG C of areas；8th area: 100 DEG C；9th area: 80 DEG C；Screw speed is 300-450 rpm
Clock；The cooling temperature of water is controlled at 0-15 DEG C；
(4) the low temperature 3D printing material granule is put into moisture drying machine and carries out drying and processing, obtain low temperature 3D printing
Material dry particle, moisture drying machine temperature setting are 35-40 DEG C, drying time 2-3h；
(5) the low temperature 3D printing material dry particle after step (4) drying is added in single screw extrusion machine and is processed
The low temperature 3D printing material is obtained, the wire rod line footpath specification of finished product is 1.5-4.0MM.
Comparative example 1
For comparative example 1 other than without blanc fixe and nanoparticle, remaining is same as Example 1.
Comparative example 2
Comparative example 2 is other than without composite epoxy resin and diisooctyl phthalate, remaining and 1 phase of embodiment
Together.
Table 1: quantitative measurement.
Regular grade 3D printer and common 3D printing pen is often used to test using desktop, printer does not need bottom plate heating, horse
It is unsuitable too long up to nozzle distance is fed to, it controls in 6 centimetres (polycaprolactone belongs to soft material, it is not recommended that long range feeding), surveys
Trial product consumptive material diameter specifications are 1.75MM, nozzle print speed is 20-60mm/s, extrusion output 0.09-0.12 cubic centimetre/point
Clock rate degree is adjustable, and the nozzle diameter of 3D printer is 0.2-0.8MM.
The embodiment of the present invention 1, embodiment 2 can meet the requirement of 3D printing low temperature moulding as can be seen from Table 1, right
DIY fan especially children had both remained original energy-saving and environment-friendly reason in use, the phenomenon that avoiding burn and scald generation
It reads, while improving using operation sense, the hardness of the D printing consumables of the low temperature in the embodiment of the present invention 1 is 95shorA, is made
FDM-3D printer gear occlusion more closely conveying material it is smooth, printing can be formed normally, in 3D printing pen in use,
It feeds smooth, is not in fracture and deformation.And comparative example 1 and comparative example 2 can not achieve the effect of surface-brightening, print simultaneously
Temperature is higher, can not meet the requirement of 3D printing low temperature moulding.
It, will be so that frictional force increases, if print temperature is more than 100 if hardness is in 85shorA or following, rough surface
Degree just cannot achieve low temperature moulding, where the value for losing low temperature functional.In addition, lacking composite epoxy by test discovery
Resin and polypropylene terephthalate can reduce crystallization hardness and surface gloss.
Above experiments have shown that the low temperature 3D printing material surface smoothness of the embodiment of the present invention is good, hardness is higher, mobility
Preferably, 3D printing molding is fast, and print temperature is low, will be so that 3D printing product has preferably degree physical property, in this way can be significantly
PCL material is opened up in the practicability in 3D printing industrial application field.
Above is only a specific embodiment of the present invention, it is not intended to limit the scope of the invention, all utilizations
The equivalent transformation that the present invention makees, is applied directly or indirectly in other relevant technical fields, similarly includes of the invention
Among scope of patent protection.
Claims (10)
1. a kind of low temperature 3D printing material, which is characterized in that according to parts by weight, including following components:
The composite epoxy resin includes bisphenol A type epoxy resin and bisphenol f type epoxy resin, the bisphenol A type epoxy resin
Weight ratio with bisphenol f type epoxy resin is 2-5:1.
2. low temperature 3D printing material according to claim 1, which is characterized in that the molecular weight of the polycaprolactone is
40000-80000。
3. low temperature 3D printing material according to claim 1, which is characterized in that the epoxy of the bisphenol A type epoxy resin
Value is 0.23-0.38, and the epoxide number of bisphenol f type epoxy resin is 0.2-0.5.
4. low temperature 3D printing material according to claim 1, which is characterized in that the crosslinking agent is vinyl monomer.
5. low temperature 3D printing material according to claim 1, which is characterized in that the crosslinking agent is acrylic acid, acrylic acid
One of hydroxyl ethyl ester, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxymethyl acrylamide are a variety of.
6. low temperature 3D printing material according to claim 1, which is characterized in that the blanc fixe is 5000-8000
The powder of mesh number.
7. low temperature 3D printing material according to claim 1, which is characterized in that the nanoparticle includes nanometer titanium dioxide
Titanium and nano lanthanum oxide.
8. low temperature 3D printing material according to claim 7, which is characterized in that the partial size of the nano-titanium dioxide is
10-100nm；The partial size of the nano lanthanum oxide is 50-100nm.
9. low temperature 3D printing material according to claim 1, which is characterized in that the nucleating agent is sorbierite.
10. a kind of preparation method of low temperature 3D printing material according to claim 1 to 9, which is characterized in that
The following steps are included:
(1) polycaprolactone, lubricant are put into high speed mixer, are uniformly mixed at 2-38 DEG C；
(2) composite epoxy resin, polypropylene terephthalate, diisooctyl phthalate, nucleating agent, friendship is then added
Join agent, blanc fixe, nanoparticle, is stirred evenly at 5-38 DEG C；
(3) double screw extruder will be added through the mixed material of step (2) be granulated, blended melting extrusion, water is cooling,
Traction, surface air-dry water removal, obtain low temperature 3D printing material granule；
The wherein temperature setting of double screw extruder an are as follows: area: 60-70 DEG C；2nd area: 80-90 DEG C；3rd area: 90-100 DEG C；Four
Area: 100-110 DEG C；5th area: 90-110 DEG C；6th area: 80-110 DEG C；Seven 80-100 DEG C of areas；8th area: 90-110 DEG C；9th area: 70-
80℃；Screw speed is 300-450 rev/min；The cooling temperature of water is controlled at 0-15 DEG C；
(4) the low temperature 3D printing material granule is put into moisture drying machine and carries out drying and processing, obtain low temperature 3D printing material
Dry particle, moisture drying machine temperature setting are 35-40 DEG C, drying time 2-3h；
(5) the low temperature 3D printing material dry particle addition single screw extrusion machine after step (4) drying is processed to obtain described
Low temperature 3D printing material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880313A (en) * | 2019-02-11 | 2019-06-14 | 福建师范大学 | A kind of dendritic phthalocyanine@SiO2Water disposal device and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105400164A (en) * | 2015-12-03 | 2016-03-16 | 深圳光华伟业股份有限公司 | Low-temperature 3D printing material and preparation method thereof |
| CN106867214A (en) * | 2017-02-28 | 2017-06-20 | 华南理工大学 | It is a kind of for the low-temperature thermoplastic 3 D-printing material of BUILDINGS MODELS product and preparation |
| KR20170093315A (en) * | 2016-02-04 | 2017-08-16 | 서강대학교산학협력단 | Composition for Manufacturing Radiation Shielding material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105400164A (en) * | 2015-12-03 | 2016-03-16 | 深圳光华伟业股份有限公司 | Low-temperature 3D printing material and preparation method thereof |
| KR20170093315A (en) * | 2016-02-04 | 2017-08-16 | 서강대학교산학협력단 | Composition for Manufacturing Radiation Shielding material |
| CN106867214A (en) * | 2017-02-28 | 2017-06-20 | 华南理工大学 | It is a kind of for the low-temperature thermoplastic 3 D-printing material of BUILDINGS MODELS product and preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880313A (en) * | 2019-02-11 | 2019-06-14 | 福建师范大学 | A kind of dendritic phthalocyanine@SiO2Water disposal device and preparation method thereof |
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