Application of low-viscosity light-cured resin in 3D (three-dimensional) printing materials

A light-curing resin and 3D printing technology, applied in the field of 3D printing, can solve the problems of dependence on foreign imports of molding resins, few suitable materials for light-curing, and obstacles to rapid development, etc., to reduce amine mobility, no catalyst residue, and curing shrinkage Reduced effect

Active Publication Date: 2015-09-09
新丰博兴聚合材料有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In China, few companies can own this technology. Although they have developed printer equipment, most of the molding resins still rely on foreign imports. The price of molding materials is as high as 600-1200 yuan / Kg, and the most expensive one reaches tens of thousands of yuan per kilogram. , the cost of completing an object is extremely high, which greatly hinders its rapid development
[0004] The comprehensive requirements of 3D printing light-curing materials include low viscosity, fast curing, moderate curing strength and flexibility, small shrinkage and low price. However, there are few suitable light-curing materials that can meet the above factors at the same time. The method of mixing resin and reactive diluent monomer is difficult to meet the performance requirements

Method used

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  • Application of low-viscosity light-cured resin in 3D (three-dimensional) printing materials
  • Application of low-viscosity light-cured resin in 3D (three-dimensional) printing materials
  • Application of low-viscosity light-cured resin in 3D (three-dimensional) printing materials

Examples

Experimental program
Comparison scheme
Effect test

Synthetic example 1

[0067] Synthesis Example 1 Polyether Acrylate 1

[0068] A kind of polyether acrylate and preparation method thereof, comprises following two steps:

[0069] a. Transesterification reaction: Take 400g polyether triol (Mn≈700, Dow VOANOL 2070), 343.2g ethyl acrylate, 1.2g trinonylphenyl phosphite, 0.2g 2,6-di-tert-butyl Base-4-methylphenol, after uniform dispersion, add 5g of immobilized enzyme Novozyme 435 and 0.1g of lanthanum dodecylsulfonate, stir and react at 40°C for 24h;

[0070] b. Purification treatment: After filtering the mixture obtained in the previous step, the filtrate was subjected to vacuum rotary evaporation, and the ethanol and excess methacrylic acid generated by the reaction were removed to obtain 490.2 g of transparent and colorless esterified product (solid content 99.2%, viscosity 85 mPa ·s / 25°C, the esterification rate (based on polyether polyol as the base substrate, the same below) is 97.4%), the molecular weight of the obtained product is 862,...

Synthetic example 2

[0071] Synthesis Example 2 Branched Polyether Acrylate 2 (Mn≈1022, Functionality 9)

[0072] A kind of branched polyether acrylate and preparation method thereof, concrete steps are as follows:

[0073] (1) Synthesis of branched polyether polyols

[0074] Glycerol is used as raw material to form branched polyether polyols (Mn≈536, functionality 9, branching degree 0.72) through one-step condensation under acidic conditions;

[0075] (2) Enzyme-catalyzed transesterification reaction, including the following two steps:

[0076] a. Transesterification reaction: take 300g of the above-mentioned branched polyether polyol, 550.0g methyl acrylate, 1.8g trinonylphenyl phosphite, 0.25g p-hydroxyanisole, after dispersing evenly, add 8g of curing enzyme Novozyme 435 and 0.1g lanthanum dodecylsulfonate, stirred and reacted at 50°C for 24h; the chemical reaction formula is as follows:

[0077]

[0078] b. Purification treatment: After filtering the mixture obtained in the previous ...

Synthetic example 3

[0079] Synthesis example 3 polycyclic amine modified branched polyether acrylate 3

[0080] (1) Synthesis of heteropolycyclic amines

[0081] Add 218.2g of 4,4'-difluorobenzophenone, 175.0g of anhydrous piperazine, 150.0g of anhydrous potassium carbonate and 300ml of dimethyl sulfoxide to a four-necked flask equipped with a condenser tube, a thermometer and a stirrer ; Under the protection of nitrogen, heat up to 100 ° C for 12 hours; when it is cooled to 80 ° C, filter while it is hot, wash the filtrate twice with water, add anhydrous sodium sulfate to dry, filter again, and distill off the solvent under reduced pressure to obtain Heteropolycyclic semi-finished product 345.0g, yield 87.7%; Reaction equation is as follows:

[0082]

[0083] (2) Preparation of polycyclic amine modified polyether acrylate 1

[0084] Take 35.1g (0.1mol) of the heteropolycyclic amine prepared in step (1) and put it into a three-necked flask, add 0.6g of DBU catalyst, and gradually raise the...

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Abstract

The invention relates application of low-viscosity light-cured resin in 3D (three-dimensional) printing materials. The low-viscosity light-cured resin is (branched) polyether acrylate or heterocyclic amine modified (branched) polyether acrylate. A 3D printing material prepared from the low-viscosity light-cured resin is of low viscosity and high curing speed, is low in curing shrinkage, low in yellowing property, moderate in rigidity and flexibility, high in forming speed and high in product dimensional precision, is free of curing incompleteness, edge warping and the like, and is very suitable for being applied to 3D printing materials based on the SLA (stereolithography) or 3DP (three-dimensional printing) technology.

Description

technical field [0001] The invention relates to the technical field of 3D printing, in particular to the application of a low-viscosity photocurable resin in 3D printing materials. Background technique [0002] The popularity of 3D printing technology has been hailed as the representative of the "third industrial revolution". At present, 3D printing technology is in a period of vigorous development. The more mature 3D printing technologies include stereolithography (SLA), wire extrusion hot-melt molding (FDM, FFF, etc.), selective laser sintering (SLS), and three-dimensional printing. Bonded molding (3DP) and layered solid manufacturing (LOM), etc. Among them, FDM technology is the mainstream of domestic 3D printing technology, and has formed a certain scale of industrial chain, such as in the application of mannequin manufacturing and personalized model construction. However, limited by the technology itself, there are generally disadvantages such as slow molding, limited...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08L51/08C08L75/14C08G83/00C08F283/06C08F220/18C08F220/14B33Y70/00
Inventor 庞来兴李志云巫朝剑汪慧曾贤健
Owner 新丰博兴聚合材料有限公司
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