CN110669163A - 3D printing photopolymer composition - Google Patents
3D printing photopolymer composition Download PDFInfo
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- CN110669163A CN110669163A CN201910977206.2A CN201910977206A CN110669163A CN 110669163 A CN110669163 A CN 110669163A CN 201910977206 A CN201910977206 A CN 201910977206A CN 110669163 A CN110669163 A CN 110669163A
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- parts
- printing
- acryloyl monomer
- composition
- acrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a 3D printing photosensitive polymer composition which comprises 20-40 parts of an acryloyl monomer, 10-40 parts of acrylate, 0.4-8 parts of a photoinitiator and 0.1-0.5 part of a light stabilizer. The invention also discloses a preparation method thereof, which comprises the steps of placing the acryloyl monomer and the light stabilizer into a reaction kettle, controlling the temperature at 30-50 ℃, introducing nitrogen, pre-reacting for 30-1h, then putting the acrylate and the photoinitiator into an S1 reaction kettle, and stirring for 1-3 h. The invention can be used in the 3D printing technology of Stereolithography (SLA) and Digital Light Processing (DLP). The preparation method is simple in preparation process, and the prepared product is high in strength and good in stability.
Description
Technical Field
The invention belongs to the field of 3D printing consumable manufacturing, and particularly relates to a 3D printing photopolymer composition and a preparation method thereof.
Background
3D printing, one of the rapid prototyping technologies, is a technology for constructing an object by using an adhesive material such as powdered metal or plastic based on a digital model file and by printing layer by layer. 3D printing is typically achieved using digital technology material printers. The method is often used for manufacturing models in the fields of mold manufacturing, industrial design and the like, and is gradually used for directly manufacturing some products, and parts printed by the technology are already available. The technology has applications in jewelry, footwear, industrial design, construction, engineering and construction (AEC), automotive, aerospace, dental and medical industries, education, geographic information systems, civil engineering, firearms, and other fields.
The common printer used in daily life can print planar articles designed by a computer, the working principle of the 3D printer is basically the same as that of the common printer, only the printing materials are different, the printing materials of the common printer are ink and paper, the 3D printer is filled with different printing materials such as metal, ceramic, plastic, sand and the like, the printing materials are actual raw materials, after the printer is connected with the computer, the printing materials can be stacked layer by layer through computer control, and finally, a blueprint on the computer is changed into an actual object. Colloquially, a 3D printer is a device that can "print" out real 3D objects, such as printing a robot, printing a toy car, printing various models, even food, and so on. The generic name "printer" refers to the technical principle of a common printer, since the process of layered processing is very similar to inkjet printing. This printing technique is called a 3D stereoscopic printing technique.
There are many different techniques for 3D printing. They differ in the way the building components are built up in different layers, in the way the materials are available. Among these 3D printing techniques, photopolymerization techniques such as Stereolithography (SLA) and Digital Light Processing (DLP) generally use liquid to produce products through polymerization, and compared with other 3D printing techniques using solid materials such as powder and filament materials, the produced products have better intermolecular binding degree, higher precision and smoother surface.
In view of the need for photopolymerization technology and the deficiencies of existing 3D printing materials, there is a need to produce photopolymer compositions with better properties.
Disclosure of Invention
The invention aims to provide a photopolymer composition for 3D printing. The photosensitive resin has the advantages of high forming speed, simple preparation process, low viscosity and the like, and can be directly applied to 3D printing and manufacturing of products with complex structures.
The 3D printing photopolymer composition comprises the following raw materials in parts by weight:
20-40 parts of acryloyl monomer, 10-40 parts of acrylate, 0.4-8 parts of photoinitiator and 0.1-0.5 part of light stabilizer.
Preferably, the viscosity of the acryl monomer is 0.1 to 50 pas.
Preferably, the acryl monomer includes: one or more of carboxyl acryloyl monomer, acid group acryloyl monomer, amine acryloyl monomer and hydroxyl acryloyl monomer.
Preferably, the acrylate is one or more of tricyclodecane dimethanol diacrylate, 2-methyl-1, 3-propanediol diacrylate, 2-butyl-2-ethyl-1, 3-propanediol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, propoxylated glycerol triacrylate, aliphatic acrylates, urethane acrylates, and epoxy acrylates.
Preferably, the photoinitiator is one or more of 184D, 1-hydroxycyclohexyl phenyl ketone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and the light stabilizer is benzotriazole.
Preparation method of 3D printing photopolymer composition: the method comprises the following steps:
s1, placing the acryloyl monomer and the light stabilizer into a reaction kettle, controlling the temperature at 30-50 ℃, introducing nitrogen, and pre-reacting for 30-1 h;
s2, putting the acrylate and the photoinitiator into an S1 reaction kettle, and stirring for 1-3h to prepare the 3D printing photopolymer composition.
The 3D printing photopolymer composition prepared by the invention is used for 3D printing technologies of Stereolithography (SLA) and Digital Light Processing (DLP).
The invention has the beneficial effects that:
the polymer composition has excellent physical properties (high strength, high toughness, deformation resistance and stability), can greatly improve the performance characteristics of the existing 3D printing material, can replace and exceed similar imported products, and meanwhile, the preparation cost is greatly reduced, the reaction process is simple, safe and environment-friendly, and the polymer composition is very suitable for industrial mass production and has good economic benefit.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 3D printing photopolymer composition preparation method below: the method is characterized by comprising the following steps:
s1, placing the acryloyl monomer and the light stabilizer into a reaction kettle, controlling the temperature at 30-50 ℃, introducing nitrogen, and pre-reacting for 30-1 h;
s2, putting the acrylate and the photoinitiator into an S1 reaction kettle, and stirring for 1-3h to prepare the 3D printing photopolymer composition.
Example 1
Carboxyl acryloyl monomer 10 parts
Acid radical acryloyl monomer 10 parts
Aminopropenyl monomer 10 parts
10 parts of hydroxyl acryloyl monomer
5 parts of tricyclodecane dimethanol diacrylate
Pentaerythritol triacrylate 5 parts
5 parts of epoxy acrylate
6 parts of 1-hydroxycyclohexyl phenyl ketone
0.5 part of benzotriazole.
Example 2
Carboxyl acryloyl monomer 5 parts
Acid radical acryloyl monomer 5 parts
5 parts of amine acryloyl monomer
5 parts of hydroxyl acryloyl monomer
Ethylene glycol dimethacrylate 10 parts
8 parts of dipentaerythritol pentaacrylate
Pentaerythritol triacrylate 15 parts
0.8 part of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide
4 parts of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide
0.5 part of benzotriazole.
Example 3
Carboxyl acryloyl monomer 10 parts
Acid radical acryloyl monomer 15 parts
Aminopropenyl monomer 10 parts
5 parts of hydroxyl acryloyl monomer
Ethylene glycol dimethacrylate 10 parts
Aliphatic acrylate 20 parts
Pentaerythritol triacrylate 8 parts
3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide
2 parts of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide
0.5 part of benzotriazole.
The photopolymer composition was tested for cure using a 3D printer and the physical properties were measured as follows:
| item | Example 1 | EXAMPLE 2 | Example 3 |
| Hardness D | 65 | 70 | 71 |
| Density g/ml | 1.123 | 1.021 | 1.074 |
| Polymer density g/ml | 1.187 | 1.103 | 1.191 |
| Volume shrinkage percentage% | 3.25 | 3.45 | 3.11 |
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
- The 3D printing photopolymer composition is characterized by comprising the following raw materials in parts by weight:20-40 parts of acryloyl monomer, 10-40 parts of acrylate, 0.4-8 parts of photoinitiator and 0.1-0.5 part of light stabilizer.
- 2. The composition of claim 1, wherein the acryl monomer has a viscosity of 0.1 to 50 Pa-s.
- 3. The composition of claim 1 or 2, wherein the acryloyl monomer comprises: one or more of carboxyl acryloyl monomer, acid group acryloyl monomer, amine acryloyl monomer and hydroxyl acryloyl monomer.
- 4. The composition of claim 1, wherein the acrylate is one or more of tricyclodecane dimethanol diacrylate, 2-methyl-1, 3-propanediol diacrylate, 2-butyl-2-ethyl-1, 3-propanediol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, propoxylated glycerol triacrylate, aliphatic acrylates, urethane acrylates, and epoxy acrylates.
- 5. The composition of claim 1, wherein the photoinitiator is one or more of 184D, 1-hydroxycyclohexyl phenyl ketone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and the light stabilizer is benzotriazole.
- 6.3D printing photopolymer composition preparation method: the method is characterized by comprising the following steps:s1, placing the acryloyl monomer and the light stabilizer into a reaction kettle, controlling the temperature at 30-50 ℃, introducing nitrogen, and pre-reacting for 30-1 h;s2, putting the acrylate and the photoinitiator into an S1 reaction kettle, and stirring for 1-3h to prepare the 3D printing photopolymer composition.
- 7. The composition according to claim 1, characterized by 3D printing techniques useful for Stereolithography (SLA) and Digital Light Processing (DLP).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910977206.2A CN110669163A (en) | 2019-10-15 | 2019-10-15 | 3D printing photopolymer composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910977206.2A CN110669163A (en) | 2019-10-15 | 2019-10-15 | 3D printing photopolymer composition |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105259736A (en) * | 2015-11-10 | 2016-01-20 | 上海移石新材料科技有限公司 | Photosensitive resin for 3D printer and preparation method of photosensitive resin |
| CN106750049A (en) * | 2016-11-30 | 2017-05-31 | 辽宁大学 | A kind of 3D printing rapid shaping photocurable resin material and its preparation method and application |
| CN109401259A (en) * | 2018-09-20 | 2019-03-01 | 大赛璐（中国）投资有限公司 | Solid material composition and its preparation method and application |
| CN109803989A (en) * | 2016-10-21 | 2019-05-24 | 可乐丽则武齿科株式会社 | Optical stereo moulding composition |
-
2019
- 2019-10-15 CN CN201910977206.2A patent/CN110669163A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105259736A (en) * | 2015-11-10 | 2016-01-20 | 上海移石新材料科技有限公司 | Photosensitive resin for 3D printer and preparation method of photosensitive resin |
| CN109803989A (en) * | 2016-10-21 | 2019-05-24 | 可乐丽则武齿科株式会社 | Optical stereo moulding composition |
| CN106750049A (en) * | 2016-11-30 | 2017-05-31 | 辽宁大学 | A kind of 3D printing rapid shaping photocurable resin material and its preparation method and application |
| CN109401259A (en) * | 2018-09-20 | 2019-03-01 | 大赛璐（中国）投资有限公司 | Solid material composition and its preparation method and application |
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Application publication date: 20200110 |
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