CN112063158A - 3D printing material and preparation method thereof - Google Patents
3D printing material and preparation method thereof Download PDFInfo
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- CN112063158A CN112063158A CN202010850383.7A CN202010850383A CN112063158A CN 112063158 A CN112063158 A CN 112063158A CN 202010850383 A CN202010850383 A CN 202010850383A CN 112063158 A CN112063158 A CN 112063158A
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- filler
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- 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
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a 3D printing material and a preparation method thereof. According to the 3D printing material disclosed by the invention, isocyanate and polyester polyol can be subjected to polymerization reaction to generate the polyurethane polymer containing the NCO active group end capping. And the isocyanate can promote polyurethane crystallization, improve the crystallinity of the polymer, and further improve the initial adhesion performance of the polyurethane material, so that the initial adhesion of the prepared material between section layers in the 3D printing process is improved. In the 3D printing material, the ester-based polar group and the terpene resin contained in the ethyl acrylate can improve the processing performance and the bonding strength of the material.
Description
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to a 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 have been obtained for one month 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.
At present, the raw materials used by FDM are usually thermoplastic polymer materials, including acrylonitrile-butadiene-styrene copolymer (ABS), polylactic acid (PLA), Polycarbonate (PC), polyphenylsulfone (PPSF), etc., but these materials have more or less problems of large shrinkage, poor toughness, poor mechanical properties, etc., and because FDM uses a layer-by-layer printing method, the problem of the FDM printing raw materials directly causes the problem of small interlayer bonding force of the product obtained by the FDM process.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. For this reason, the invention provides a 3D printing material.
The invention also provides a preparation method of the 3D printing material.
The invention provides a 3D printing material, which comprises the following preparation raw materials in parts by weight:
isocyanate: 40-60 parts of (A) a water-soluble polymer,
polyester polyol: 10-20 parts of (A) a water-soluble polymer,
ethyl acrylate: 10-15 parts of (a) a water-soluble polymer,
terpene resin: 5 to 10 parts by weight of a surfactant,
tackifying and filling materials: 5 to 15 parts of (A) a water-soluble polymer,
a stabilizer: 0.5-1 part.
According to one embodiment of the invention, the isocyanate is selected from at least one of toluene diisocyanate, hexamethylene diisocyanate and 2, 2, 4-trimethylhexane diisocyanate.
According to one embodiment of the present invention, the terpene resin is at least one selected from the group consisting of an α -terpene resin, a β -terpene resin, and a terpene phenolic resin.
According to one embodiment of the invention, the tackifying filler is a linear tackifying filler and a particulate tackifying filler in a mass ratio of 1: (3-5) a mixed filler.
The tackifying filler is linear tackifying filler and granular tackifying filler according to the mass ratio of 1: the mixed filler in the step (3-5), on one hand, the linear tackifying filler can tightly connect the printed material of the previous layer with the printed material of the next layer, so that the bonding force between the layers is greatly improved; on the other hand, the granular tackifying filler can keep good fluidity of the 3D printing material. The synergistic cooperation of the linear tackifying filler and the granular tackifying filler enables the interlayer bonding force of the 3D printing material to be greatly improved while keeping good fluidity.
According to one embodiment of the invention, the linear tackifying filler is carbon fiber filaments.
According to one embodiment of the invention, the particulate tackifying filler is alumina microspheres or titanium dioxide microspheres.
According to one embodiment of the present invention, the particulate thickening filler is a mixture of a large-particle-size particulate filler and a small-particle-size particulate filler at a mass ratio of 1: 5.
According to an embodiment of the present invention, D50 of the large-particle-size particulate filler is 15 to 25 μm; the D50 of the small-particle-diameter granular filler is 2-5 mu m.
A second aspect of the present invention provides a method of preparing the above 3D printed material, comprising the steps of:
s1: uniformly mixing polyester polyol, terpene resin, tackifying filler and stabilizer to obtain a premix;
s2: and (4) mixing the premix obtained in the step S1 with isocyanate in a protective atmosphere, carrying out polymerization reaction, and carrying out vacuum defoaming to obtain the 3D printing material.
According to an embodiment of the present invention, the temperature of the polymerization reaction is 85 to 95 ℃.
According to an embodiment of the present invention, the time of the polymerization reaction is 8 to 12 hours.
The 3D printing material disclosed by the invention at least has the following technical effects:
in the 3D printing material, isocyanate and polyester polyol can be subjected to polymerization reaction to generate a polyurethane polymer containing NCO active group end capping. And the isocyanate can promote polyurethane crystallization, improve the crystallinity of the polymer, and further improve the initial adhesion performance of the polyurethane material, so that the initial adhesion of the prepared material between section layers in the 3D printing process is improved.
In the 3D printing material, the ester-based polar group and the terpene resin contained in the ethyl acrylate can improve the processing performance and the bonding strength of the material.
Generally, the layer/interlayer bonding force of a 3D printed sample piece is weak, and the tackifying filler in the invention can be exposed on the surface of a previous layer printed material, so that the previous layer printed material and a next layer printed material are tightly connected together, the bonding force between layers is greatly improved, and other tackifying resins are not required to be additionally added.
In the 3D printing material, the stabilizer can prevent isocyanate and polyester polyol from generating gel in the reaction process, and can also prevent the viscosity of the material from being increased due to repeated heating in the use process so as to weaken the fluidity of the material.
The preparation method of the 3D printing material provided by the invention is simple in process, easy to control conditions and easy to realize industrial production.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The embodiment provides a 3D printing material, which comprises the following preparation raw materials in parts by weight:
isocyanate: 40 parts, polyester polyol: 10 parts of ethyl acrylate: 10 parts, terpene resin: 5 parts of tackifying filler: 5 parts, stabilizer: 0.5 part.
Wherein the isocyanate is toluene diisocyanate. The terpene resin is alpha-terpene resin.
The tackifying filler is linear tackifying filler and granular tackifying filler according to the mass ratio of 1:5 in a mixture. The linear tackifying filler is carbon fiber filaments. The granular tackifying filler is alumina microspheres. The granular tackifying filler is a mixture of a large-particle-size granular filler and a small-particle-size granular filler according to a mass ratio of 1: 5. D50 of the large-particle-size granular filler was 20 μm; the D50 of the small particle size particulate filler was 5 μm.
The preparation method comprises the following steps:
s1: uniformly mixing polyester polyol, terpene resin, tackifying filler and stabilizer to obtain a premix;
s2: and (4) mixing the premix obtained in the step S1 with isocyanate in a protective atmosphere, carrying out polymerization reaction, and carrying out vacuum defoaming to obtain the 3D printing material.
Wherein the temperature of the polymerization reaction is 95 ℃, and the time of the polymerization reaction is 10 h.
Example 2
The embodiment provides a 3D printing material, which comprises the following preparation raw materials in parts by weight:
isocyanate: 40 parts, polyester polyol: 10 parts of ethyl acrylate: 10 parts, terpene resin: 5 parts of tackifying filler: 15 parts, stabilizer: 0.5 part.
Wherein the isocyanate is hexamethylene diisocyanate. The terpene resin is alpha-terpene resin.
The tackifying filler is linear tackifying filler and granular tackifying filler according to the mass ratio of 1:5 in a mixture. The linear tackifying filler is carbon fiber filaments. The granular tackifying filler is titanium dioxide microspheres. The granular tackifying filler is a mixture of a large-particle-size granular filler and a small-particle-size granular filler according to a mass ratio of 1: 5. D50 of the large-particle-size granular filler was 20 μm; the D50 of the small particle size particulate filler was 5 μm.
The preparation method comprises the following steps:
s1: uniformly mixing polyester polyol, terpene resin, tackifying filler and stabilizer to obtain a premix;
s2: and (4) mixing the premix obtained in the step S1 with isocyanate in a protective atmosphere, carrying out polymerization reaction, and carrying out vacuum defoaming to obtain the 3D printing material.
Wherein the temperature of the polymerization reaction is 95 ℃, and the time of the polymerization reaction is 10 h.
Example 3
The embodiment provides a 3D printing material, which comprises the following preparation raw materials in parts by weight:
isocyanate: 40 parts, polyester polyol: 10 parts of ethyl acrylate: 10 parts, terpene resin: 5 parts of tackifying filler: 15 parts, stabilizer: 0.5 part.
Wherein the isocyanate is 2, 2, 4-trimethylhexane diisocyanate. The terpene resin is terpene phenolic resin.
The tackifying filler is linear tackifying filler and granular tackifying filler according to the mass ratio of 1: 3, a mixed filler. The linear tackifying filler is carbon fiber filaments. The granular tackifying filler is titanium dioxide microspheres. The granular tackifying filler is a mixture of a large-particle-size granular filler and a small-particle-size granular filler according to a mass ratio of 1: 5. D50 of the large-particle-size granular filler was 20 μm; the D50 of the small particle size particulate filler was 5 μm.
The preparation method comprises the following steps:
s1: uniformly mixing polyester polyol, terpene resin, tackifying filler and stabilizer to obtain a premix;
s2: and (4) mixing the premix obtained in the step S1 with isocyanate in a protective atmosphere, carrying out polymerization reaction, and carrying out vacuum defoaming to obtain the 3D printing material.
Wherein the temperature of the polymerization reaction is 95 ℃, and the time of the polymerization reaction is 10 h.
Comparative example 1
The embodiment provides a 3D printing material, which comprises the following preparation raw materials in parts by weight:
isocyanate: 40 parts, polyester polyol: 10 parts of ethyl acrylate: 10 parts, terpene resin: 5 parts of tackifying filler: 15 parts, stabilizer: 0.5 part.
Wherein the isocyanate is 2, 2, 4-trimethylhexane diisocyanate. The terpene resin is terpene phenolic resin.
The tackifying filler comprises only linear tackifying filler.
Comparative example 2
The embodiment provides a 3D printing material, which comprises the following preparation raw materials in parts by weight:
isocyanate: 40 parts, polyester polyol: 10 parts of ethyl acrylate: 10 parts, terpene resin: 5 parts of tackifying filler: 15 parts, stabilizer: 0.5 part.
Wherein the isocyanate is 2, 2, 4-trimethylhexane diisocyanate. The terpene resin is terpene phenolic resin.
The tackifying filler comprises only a particulate tackifying filler. The granular tackifying filler is alumina microspheres. The granular tackifying filler is a mixture of a large-particle-size granular filler and a small-particle-size granular filler according to a mass ratio of 1: 5. D50 of the large-particle-size granular filler was 20 μm; the D50 of the small particle size particulate filler was 5 μm.
The preparation method comprises the following steps:
s1: uniformly mixing polyester polyol, terpene resin, tackifying filler and stabilizer to obtain a premix;
s2: and (4) mixing the premix obtained in the step S1 with isocyanate in a protective atmosphere, carrying out polymerization reaction, and carrying out vacuum defoaming to obtain the 3D printing material.
Wherein the temperature of the polymerization reaction is 95 ℃, and the time of the polymerization reaction is 10 h.
Comparative example 3
The embodiment provides a 3D printing material, which comprises the following preparation raw materials in parts by weight:
isocyanate: 40 parts, polyester polyol: 10 parts of ethyl acrylate: 10 parts, terpene resin: 5 parts, stabilizer: 0.5 part.
Wherein the isocyanate is 2, 2, 4-trimethylhexane diisocyanate. The terpene resin is terpene phenolic resin.
The preparation method comprises the following steps:
s1: uniformly mixing polyester polyol, terpene resin, tackifying filler and stabilizer to obtain a premix;
s2: and (4) mixing the premix obtained in the step S1 with isocyanate in a protective atmosphere, carrying out polymerization reaction, and carrying out vacuum defoaming to obtain the 3D printing material.
Wherein the temperature of the polymerization reaction is 95 ℃, and the time of the polymerization reaction is 10 h.
Example of detection
The 3D printed materials prepared in examples 1 to 3 and comparative examples 1 to 3 were printed using Stratasys ABS-M30 melt molding technique and the properties of the products were tested, and the results are shown in table 1.
TABLE 1
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (10)
1. The 3D printing material is characterized by comprising the following preparation raw materials in parts by weight:
isocyanate: 40-60 parts of (A) a water-soluble polymer,
polyester polyol: 10-20 parts of (A) a water-soluble polymer,
ethyl acrylate: 10-15 parts of (a) a water-soluble polymer,
terpene resin: 5 to 10 parts by weight of a surfactant,
tackifying and filling materials: 5 to 15 parts of (A) a water-soluble polymer,
a stabilizer: 0.5-1 part.
2. The 3D printed material according to claim 1, wherein the isocyanate is selected from at least one of toluene diisocyanate, hexamethylene diisocyanate, and 2, 2, 4-trimethylhexane diisocyanate.
3. The 3D printed material according to claim 1, wherein the terpene resin is selected from at least one of an alpha terpene resin, a beta terpene resin, and a terpene phenolic resin.
4. The 3D printed material according to claim 1, wherein the tackifying filler is a linear tackifying filler and a granular tackifying filler in a mass ratio of 1: (3-5) a mixed filler.
5. The 3D printed material according to claim 4, wherein the linear tackifying filler is carbon fiber filaments.
6. The 3D printing material according to claim 4, wherein the particulate tackifying filler is a mixture of a large-particle-size particulate filler and a small-particle-size particulate filler in a mass ratio of 1: 5.
7. The 3D printing material according to claim 6, wherein the D50 of the large-particle-size particulate filler is 15-25 μm; the D50 of the small-particle-diameter granular filler is 2-5 mu m.
8. A method of preparing a 3D printed material according to any of claims 1 to 7, comprising the steps of:
s1: uniformly mixing polyester polyol, terpene resin, tackifying filler and stabilizer to obtain a premix;
s2: and (4) mixing the premix obtained in the step S1 with isocyanate in a protective atmosphere, carrying out polymerization reaction, and carrying out vacuum defoaming to obtain the 3D printing material.
9. The method according to claim 8, wherein the polymerization temperature is 85 to 95 ℃.
10. The method according to claim 8, wherein the polymerization reaction time is 8 to 12 hours.
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| CN202010850383.7A CN112063158A (en) | 2020-08-21 | 2020-08-21 | 3D printing material and preparation method thereof |
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