Degradable photoresist and application thereof in 3D printing

A 3D printing and photoresist technology, applied in the field of degradable photoresist preparation, can solve the problems of complex organic synthesis, difficult doping printing, harsh reaction conditions, etc., and achieve fast preparation, simple method and mild degradation conditions. Effect

Pending Publication Date: 2022-07-22
SOUTHEAST UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantage is that most of the functional monomers require complex organic synthesis, and some are very harsh on the reaction conditions
[0005] The second aspect is that due to the limitation of the principle of two-photon lithography, only a single material structure can be printed at a time. When doping with other functional monomers, it is very difficult to print with doping, such as photonic crystals, conductive materials, etc. First, compatibility Not good, the second is the disturbance of the light by the particles

Method used

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  • Degradable photoresist and application thereof in 3D printing
  • Degradable photoresist and application thereof in 3D printing
  • Degradable photoresist and application thereof in 3D printing

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] (1) Preparation of crosslinking agent main body with two acrylate double bonds and disulfide bonds

[0033] The specific steps are as follows:

[0034] Bis(2-hydroxyethyl)disulfide and triethylamine in a molar ratio of 1:8 were dissolved in anhydrous tetrahydrofuran. Then, the flask containing the solution was immersed in an ice-water bath, and methacryloyl chloride with a molar equivalent of 4 was slowly added dropwise to the stirred mixed solution. The resulting heterogeneous mixture was stirred at 20°C for 24 hours, then filtered, evaporated to remove the solvent and the crude product was dissolved in chloroform. Then this solution was dissolved in 0.1mol / L Na 2 CO 3 washed three times in aqueous solution, then three times with deionized water, and finally with anhydrous MgSO 4 dry. Distillation under reduced pressure gave pale yellow liquid dimethyl dithioacrylate (DSDMA), which was stored in a refrigerator in the dark. That 1 HNMR spectrum as figure 2 show...

Embodiment 2

[0042] (1) Preparation of crosslinking agent main body with two acrylate double bonds and disulfide bonds

[0043] The specific steps are as follows:

[0044] Dissolve bis(2-hydroxyethyl) disulfide and triethylamine in a molar ratio of 1:4 in anhydrous tetrahydrofuran in an ice-water bath, and then add methacryloyl chloride (molar equivalent of 4) drop by drop during stirring. ), the reaction was stirred at room temperature for 24 hours, and the solvent was removed by filtration under reduced pressure. Use 0.2M Na for the crude product 2 CO 3 It was washed three times, and further purified by silica gel-60 column chromatography with chloroform as mobile phase. The final dithiodimethacrylate product is a yellowish liquid and is stored in the refrigerator away from light.

[0045] (2) Preparation method of degradable photoresist

[0046] The ratio of double bonds in the photopolymerizable monomer and the photopolymerizable crosslinking agent is 1:1, and then the light absor...

Embodiment 3

[0052] (1) Preparation of crosslinking agent main body with two acrylate double bonds and disulfide bonds

[0053] The specific steps are as follows:

[0054] Dissolve bis(2-hydroxyethyl)disulfide and triethylamine in a molar ratio of 1:4 in anhydrous tetrahydrofuran in an ice-water bath, and then add methacryloyl chloride (molar equivalent of 2) drop by drop during stirring. ), the reaction was stirred at room temperature for 24 hours, and the solvent was removed by filtration under reduced pressure. Use 0.1M Na for crude product 2 CO 3 The solution was washed three times and further purified by silica gel-60 column chromatography using chloroform as mobile phase. The final dithiodimethacrylate product is a yellowish liquid and is stored in the refrigerator away from light.

[0055] (2) Preparation method of degradable photoresist

[0056] The ratio of double bonds in the photopolymerizable monomer and the photopolymerizable crosslinking agent is 1:2, and then the light ...

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Abstract

The invention discloses a preparation method and a use method of a degradable photoresist capable of being used for two-photon polymerization printing, and the preparation method comprises the following steps: using disulfide dimethacrylate (DSDMA) containing a reversible disulfide bond as a cross-linking agent, using a multi-sulfydryl molecule as a monomer, and carrying out cross-linking through ultraviolet light or two-photon polymerization; degradation of the photoresist can be realized in an organic solution of dithiothreitol (DTT), diethyl phosphate or other reducing reagents or a Tris-HCl aqueous solution of which the pH value is greater than 7, and a degradation product is dissolved in water; the cross-linking agent, the monomer, the photoinitiator and the polymerization inhibitor are mixed to obtain the photoresist system, the photoresist can be used for 3D printing based on two-photon polymerization, shows good printing performance and degradation performance, solves the problem that commercial photoresist lacks an additional degradation function, and can be applied to multi-material printing, biological scaffolds and the like.

Description

technical field [0001] The invention belongs to the field of functional photoresist 3D printing, and particularly relates to a preparation method and application of a degradable photoresist. Background technique [0002] 3D printing, also known as additive manufacturing, has emerged as a versatile and mature technology that can create complex functional 3D structures using materials such as metals, ceramics and polymers. Firstly, the 3D model is simulated by computer and digitally processed, and the designed three-dimensional object is produced layer by layer in the translation stage controlled by the computer. Today, more than 50 3D printing technologies based on different principles have been developed for different materials, speed and precision requirements. Among them, the precision of 3D printing (TPL) based on two-photon polymerization can reach the sub-nanometer level. The high precision and structural versatility of TPL make it an ideal tool for fabricating precise...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F220/38C08F222/24C08F2/48C08F2/46C07C319/22C07C323/12B33Y70/00C08J11/28C08L33/14
CPCC08F220/38C08F2/48C08F2/46C07C319/22B33Y70/00C08J11/28C08J2333/14C07C323/12C08F222/104C08F222/103
Inventor 顾忠泽杨潇杜鑫
Owner SOUTHEAST UNIV
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