CN113185646A - Conductive 3D printing material and preparation method thereof - Google Patents
Conductive 3D printing material and preparation method thereof Download PDFInfo
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- CN113185646A CN113185646A CN202110657470.5A CN202110657470A CN113185646A CN 113185646 A CN113185646 A CN 113185646A CN 202110657470 A CN202110657470 A CN 202110657470A CN 113185646 A CN113185646 A CN 113185646A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- 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
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- C08K3/02—Elements
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- 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
- C08K3/02—Elements
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- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a conductive 3D printing material and a preparation method thereof, wherein the conductive 3D printing material comprises acrylate oligomer resin, acrylate reactive diluent, photoinitiator, conductive filler and dispersant; the acrylate oligomer resin comprises beta-hydroxyethyl methacrylate and urethane acrylate; the polyurethane acrylate is one or more of aromatic hexafunctionality polyurethane acrylate, aliphatic hexafunctionality polyurethane acrylate and aliphatic trifunctional polyurethane acrylate. The preparation method comprises the following steps: mixing an acrylic acid active diluent and a dispersing agent, adding a conductive filler, and grinding to obtain a mixed solution A; adding acrylic acid oligomer resin into the mixed solution A, and stirring to obtain mixed solution B; and adding a photoinitiator into the mixed solution B, and stirring to obtain the conductive 3D printing material. The product printed by the conductive 3D printing material has the advantages of high mechanical strength, high hardness, good toughness, strong wear resistance and the like.
Description
Technical Field
The invention belongs to the field of resin, and relates to a conductive 3D printing material and a preparation method thereof.
Background
3D printing, also known as additive manufacturing, is one of rapid prototyping technologies, and is known as the core technology of the third industrial revolution. The material is the basis of 3D printing and is also the bottleneck restricting the 3D printing development at present.
At present, 3D printing materials mainly include engineering plastics, photosensitive resins, rubber materials, metal materials, ceramic materials, and the like, and besides, food materials such as color gypsum materials, artificial bone powder, cell biological raw materials, granulated sugar, and the like are also applied in the field of 3D printing. The raw materials used for 3D printing are developed specifically for 3D printing equipment and processes, and are distinguished from common plastics, plaster, resins, and the like, and the forms thereof generally include powder, thread, laminated sheet, liquid, and the like.
The engineering plastic is an industrial plastic used as an industrial zero-valent or housing material, and is a plastic excellent in strength, impact resistance, heat resistance, hardness, and aging resistance. Engineering plastics are the most widely used 3D printing materials at present, and common materials include ABS (Acrylonitrile Butadiene Styrene, ABS for short), PC (Polycarbonate, PC for short), nylon materials, and the like. The ABS material is a thermoplastic engineering plastic commonly used in an FDM (Fused Deposition Modeling, FDM for short) rapid forming process, has the advantages of high strength, good toughness, impact resistance and the like, has a normal deformation temperature of over 90 ℃, and can be subjected to machining (drilling and tapping), paint spraying and electroplating. The photosensitive resin consists of polymer monomer and prepolymer, in which photoinitiator is added, and under the irradiation of UV light with a certain wavelength it can immediately make polymerization reaction to complete curing. The photosensitive resin is generally in liquid state and can be used for manufacturing high-strength, high-temperature-resistant and waterproof materials. The rubber material has the characteristics of various grades of elastic materials, and the hardness, the elongation at break, the tear strength and the tensile strength of the materials make the rubber material very suitable for application fields requiring anti-skid or soft surfaces, and 3D printed rubber products mainly comprise consumer electronics, medical equipment, automotive interiors, tires, gaskets and the like. In the aspect of metal materials, metal powder used in 3D printing generally requires high purity, good sphericity, narrow particle size distribution and low oxygen content, and the metal powder materials applied to 3D printing at present mainly comprise titanium alloy, cobalt-chromium isolated stainless steel, aluminum alloy materials and the like. The ceramic powder for 3D printing is a mixture of ceramic powder and a certain binder powder.
The photosensitive resin has the advantages of high utilization rate, high curing speed, short forming period, environmental protection and the like, but the cured formed part has low hardness, poor heat resistance and poor mechanical property, and the defects influence the service performance of the photosensitive resin. Meanwhile, the 3D printing material is more and more wide in application scene and higher in demand, and various application occasions require the performances of electric conduction, heat conduction and the like. In general, a printed member is provided with a certain function by post-processing and adding a functional thin layer, and the process is complicated and the functionalization effect is limited. If directly add heat conduction filler on photosensitive resin, because the volume of adding of heat conduction interpolation is high, influenced the mechanical properties of 3D printing more.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, and the invention provides the conductive 3D printing material, wherein the nano conductive filler is added into the UV curing resin, so that the nano conductive filler has small specific gravity and good dispersibility, cannot generate sedimentation and agglomeration in the storage and printing processes, has good nano size and light penetrability, cannot influence UV printing, and cannot influence the final visible light transmittance.
In order to solve the technical problems, the invention provides a conductive 3D printing material, which comprises acrylate oligomer resin, acrylate reactive diluent, a photoinitiator, conductive filler and a dispersant; the acrylate oligomer resin comprises beta-hydroxyethyl methacrylate and urethane acrylate;
the polyurethane acrylate is one or more of aromatic six-functionality polyurethane acrylate, aliphatic six-functionality polyurethane acrylate and aliphatic three-functionality polyurethane acrylate.
In the conductive 3D printing material, the urethane acrylate is a mixture of aromatic hexa-functional urethane acrylate, aliphatic hexa-functional urethane acrylate and aliphatic tri-functional urethane acrylate mixed in a mass ratio of 1:1: 1.
In the conductive 3D printing material, the acrylate reactive diluent is one or more selected from isobornyl methacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate.
In the conductive 3D printing material, the acrylate reactive diluent is a mixture of isobornyl methacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate mixed at a ratio of 1:1: 1.
In the conductive 3D printing material, the photoinitiator is a mixture of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and benzoyl formate mixed according to a ratio of 1: 1.
Further, the conductive filler is one or more of single-walled carbon nanotubes, nano-graphene and carbon black. .
The conductive 3D printing material is further characterized in that the dispersant is Tego610S and/or Surfynol CT-136.
The conductive 3D printing material further comprises 65wt% -85 wt% of acrylate oligomer resin, 9.9wt% -10.9 wt% of acrylate reactive diluent, 3wt% of photoinitiator, 1wt% -20 wt% of conductive filler and 0.1wt% -2 wt% of dispersant.
Based on a general technical concept, the invention also provides a preparation method of the conductive 3D printing material, which comprises the following steps:
s1, mixing the acrylic acid reactive diluent and the dispersing agent, adding the conductive filler, and grinding to obtain a mixed solution A;
s2, adding acrylic acid oligomer resin into the mixed solution A, and stirring to obtain mixed solution B;
and S3, adding a photoinitiator into the mixed solution B, and stirring to obtain the conductive 3D printing material.
In the preparation method, the conductive filler in the step S1 is added in three times, the conductive filler is added for the first time and then ground for 10min to 60min at a speed of 1000r/min to 2000r/min, ground for 10min to 120min at a speed of 100 r/min to 2000r/min for the second time, and ground for 60min at a speed of 100 r/min to 2000r/min for the third time.
In the above preparation method, further, in S2, the stirring is performed in a double planetary stirring tank at a shear rate: 1-8 m/s, revolution speed: 0.1-0.6 m/s, stirring for 10-60 min.
In the above preparation method, further, in S3, the stirring is performed in a double planetary stirring tank at a shear rate: 1-8 m/s, revolution speed: 0.1-0.5 m/s, stirring for 5-60 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a conductive 3D printing material, which needs to be modified by urethane acrylate in order to not influence the mechanical property of the 3D printing material because a conductive filler with a larger specific gravity needs to be added. The single polyurethane acrylate has excellent wear resistance and flexibility, but has slow photocuring rate, high viscosity, low hardness after curing and poor corrosion resistance. According to the invention, methacrylic acid-beta-hydroxyethyl ester and urethane acrylate are taken as raw materials, carboxyl (-COO-) in the urethane acrylate and hydroxyl (-OH-) in methacrylic acid-beta-Hydroxyethyl Ester (HEMA) form hydrogen bonds, and the interaction between the hydrogen bonds increases the crosslinking density and compatibility of a curing system, so that the mechanical property of the 3D printing resin material is improved.
Furthermore, the polyurethane acrylate is prepared by mixing aliphatic hexa-functionality polyurethane acrylate, aromatic hexa-functionality polyurethane acrylate and aliphatic tri-functionality polyester acrylate UV light-cured resin. The aliphatic polyurethane acrylic resin has the advantages of high curing speed, high adhesive force and high flexibility. The aromatic polyurethane acrylic resin has high wear resistance, high toughness and good wear resistance. The combination of the two can improve the comprehensive performance of the polyurethane acrylate. Meanwhile, the invention mixes the polyurethane acrylate with six optical energy groups and the acrylate with three functional groups for use, and can form a network three-dimensional structure after the initiation of crosslinking by the photoinitiator, and has the advantages of high mechanical strength, high hardness, good toughness, strong wear resistance and the like.
(2) The invention provides a conductive 3D printing material, wherein the reactive diluent is one or more of isobornyl methacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate, the reactive diluent has the characteristics of low viscosity, thermal stability and low volume shrinkage rate, the viscosity of a 3D printing material system can be reduced, and the reactive diluent has a reactive group and can promote the curing reaction to a certain extent.
In general, the higher the monomer content, the lower the viscosity, but the higher the shrinkage after curing, the lower the mechanical properties of the cured product. According to the invention, isobornyl methacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate are mixed to be used as the reactive diluent, and the isobornyl methacrylate, the ethoxylated trimethylolpropane triacrylate and the propoxylated glycerol triacrylate are self-provided with reactive groups to participate in a curing reaction, so that a reticular polymer can be obtained after curing, the crosslinking density is high, and the mechanical property is further improved.
(3) The invention provides a conductive 3D printing material, wherein a photoinitiator is obtained by mixing phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and benzoyl formate according to the mass ratio of 1: 1. Phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide has excellent absorption performance, can be applied to a thick film system, and has the advantages of fast light absorption and low yellow cured system. The benzoyl formate is a low-yellowing liquid ultraviolet initiator and is used for initiating the UV polymerization reaction of an unsaturated prepolymerization system. A good balance is achieved between low residual odor, low exotherm after cure, and cure efficiency. The invention combines the two components, which can ensure rapid curing and give consideration to the problem of heat release in the curing reaction, so that after photoinitiation, the reaction speed is ensured to be rapid and controllable, and the yellowing resistance after reaction is good.
(4) The invention provides a conductive 3D printing material, wherein nano conductive filler is added into resin liquid for 3D printing, and the purpose of adding the nano conductive filler is to increase the conductivity of the resin liquid and at least conduct static electricity. In addition, the nano-scale conductive filler does not hinder the light transmission to a great extent due to small particle size. The UV printing ink has the advantages of small specific gravity, good dispersibility, no sedimentation and agglomeration in the storage and printing processes, and simultaneously, the nano size and the light penetrability are good, the UV printing cannot be influenced, and the final visible light transmittance cannot be influenced. The invention specifically defines that the conductive filler is a mixture of carbon nano tubes, graphene and carbon black, the carbon nano tubes and the graphene form a line-plane conductive model, and if some carbon black is added, the line-plane conductive model is a point-line-plane conductive model, so that the conductive effect is better.
(5) The preparation method of the conductive 3D printing material provided by the invention is simple in preparation process, uniform in material mixing, and capable of improving the dispersibility of the material, so that the finally manufactured printing piece has good precision and light transmittance. If the materials are not uniformly mixed, the main influence is the filler dispersibility, the filler dispersibility is poor, the light transmittance is poor, the low light transmittance can influence the curing degree of the primary curing, and the size and shape precision of a printed product are not high.
(6) The invention provides application of a conductive 3D printing material, the conductive 3D printing material is applied to SLA printing, the forming speed is high, the automation degree is high, any complex shape can be formed, the size precision is high, and the conductive 3D printing material is mainly applied to rapid forming of complex and high-precision fine workpieces.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a flow chart of a preparation process of the conductive 3D printing material in embodiment 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. Tego610S (digaku chemical wetting dispersant) and Surfynol CT-136 (air chemistry, dispersant).
Example 1
A conductive 3D printing material of embodiment 1 of the present invention includes 65wt% of acrylate oligomer resin, 9.9wt% of acrylate reactive diluent, 0.1wt% of fluorescent whitening agent, 3wt% of photoinitiator, 20wt% of conductive filler, and 2wt% of dispersant.
The acrylate oligomer resin was composed of 20wt% of beta-hydroxyethyl methacrylate (available from Guangzhou high Industrial Co., Ltd.) and 80wt% of urethane acrylate. The polyurethane acrylate is prepared by mixing hexafunctionality polyurethane acrylate (purchased from Changxing, Etercure6145-100, Taiwan, China), aliphatic hexafunctionality polyurethane acrylate (purchased from Sanwang chemical materials Co., Ltd., product number SW5000, Guangzhou) and trifunctional polyester acrylate UV light-cured resin (purchased from Xiamena, Akama chemical materials Co., Ltd., product number ACC 301) according to the mass ratio of 1:1: 1.
The acrylate reactive diluent is prepared by mixing isobornyl methacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate according to the mass ratio of 1:1: 1.
The optical brightener is a high molecular weight optical brightener of the thiophene benzotriazole type (available from basf Tinopal OB CO, germany).
The photoinitiator is phenyl bis (2,4, 6-trimethyl benzoyl) phosphine oxide (CAS Number)162881-26-7, from Pasteur photoinitiators, Germany, and benzoyl formate (formula C)20H20O7(ii) a CAS Number:211510-16-6, from Pasteur, Germany) in a mass ratio of 1: 1.
The conductive filler is prepared by mixing single-walled carbon nanotubes, graphene and carbon black according to the mass ratio of 1:1: 1.
The dispersing agent is prepared by mixing Tego610S (high molecular weight fatty acid derivative solution containing organic modified polysiloxane) and Surfynol CT-136 (nonionic surfactant) according to the mass ratio of 1: 1.
The preparation method of the conductive 3D printing material of this embodiment 1, referring to fig. 1, specifically includes the following steps:
(1) and uniformly mixing the acrylic acid active diluent and the dispersing agent to obtain a mixed solution.
(2) And adding the conductive filler into the mixed solution for three times, grinding at a shearing rate of 1000r/min after adding the conductive filler for the first time, and stirring for 20min, 1000r/min for the second time, 40min for the third time, 1000r/min for the third time, and 60min to obtain a mixed solution A.
(3) Transferring the mixed solution into a double-planet stirring kettle, adding methacrylic acid-beta-hydroxyethyl (acrylic resin-1) and urethane acrylate (acrylic resin-2), and then, shearing: 4m/s, revolution speed: 0.3m/s, stirring for 30min to obtain a mixed solution B.
(4) Adding the fluorescent whitening agent and other pigments into the mixed solution B, and stirring at a shear rate: 4m/s, revolution speed: 0.3m/s, stirring for 20min to obtain a mixed solution C.
(5) Adding a photoinitiator, and mixing at a shear rate: 4m/s, revolution speed: stirring for 20min at 0.2m/s to obtain the 3D printing material.
The conductive 3D printing material of example 1 above was subjected to a performance test:
1. and (3) viscosity testing: the viscosity was measured at room temperature and at the working temperature for the 3D printed material using a viscometer.
2. Surface tension test: the surface tension was measured at room temperature and at operating temperature for the 3D printed material using a tensiometer.
3. Volume shrinkage: measuring the density rho of the photosensitive resin before curing at 25 ℃ by adopting a pycnometer method and taking water as reference1And its density after complete curing rho2The volume shrinkage was calculated according to the following test:
volume shrinkage% = (ρ)2-ρ1）÷ρ2×100%。
4. And (3) hardness testing: and printing the conductive 3D printing material into a small square by using a 3D printer, and testing indentation hardness by using a hardness tester.
5. And (3) testing the bending property: the 3D printer is used for printing the conductive 3D printing material into a long strip, and the bending performance of the conductive 3D printing material is tested.
6. And (3) wear resistance test: according to international standard ISO 9352-: using a Taber abrader 5135, an H-10 wheel was selected, and a load of 8.0N was applied to both wheels and brought into contact with the specimen at a rotation speed of 30r/min, and after the specimen had been rubbed a prescribed number of times, the mass loss was calculated.
7. Testing the heat distortion temperature: the conductive 3D printing material is printed into a long strip by a 3D printer, and the thermal deformation temperature (0.45 MPa) of the conductive 3D printing material is detected.
8. Conductivity: method for testing volume resistivity of conductive and antistatic plastic according to standard GB T15662-
The detection result is as follows: the conductive 3D printing material of example 1 had a viscosity of 62.5cps at room temperature and a surface tension of 31.5 dyn/cm; viscosity at working temperature (60 ℃) is 13.5cps, surface tension is 30.8 dyn/cm; the shrinkage was 4.78%; the hardness is 90HD, the bending strength is 89Mpa, and the wear resistance is 0.054Kg/1000 r; the heat distortion temperature is 99 ℃, the granularity performance is excellent, and the conductive performance is good (3.0 x 10)2）。
Example 2
The influence of the weight ratio of beta-hydroxyethyl methacrylate and urethane acrylate on the performance of the 3D printing material was examined.
Beta-hydroxyethyl methacrylate and urethane acrylate were mixed in mass ratios of 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, and 10:0, respectively, and the remaining components and ratios were the same as in example 1, and the effects of the mass ratios on the properties of the 3D printing materials were examined, and the results are listed in table 1.
Table 1: table of the results of the effect of the ratio of beta-hydroxyethyl methacrylate and urethane acrylate on the performance of the 3D printing materials
| Mass ratio of | Volume shrinkage (%) | Hardness (HD) | Bending property (Mpa) | Wear resistance (Kg/1000 r) | Viscosity (cps) |
| 0:10 | 4.53 | 76 | 96 | 0.061 | 13.5 |
| 1:9 | 4.62 | 83 | 91 | 0.035 | 11.2 |
| 2:8 | 4.78 | 90 | 89 | 0.054 | 10.3 |
| 3:7 | 4.88 | 90 | 85 | 0.067 | 10.5 |
| 4:6 | 4.92 | 91 | 80 | 0.083 | 10.0 |
| 5:5 | 4.98 | 93 | 76 | 0.095 | 9.5 |
| 6:4 | 5.13 | 94 | 75 | 0.101 | 9.2 |
| 7:3 | 5.26 | 95 | 72 | 0.125 | 9.0 |
| 8:2 | 5.33 | 98 | 68 | 0.135 | 8.9 |
| 9:1 | 5.34 | 99 | 66 | 0.176 | 8.7 |
| 10:0 | 5.6 | 98 | 50 | 0.345 | 8.2 |
From the results of table 1, it can be seen that: if only containing urethane acrylate, the system has high viscosity, high bending property and wear resistance and low hardness; if only beta-hydroxyethyl methacrylate is contained, the flexibility of the material is poor. With the increase of the content of the urethane acrylate, the bending property, the wear resistance and the like are higher and higher, and the volume shrinkage rate and the hardness are smaller and smaller; when the mass ratio of the methacrylic acid-beta-hydroxyethyl ester to the urethane acrylate is 2:8, the hardness, the bending property and the wear resistance can reach the maximum, but the mechanical property is reduced as the content of the urethane acrylate is continuously increased.
The polyurethane acrylate is prepared by two reactions of isocyanate, long-chain diol and acrylate hydroxy ester, and has excellent wear resistance and flexibility. The methacrylic acid-beta-hydroxyethyl ester is prepared by ring-opening esterification of epoxy resin and acrylic acid under the action of a catalyst, and has excellent mechanical properties of the epoxy resin. After the two are mixed according to a certain proportion, the carboxyl (-COO-) in the urethane acrylate and the hydroxyl (-OH-) in the methacrylic acid-beta-hydroxyethyl ester form hydrogen bonds, and the interaction between the hydrogen bonds increases the crosslinking density and compatibility of a curing system, so that the curing material with excellent comprehensive performance is formed.
Example 3
The effect of acrylate oligomer resin, acrylate reactive diluent, fluorescent whitening agent, photoinitiator, conductive filler and dispersant on the performance of 3D printing material was examined.
Component 1: comprises 60wt% of acrylate oligomer resin, 9.9wt% of acrylate reactive diluent, 0.1wt% of fluorescent brightener, 3wt% of photoinitiator, 25wt% of conductive filler and 2wt% of dispersant. Wherein the components and the proportion of the components are consistent with those in the example 1.
And (2) component: comprises 65wt% of acrylate oligomer resin, 9.9wt% of acrylate reactive diluent, 0.1wt% of fluorescent brightener, 3wt% of photoinitiator, 20wt% of conductive filler and 2wt% of dispersant. Wherein the components and the proportion of the components are consistent with those in the example 1.
And (3) component: comprises 75wt% of acrylate oligomer resin, 10.9wt% of acrylate reactive diluent, 0.1wt% of fluorescent brightener, 3wt% of photoinitiator, 10wt% of conductive filler and 1wt% of dispersant. Wherein the components and the proportion of the components are consistent with those in the example 1.
And (4) component: comprises 85wt% of acrylate oligomer resin, 10.8wt% of acrylate reactive diluent, 0.1wt% of fluorescent brightener, 3wt% of photoinitiator, 1wt% of conductive filler and 0.1wt% of dispersant. Wherein the components and the proportion of the components are consistent with those in the example 1.
And (5) component: comprises 90wt% of acrylate oligomer resin, 5.8wt% of acrylate reactive diluent, 0.1wt% of fluorescent whitening agent, 3wt% of photoinitiator, 1wt% of conductive filler and 0.1wt% of dispersant. Wherein the components and the proportion of the components are consistent with those in the example 1.
And (4) component 6: comprises 65wt%, 9.9wt% of acrylate reactive diluent, 0.1wt% of fluorescent whitening agent, 3wt% of photoinitiator, 20wt% of conductive filler and 2wt% of dispersant. Wherein the urethane acrylate is only aliphatic hexa-functional urethane acrylate (purchased from sanwang chemical materials limited, guangzhou, product number SW 5000), and the other components and the proportion are consistent with those in example 1.
And (4) component 7: comprises 65wt% of acrylate oligomer resin, 9.9wt% of acrylate reactive diluent, 0.1wt% of fluorescent brightener, 3wt% of photoinitiator, 20wt% of conductive filler and 2wt% of dispersant. Wherein the urethane acrylate is only trifunctional polyester acrylate UV light-cured resin (purchased from Xiamen Akama chemical Co., Ltd., product number ACC 301), and the rest components and the proportion are consistent with those in example 1.
The content ratios of the components and the performance results are shown in Table 2.
Table 2: result table of influence of distribution ratio of components on performance of D printing material
From the results of table 2, it can be seen that: with the increase of the content of the acrylic resin, the viscosity of the 3D printing resin is higher and higher; however, when the dispersant is added, the viscosity of the system can be effectively reduced with the increase of the content of the dispersant, but the shrinkage rate after curing is increased, and the mechanical properties of the cured product are also reduced. In order to maintain the balance of the mechanical property and the conductive property of the material system, the content of the acrylate oligomer resin is 65-85 wt%, the content of the acrylate reactive diluent is 9.9-10.9 wt%, the content of the photoinitiator is 3wt%, the content of the conductive filler is 1-20 wt%, the content of the dispersant is 0.1-2 wt%, and the effect is optimal.
Meanwhile, the polyurethane acrylate in the component 6 and the component 7 only adopts one component, so that the shrinkage rate of the system is obviously increased, and the performances such as hardness, bending strength and the like are poorer than those of the components 2 to 4.
Example 4
Examining the influence of different photoinitiators on the performance of the 3D printing material, the following photoinitiators were designed according to the formulation of example 1:
the photoinitiator 1 is phenyl bis (2,4, 6-trimethyl benzoyl) phosphine oxide;
photoinitiator 2 is benzoyl formate;
photoinitiator 3: TPO (acylphosphine oxide free radical photoinitiator)
The photoinitiator 4 is obtained by mixing phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and benzoyl formate according to the mass ratio of 1: 1.
Photoinitiator 5: phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and TPO are mixed according to the mass ratio of 1: 1.
Photoinitiator 6: TPO and benzoyl formate are mixed according to the mass ratio of 1: 1.
The influence of different photoinitiators on the properties of the 3D printing material was investigated,
the method for investigating the photocuring time comprises the following steps: and (3) judging whether the free radical 3D printing photosensitive resin is completely cured or not by a finger touch dry method according to GB1728-79 at the measurement temperature of 25 ℃.
The results are shown in Table 3.
Table 3: performance test result table of each 3D printing material
| Photoinitiator | 1 | 2 | 3 | 4 | 5 | 6 |
| Curing time(s) | 26 | 29 | 30 | 12 | 20 | 19 |
| Yellowing resistance | Difference (D) | Good effect | In general | Is excellent in | Good effect | Good effect |
| Shrinkage (%) | 4.57 | 4.68 | 5.12 | 4.38 | 4.41 | 4.49 |
| Hardness of | 90 | 92 | 86 | 95 | 92 | 93 |
| Flexural strength (Mpa) | 89 | 86 | 82 | 89 | 86 | 88 |
| Abrasion resistance (Kg/1000 r) | 0.135 | 0.156 | 0.357 | 0.054 | 0.089 | 0.105 |
| Heat distortion temperature (. degree. C.) | 94 | 96 | 92 | 99 | 94 | 95 |
From the results in table 3, it can be seen that: phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide has excellent absorption performance, can be applied to a thick film system, and has the advantages of fast light absorption and low yellow cured system. The benzoyl formate is a low-yellowing liquid ultraviolet initiator and is used for initiating the UV polymerization reaction of an unsaturated prepolymerization system. A good balance is achieved between low residual odor, low exotherm after cure, and cure efficiency. The two are combined for use, so that the rapid curing can be ensured, the heat release problem in the curing reaction can be considered, the reaction speed is ensured to be rapid and controllable after the photoinitiation, and the yellowing resistance performance after the reaction is good. Meanwhile, the mechanical property of the 3D printing piece is improved.
Example 5
Examining the influence of different photoinitiators on the performance of the 3D printing material, the following conductive fillers were respectively designed according to the formulation of example 1:
conductive filler 1: single-walled carbon nanotubes.
Conductive filler 2: graphene.
Conductive filler 3: carbon black.
Conductive filler 4: the graphene composite material is prepared by mixing a single-walled carbon nanotube and graphene according to the mass ratio of 1: 1.
Conductive filler 5: the carbon black is obtained by mixing single-walled carbon nanotube carbon black according to the mass ratio of 1: 1.
Conductive filler 6: the graphene oxide/carbon black composite material is prepared by mixing a single-walled carbon nanotube, graphene and carbon black according to the mass ratio of 1:1: 1.
The effect of different conductive fillers on the performance of the 3D printed material was examined and the results are listed in table 4.
Table 4: performance test result table of each 3D printing material
| Photoinitiator | 1 | 2 | 3 | 4 | 5 | 6 |
| Conductivity (volume resistivity omega cm) | 3.1*105 | 1.2*105 | 2.1*107 | 1.8*103 | 7.9*103 | 3.0*102 |
From the results in table 4, it can be seen that: the single conductive filler is adopted, so that the conductivity of the conductive graphene is improved to a certain extent, and if the carbon nano tube and the graphene are mixed, a line-plane type conductive model is formed between the carbon nano tube and the graphene, so that the conductive efficiency of the conductive graphene is obviously improved; if some carbon black is added, the point-line-surface conductive model has better conductive effect.
Example 6:
considering the effect of different acrylate reactive diluents on the performance of 3D printing materials, the following conductive fillers were designed according to the formulation of example 1:
diluent 1: a monofunctional monomer.
Diluent 2: isobornyl methacrylate.
Diluent 3: ethoxylated trimethylolpropane triacrylate.
Diluent 4: glycerol oxide triacrylate.
Diluent 5: the monomer is obtained by mixing a monofunctional monomer and isobornyl methacrylate according to the mass ratio of 1: 1.
Diluent 6: is prepared by mixing isobornyl methacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate according to the mass ratio of 1:1: 1.
The effect of different acrylate reactive diluents on the performance of the 3D printing material was examined and the results are listed in table 5.
Table 5: performance test result table of each 3D printing material
From the results of table 5, it can be seen that: the mechanical properties of the diluted printing system of the monofunctional monomer are better than those of isobornyl methacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate. Meanwhile, the diluent obtained by mixing the monofunctional monomer and the isobornyl methacrylate according to the mass ratio of 1:1 is not as good as the mixture of isobornyl methacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate in effect, because: isobornyl methacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate are mixed to serve as an active diluent, and the active diluent has active groups to participate in a curing reaction, so that a reticular polymer can be obtained after curing, the crosslinking density is high, and the mechanical property of the polymer is further improved.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (10)
1. The conductive 3D printing material is characterized by comprising acrylate oligomer resin, acrylate reactive diluent, photoinitiator, conductive filler and dispersant; the acrylate oligomer resin comprises beta-hydroxyethyl methacrylate and urethane acrylate;
the polyurethane acrylate is one or more of aromatic six-functionality polyurethane acrylate, aliphatic six-functionality polyurethane acrylate and aliphatic three-functionality polyurethane acrylate.
2. The conductive 3D printing material according to claim 1, wherein the urethane acrylate is a mixture of an aromatic hexafunctional urethane acrylate, an aliphatic hexafunctional urethane acrylate, and an aliphatic trifunctional urethane acrylate mixed in a mass ratio of 1:1: 1.
3. The conductive 3D printed material according to claim 1, wherein the acrylate reactive diluent is one or more of isobornyl methacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate.
4. The conductive 3D printing material according to claim 3, wherein the acrylate reactive diluent is a mixture of isobornyl methacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate mixed in a 1:1:1 ratio.
5. The conductive 3D printing material of claim 1, wherein the photoinitiator is a mixture of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and benzoyl formate mixed in a 1:1 ratio.
6. The conductive 3D printed material according to claim 1, wherein the conductive filler is one or more of single-walled carbon nanotubes, nanographene, and carbon black.
7. The conductive 3D printed material according to claim 1, wherein the dispersant is Tego610S and/or Surfynol CT-136.
8. The conductive 3D printing material according to any one of claims 1 to 7, wherein the acrylate oligomer resin is 65wt% to 85wt%, the acrylate reactive diluent is 9.9wt% to 10.9wt%, the photoinitiator is 3wt%, the conductive filler is 1wt% to 20wt%, and the dispersant is 0.1wt% to 2 wt%.
9. Method for the preparation of a conductive 3D printed material according to any of the claims 1 to 8, characterized in that it comprises the following steps:
s1, mixing the acrylic acid reactive diluent and the dispersing agent, adding the conductive filler, and grinding to obtain a mixed solution A;
s2, adding acrylic acid oligomer resin into the mixed solution A, and stirring to obtain mixed solution B;
and S3, adding a photoinitiator into the mixed solution B, and stirring to obtain the conductive 3D printing material.
10. The preparation method according to claim 9, wherein the conductive filler in S1 is added in three times, and after the conductive filler is added for the first time, the conductive filler is ground at 1000r/min for 20min, the conductive filler is ground at 1000r/min for 40min for the second time, and the conductive filler is ground at 1000r/min for 60min for the third time;
and/or in the step S2, the stirring is performed in a double planetary stirring kettle at a shear rate: 4m/s, revolution speed: stirring for 30min at 0.3 m/s;
and/or in the step S3, the stirring is performed in a double planetary stirring kettle at a shear rate: 4m/s, revolution speed: 0.2m/s, stirring for 20 min.
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| CN114806063B (en) * | 2022-05-09 | 2024-01-05 | 江苏大学 | Composite material with electric conduction, heat conduction and shape memory properties and preparation method thereof |
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Application publication date: 20210730 |