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Heterocyclic modified two-photon polymerization initiator based on phenothiazine or carbazole and preparation method thereof

A technology of two-photon polymerization and phenothiazine, which is applied in the direction of organic chemistry, can solve the problems of insufficient additive manufacturing and low efficiency of two-photon polymerization initiators, and achieve the goal of short time required, good stability and high product purity. Effect

Active Publication Date: 2021-09-21
LASER FUSION RES CENT CHINA ACAD OF ENG PHYSICS
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, current two-photon polymerization initiators are still relatively inefficient and insufficient for large-scale additive manufacturing

Method used

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  • Heterocyclic modified two-photon polymerization initiator based on phenothiazine or carbazole and preparation method thereof
  • Heterocyclic modified two-photon polymerization initiator based on phenothiazine or carbazole and preparation method thereof
  • Heterocyclic modified two-photon polymerization initiator based on phenothiazine or carbazole and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047] Step 1. Slowly add NaH (stored in 60% mineral oil, 3.00 g, 75 mmol) into an 80 mL DMF solution flask containing phenothiazine (10 g, 50 mmol), the flask is placed in a water bath containing ice-water mixture, and Stir, after 15 minutes, slowly add 1-bromododecane (14.4mL, 60mmol), stir the resulting solution overnight, then slowly add deionized water, after stirring for half an hour, extract with ethyl acetate, and then use column chromatography Purified by petroleum ether: ethyl acetate = 40:1 (v:v) eluent to obtain 10-dodecyl-10H-phenothiazine as light yellow oil 14.33g, yield 78% , with a purity of 96%;

[0048] Step 2. Slowly add NBS (8.9 g, 50 mmol) to a flask containing 10-dodecyl-10H-phenothiazine (7.35 g, 20 mmol) and 80 mL of DCM cooled to 0° C., and stir the resulting suspension overnight, Then, deionized water was slowly added and stirred for 30 minutes, then, saturated brine was added and extracted to obtain an organic phase, which was then dried with magne...

Embodiment 2

[0054]Step 1, NaH (stored in 60% mineral oil, 3.00g, 75mmol) was slowly added to the 80mL DMF solution flask containing phenothiazine (10g, 50mmol) cooled to 0°C, and stirred, after 15 minutes, 1-Bromododecane (14.4 mL, 60 mmol) was slowly added, and the resulting solution was stirred for 12 hours, then deionized water was slowly added, after stirring for half an hour, extracted with ethyl acetate, and then purified by column chromatography, using petroleum Ether: ethyl acetate = 40:1 (v:v) eluent to obtain 10-dodecyl-10H-phenothiazine as light yellow oil 14.15g with a yield of 77% and a purity of 95%;

[0055] Step 2. Slowly add NBS (8.9 g, 50 mmol) into a flask containing 10-dodecyl-10H-phenothiazine (7.35 g, 20 mmol) and 80 mL of DCM cooled to 0°C. The resulting suspension was stirred overnight, then deionized water was slowly added and stirred for 20 minutes, then saturated brine was added and extracted to obtain an organic phase, which was then dried over magnesium sulfat...

Embodiment 3

[0060] Step 1. Slowly add NaH (stored in 60% mineral oil, 4.00 g, 100mmol), after 15 minutes, 1-bromododecane (18.0mL, 75mmol) was slowly added, the resulting suspension was stirred overnight and deionized water was slowly added, filtered and washed with petroleum ether to obtain 3,6-di Bromo-9-dodecyl-carbazole, gray solid 21.61g, yield 88%, purity 96%;

[0061] Step 2, add 3,6-dibromo-9-dodecyl-carbazole (4.93g, 10mmol), CuI (190mg, 1mmol), PdCl to the 250mL three-necked flask 2 (PPh 3 ) 2 (350mg, 0.5mmol), PPh 3 (262mg, 1mmol), 1,1-dimethyl-2-butyn-1-ol (2.91mL, 30mmol) and triethylamine (80mL), under the protection of Ar, the resulting mixture was refluxed at 90°C for 8 hours , after cooling, the solvent was removed, the residue was poured into saturated brine and extracted with ethyl acetate (5×100 mL), the organic layers were combined and washed with MgSO 4 Dry, concentrate, and use petroleum ether:ethyl acetate=10:1 (v:v) as eluent, purify by column chromatography ...

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Abstract

The invention discloses a heterocyclic modified two-photon polymerization initiator based on phenothiazine or carbazole and a preparation method thereof, comprising: step 1, the raw materials phenothiazine and 3,6-dibromo-9H-carbazole Protect by adding an alkyl group by nucleophilic substitution; Step 2, carry out Sonogashira coupling reaction to the product of step 1, introduce alkynyl; Step 3, deprotect the product of step 2; Step 4, carry out Sonogashira to the product of step 3 Coupling reaction, introducing electron-withdrawing groups. The heterocyclic modified phenothiazine and carbazole derivative two-photon initiators prepared by the present invention show good stability, solubility and two-photon polymerization activity, and the scanning speed of two-photon polymerization processing with it is fast, micro The structural precision is better. The optical properties and two-photon polymerization performance of the initiator of the present invention are studied, and the results show that the TPA cross-section of the initiator with the best performance can reach 1315GM, and the scanning speed during the polymerization process can reach 14000 μm / s.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a heterocyclic modified two-photon polymerization initiator based on phenothiazine or carbazole and a preparation method thereof. Background technique [0002] As the demand for micro-nano materials increases, a new, more efficient, and higher-resolution method for fabricating micro-nano materials has emerged. Two-photon polymerization additive manufacturing has become an important new micro-nano manufacturing method due to its unique two-photon effect. In the 1930s, Goppert-Mayer theoretically predicted two-photon absorption (TPA) under intense optical excitation. It wasn't until the advent of high-energy lasers that researchers observed the phenomenon of TPA. TPA is a third-order nonlinear effect, and the probability of TPA occurrence is proportional to the square of the incident light intensity. If only the light intensity at the focal point of the in...

Claims

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Application Information

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IPC IPC(8): C08F2/46C07D401/14C07D409/14C07D417/14
CPCC07D401/14C07D409/14C07D417/14C08F2/46
Inventor 张帅李尚耕张伟尹强万翔宇朱方华李娃王宇光徐嘉靖
Owner LASER FUSION RES CENT CHINA ACAD OF ENG PHYSICS
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