阅读说明：本技术 基于吩噻嗪或咔唑的杂环改性双光子聚合引发剂及其制备方法 (Heterocyclic modified two-photon polymerization initiator based on phenothiazine or carbazole and preparation method thereof ) 是由 张帅 李尚耕 张伟 尹强 万翔宇 朱方华 李娃 王宇光 徐嘉靖 于 2019-10-28 设计创作，主要内容包括：本发明公开了一种基于吩噻嗪或咔唑的杂环改性双光子聚合引发剂及其制备方法,包括：步骤一、对原料吩噻嗪和3,6-二溴-9H-咔唑通过亲核取代加入烷基进行保护；步骤二、对步骤一的产物进行Sonogashira偶联反应,引入炔基；步骤三、对步骤二的产物进行去保护；步骤四、对步骤三的产物进行Sonogashira偶联反应,引入吸电子基团。本发明制备的杂环改性吩噻嗪和咔唑衍生物双光子引发剂,表现出良好的稳定性,溶解性和双光子聚合活性,用其进行双光子聚合反应加工的扫描速率快,微结构精度较好。研究了本发明的引发剂的光学性质和双光子聚合性能,结果表明,最佳性能的引发剂TPA截面可达到1315GM,聚合过程中扫描速度可达14000μm/s。(The invention discloses a heterocycle modified two-photon polymerization initiator based on phenothiazine or carbazole and a preparation method thereof, wherein the heterocycle modified two-photon polymerization initiator comprises the following steps: firstly, adding alkyl into phenothiazine and 3, 6-dibromo-9H-carbazole serving as raw materials for protection through nucleophilic substitution; step two, carrying out Sonogashira coupling reaction on the product obtained in the step one, and introducing alkynyl; step three, performing deprotection on the product obtained in the step two; and step four, performing Sonogashira coupling reaction on the product obtained in the step three, and introducing an electron-withdrawing group. The heterocyclic modified phenothiazine and carbazole derivative two-photon initiator prepared by the invention has good stability, solubility and two-photon polymerization activity, and the scanning rate of the two-photon polymerization reaction processing by using the heterocyclic modified phenothiazine and carbazole derivative two-photon initiator is high, and the microstructure precision is good. The optical property and the two-photon polymerization performance of the initiator are researched, and the result shows that the cross section of TPA (terephthalic acid) of the initiator with the best performance can reach 1315GM, and the scanning speed in the polymerization process can reach 14000 mu m/s.)

1. A heterocycle modified two-photon polymerization initiator based on phenothiazine or carbazole is characterized in that the initiator is formed by connecting phenothiazine or carbazole molecules with thiophene formaldehyde or quinoline groups through carbon-carbon triple bond conjugated expansion to form an A-pi-D-pi-A structure, and the molecular structural formula is as follows:

or

Or

Or

2. A method of preparing a phenothiazine or carbazole-based heterocycle modified two-photon polymerization initiator as claimed in claim 1, comprising the steps of:

firstly, adding alkyl into phenothiazine and 3, 6-dibromo-9H-carbazole serving as raw materials for protection through nucleophilic substitution; carrying out bromination reaction on phenothiazine, and introducing para-bromine;

step two, carrying out Sonogashira coupling reaction on the product obtained in the step one, and introducing alkynyl;

step three, performing deprotection on the product obtained in the step two;

and step four, performing Sonogashira coupling reaction on the product obtained in the step three, and introducing an electron-withdrawing group.

3. The method for preparing a phenothiazine-or carbazole-based heterocycle-modified two-photon polymerization initiator as claimed in claim 2, wherein the process of the first step is: slowly adding NaH stored in mineral oil into a phenothiazine-containing DMF solution which is cooled to 0-10 ℃, and slowly adding 1-bromododecane after 10-20 minutes; stirring the obtained solution at 0-10 ℃ overnight, and slowly adding deionized water; after stirring for half an hour, extraction with ethyl acetate and then purification by column chromatography using a 40: 1, petroleum ether and ethyl acetate are used as eluent to obtain 10-dodecyl-10H-phenothiazine which is light yellow oily matter;

slowly adding NBS into a solution which is cooled to 0-10 ℃ and contains 10-dodecyl-10H-phenothiazine and DCM, stirring the obtained suspension at 0-10 ℃ overnight, then slowly adding deionized water and stirring for 20-40 minutes, then adding saturated saline and extracting to obtain an organic phase; then dried over magnesium sulfate, filtered, the solvent removed, and then purified by column chromatography using a solvent in a volume ratio of 40: 1 petroleum ether: ethyl acetate is used as eluent to obtain 3, 7-dibromo-10-dodecyl-phenothiazine; is light yellow oil;

or the process of the step one is as follows: slowly adding NaH stored in mineral oil into a DMF flask containing 3, 6-dibromo-9H-carbazole and cooled to 0-10 ℃, slowly adding 1-bromododecane after 10-20 minutes, stirring the obtained suspension at 0-10 ℃ overnight, slowly adding deionized water, filtering, and washing with petroleum ether to obtain the 3, 6-dibromo-9-dodecyl-carbazole which is gray solid.

4. The method for preparing a phenothiazine-or carbazole-based heterocycle-modified two-photon polymerization initiator as claimed in claim 3, wherein in the first step, the NaH is stored in mineral oil at a mass fraction of 60%; the molar ratio of NaH to phenothiazine is 1.2-2: 1; the molar ratio of the phenothiazine to the 1-bromododecane is 1: 1-1.5; the mass-volume ratio of the phenothiazine to the DMF is 1g: 6-10 mL; the molar ratio of the 10-dodecyl-10H-phenothiazine to the NBS is 1: 2-3; the molar volume ratio of the 10-dodecyl-10H-phenothiazine to DCM is 1mmol:4 mL;

the molar ratio of NaH to 3, 6-dibromo-9H-carbazole is 1.2-2: 1; the molar ratio of the 3, 6-dibromo-9H-carbazole to the 1-bromododecane is 1: 1-1.5; the mass-volume ratio of the 3, 6-dibromo-9H-carbazole to the DMF is 1g: 4-8 mL.

5. The method for preparing a phenothiazine-or carbazole-based heterocycle-modified two-photon polymerization initiator as claimed in claim 2, wherein the process of the second step is: adding 3, 7-dibromo-10-dodecyl-phenothiazine, CuI and PdCl into a reactor₂(PPh₃)₂、PPh₃1, 1-dimethyl-2-Refluxing butyn-1-ol and triethylamine under Ar protection at 85-90 deg.C for 8-9 hr, cooling, removing solvent, pouring residue into saturated saline and extracting with ethyl acetate for 3 times (100mL each), combining organic layers, and MgSO₄Dried, concentrated, and applied at a volume ratio of 6: 1 petroleum ether and ethyl acetate as eluent, and purifying by column chromatography to obtain 4- [ 10-dodecyl-7- (3-hydroxy-3-) (methyl-butyl-1-alkynyl) -phenothiazin-3-yl]-2-methyl-but-3-yn-2-ol as a pale yellow oil;

or the process of the step two is as follows: adding 3, 6-dibromo-9-dodecyl-carbazole, CuI and PdCl into a reactor₂(PPh₃)₂、PPh₃Refluxing the mixture at 85-90 deg.C for 8-9 hr under Ar protection, cooling, removing solvent, pouring the residue into saturated saline and extracting with ethyl acetate for 3 times (100mL each time), combining the organic layers, and adding MgSO 5₄Dried, concentrated, and applied at a volume ratio of 6: 1 petroleum ether and ethyl acetate as eluent, purifying by column chromatography to obtain 4- [ 9-dodecyl-6- (3-hydroxy-3-methyl-but-1-ynyl) -carbazol-3-yl]-2-methyl-but-3-yn-2-ol as a pale yellow oil.

6. The method for preparing a phenothiazine-or carbazole-based heterocycle-modified two-photon polymerization initiator as claimed in claim 5, wherein in the second step, the molar ratio of the 3, 7-dibromo-10-dodecyl-phenothiazine to the CuI is 8-12: 1; the 3, 7-dibromo-10-dodecyl-phenothiazine and PdCl₂(PPh₃)₂The molar ratio of (A) to (B) is 18-22: 1; the 3, 7-dibromo-10-dodecyl-phenothiazine and PPh₃The molar ratio of (A) to (B) is 1: 80-120; the molar ratio of the 3, 7-dibromo-10-dodecyl-phenothiazine to the 1, 1-dimethyl-2-butyne-1-ol is 1: 2.5-4; the mass-volume ratio of the 3, 7-dibromo-10-dodecyl-phenothiazine to triethylamine is 1g: 13-17 mL;

in the second step, the molar ratio of the 3, 6-dibromo-9-dodecyl-carbazole to the CuI is 8-12: 1; the 3, 6-dibromo-9-dodecyl-carbazole and the PdCl₂(PPh₃)₂The molar ratio of (A) to (B) is 18-22: 1; the 3, 6-dibromo-9-dodecyl-carbazole and PPh₃The molar ratio of (A) to (B) is 1: 80-120; the molar ratio of the 3, 6-dibromo-9-dodecyl-carbazole to the 1, 1-dimethyl-2-butyne-1-ol is 1: 2.5-4; the mass-volume ratio of the 3, 6-dibromo-9-dodecyl-carbazole to the triethylamine is 1g: 13-17 mL.

7. The method for preparing a phenothiazine-or carbazole-based heterocycle-modified two-photon polymerization initiator as claimed in claim 2, wherein the process in the third step is: adding potassium hydroxide to an isopropanol solution containing 4- [ 10-dodecyl-7- (3-hydroxy-3-) (methyl-but-1-ynyl) -phenothiazin-3-yl ] -2-methyl-but-3-yn-2-ol, refluxing the resulting mixture at 85 to 90 ℃ for 2.5 to 4 hours under Ar protection, cooling while keeping argon gas under reflux after completion of the reaction, concentrating, dissolving in ethyl acetate, extracting 3 times with saturated saline solution, 50mL each time, drying over anhydrous magnesium sulfate and concentrating, purifying a dark brown residue by column chromatography using a volume ratio of 20: 1, and taking petroleum ether and ethyl acetate as eluent to obtain 10-dodecyl-3, 7-diacetylene-phenothiazine as light yellow oily matter;

or the process in the third step is as follows: adding potassium hydroxide into an isopropanol solution containing 4- [ 9-dodecyl-6- (3-hydroxy-3-methyl-but-1-alkynyl) -carbazol-3-yl ] -2-methyl-but-3-yn-2-ol, refluxing the obtained mixture at 85-90 ℃ for 2.5-4 hours under the protection of Ar, cooling while keeping introducing argon after the reaction is completed, concentrating, dissolving in ethyl acetate, extracting for 3 times with saturated saline solution, 50mL each time, drying with anhydrous magnesium sulfate and concentrating, purifying a dark brown residue by column chromatography, and purifying with a solvent with a volume ratio of 20: 1 with petroleum ether and ethyl acetate as eluent, to give 9-dodecyl-3, 6-diacetylene-carbazole as a pale yellow oil.

8. The method for preparing a phenothiazine-or carbazole-based heterocycle-modified two-photon polymerization initiator as claimed in claim 7, wherein the molar ratio of 4- [ 10-dodecyl-7- (3-hydroxy-3-) (methyl-but-1-ynyl) -phenothiazin-3-yl ] -2-methyl-but-3-yn-2-ol to potassium hydroxide is 1:5 to 7; the molar volume ratio of the 4- [ 10-dodecyl-7- (3-hydroxy-3-) (methyl-butyl-1-alkynyl) -phenothiazin-3-yl ] -2-methyl-butyl-3-alkyne-2-alcohol to isopropanol is 5mmol: 40-60 mL;

the molar ratio of the 4- [ 9-dodecyl-6- (3-hydroxy-3-methyl-butyl-1-alkynyl) -carbazole-3-yl ] -2-methyl-butyl-3-alkyne-2-alcohol to potassium hydroxide is 1: 5-7; the molar volume ratio of the 4- [ 10-dodecyl-7- (3-hydroxy-3-) (methyl-butyl-1-alkynyl) -phenothiazin-3-yl ] -2-methyl-butyl-3-alkyne-2-alcohol to isopropanol is 5mmol: 40-60 mL.

9. The method for preparing a phenothiazine-or carbazole-based heterocycle-modified two-photon polymerization initiator as claimed in claim 2, wherein the process of the fourth step is: adding 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole into a reactor, and then adding PdCl₂(PPh₃)₂、PPh₃5-bromo-thiophene-2-carbaldehyde, triethylamine and DMF, and degassed with Ar for 10-15 minutes, refluxing the resulting mixture for 8 hours, cooling, removing the solvent, pouring the residue into saturated brine and extracting with ethyl acetate 3 times 30mL each, combining the organic layers, MgSO 2₄Drying, concentrating and purifying by column chromatography to obtain products of molecular structural formula (I) and molecular structural formula (III);

or the process of the fourth step is as follows: adding 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole into a reactor, and then adding PdCl₂(PPh₃)₂、PPh₃6-bromo-quinoline, triethylamine and DMF, degassed with Ar for 10-15 min, refluxing the resulting mixture for 8 h, cooling, removing the solvent, pouring the residue into saturated brine and extracting with ethyl acetate 3 times 30mL each, combining the organic layers, MgSO 2₄Drying, concentrating and purifying by column chromatography to obtain the products of molecular structural formula (II) and molecular structural formula (IV).

10. The method for preparing a phenothiazine-or carbazole-based heterocycle-modified two-photon polymerization initiator as claimed in claim 9, wherein in step four: the molar ratio of the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole to the CuI is 8-12: 1; the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole and PdCl₂(PPh₃)₂The molar ratio of (A) to (B) is 18-22: 1; the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole and PPh₃The molar ratio of (A) to (B) is 1: 80-120; the molar ratio of the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole to the 5-bromo-thiophene-2-formaldehyde is 1: 2-4; the molar volume ratio of the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole to triethylamine is 1mmol:200 mL; the molar volume ratio of the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole to DMF is 1mmol:100 mL;

the molar ratio of the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole to the 6-bromo-quinoline is 1: 2-4.

Technical Field

The invention belongs to the technical field of chemical synthesis, and particularly relates to a phenothiazine or carbazole-based heterocyclic modified two-photon polymerization initiator and a preparation method thereof.

Background

With the increasing demand of micro-nano materials, a new, more effective and higher-resolution micro-nano material manufacturing method appears. Two-photon polymerization additive manufacturing becomes an important novel micro-nano manufacturing method due to the unique two-photon effect. In the 30's of the 20 th century, Goppert-Mayer theoretically predicted two-photon absorption (TPA) under intense light excitation. Until the advent of high-energy lasers, the TPA phenomenon was not observed by researchers. TPA is a third-order nonlinear effect, and the probability of TPA occurring is proportional to the square of the incident light intensity. The occurrence of TPA is limited to a small area of the cube of the wavelength of the incident light if only the light intensity at the focal point of the incident light reaches the photon density of the TPA occurrence. Thus, TPA has a high spatial selectivity. Therefore, the chemical reaction process is also induced to be concentrated only in a minute focal area. In addition, the wavelength of the TPA light source is near infrared light, so that Rayleigh scattering loss and dielectric absorption of exciting light can be effectively reduced, and better penetrability is achieved. In summary, two-photon polymeric additive manufacturing can achieve true 3D printing because it has high penetration, high spatial selectivity and high resolution. In TPPAM, polymerization of the monomer is initiated by the action of a laser after a photoinitiator is mixed with the monomer resin. The efficiency of the initiator affects the effect of the polymerization and the laser intensity and scanning speed applicable. And thus almost directly determines the fabrication resolution. However, current two-photon polymerization initiators are still relatively inefficient and insufficient for large scale additive manufacturing. Therefore, the research of the efficient two-photon polymerization initiator is very important.

Disclosure of Invention

An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.

To achieve these objects and other advantages in accordance with the present invention, there is provided a phenothiazine-or carbazole-based heterocycle modified two-photon polymerization initiator having a structure a-pi-D-pi-a, wherein a phenothiazine or carbazole molecule is extended by carbon-carbon triple bond conjugation to connect a thiophenecarboxaldehyde or quinoline group, and the molecular structure is:

the invention also provides a preparation method of the phenothiazine or carbazole-based heterocyclic modified two-photon polymerization initiator, which comprises the following steps:

firstly, adding alkyl into phenothiazine and 3, 6-dibromo-9H-carbazole serving as raw materials for protection through nucleophilic substitution; carrying out bromination reaction on phenothiazine, and introducing para-bromine;

step two, carrying out Sonogashira coupling reaction on the product obtained in the step one, and introducing alkynyl;

step three, performing deprotection on the product obtained in the step two;

and step four, performing Sonogashira coupling reaction on the product obtained in the step three, and introducing an electron-withdrawing group.

Preferably, the process of the first step is as follows: slowly adding NaH stored in mineral oil into a phenothiazine-containing DMF solution which is cooled to 0-10 ℃, and slowly adding 1-bromododecane after 10-20 minutes; stirring the obtained solution at 0-10 ℃ overnight, and slowly adding deionized water; after stirring for half an hour, extraction with ethyl acetate and then purification by column chromatography using a 40: 1, petroleum ether and ethyl acetate are used as eluent to obtain 10-dodecyl-10H-phenothiazine which is light yellow oily matter;

slowly adding NBS into a solution which is cooled to 0-10 ℃ and contains 10-dodecyl-10H-phenothiazine and DCM, stirring the obtained suspension at 0-10 ℃ overnight, then slowly adding deionized water and stirring for 20-40 minutes, then adding saturated saline and extracting to obtain an organic phase; then dried over magnesium sulfate, filtered, the solvent removed, and then purified by column chromatography using a solvent in a volume ratio of 40: 1 petroleum ether: ethyl acetate is used as eluent to obtain 3, 7-dibromo-10-dodecyl-phenothiazine; is light yellow oil;

or the process of the step one is as follows: slowly adding NaH stored in mineral oil into a DMF flask containing 3, 6-dibromo-9H-carbazole, which is cooled to 0-10 ℃, after 10-20 minutes, slowly adding 1-bromododecane, stirring the obtained suspension at 0-10 ℃ overnight, slowly adding deionized water, filtering, and washing with petroleum ether to obtain 3, 6-dibromo-9-dodecyl-carbazole which is gray solid;

preferably, in the first step, the mass fraction of the NaH stored in the mineral oil is 60%; the molar ratio of NaH to phenothiazine is 1.2-2: 1; the molar ratio of the phenothiazine to the 1-bromododecane is 1: 1-1.5; the mass-volume ratio of the phenothiazine to the DMF is 1g: 6-10 mL; the molar ratio of the 10-dodecyl-10H-phenothiazine to the NBS is 1: 2-3; the molar volume ratio of the 10-dodecyl-10H-phenothiazine to DCM is 1mmol:4 mL;

the molar ratio of NaH to 3, 6-dibromo-9H-carbazole is 1.2-2: 1; the molar ratio of the 3, 6-dibromo-9H-carbazole to the 1-bromododecane is 1: 1-1.5; the mass-volume ratio of the 3, 6-dibromo-9H-carbazole to the DMF is 1g: 4-8 mL;

preferably, the process of step two is as follows: adding 3, 7-dibromo-10-dodecyl-phenothiazine, CuI and PdCl into a reactor₂(PPh₃)₂、PPh₃1, 1-dimethyl-2-butyn-1-olAnd triethylamine, refluxing the resulting mixture at 85-90 deg.C for 8-9 hr under Ar protection, cooling, removing solvent, pouring the residue into saturated brine and extracting with ethyl acetate for 3 times (100mL each), combining the organic layers, MgSO₄Dried, concentrated, and applied at a volume ratio of 6: 1 petroleum ether and ethyl acetate as eluent, and purifying by column chromatography to obtain 4- [ 10-dodecyl-7- (3-hydroxy-3-) (methyl-butyl-1-alkynyl) -phenothiazin-3-yl]-2-methyl-but-3-yn-2-ol as a pale yellow oil;

or the process of the step two is as follows: adding 3, 6-dibromo-9-dodecyl-carbazole, CuI and PdCl into a reactor₂(PPh₃)₂、PPh₃Refluxing the mixture at 85-90 deg.C for 8-9 hr under Ar protection, cooling, removing solvent, pouring the residue into saturated saline and extracting with ethyl acetate for 3 times (100mL each time), combining the organic layers, and adding MgSO 5₄Dried, concentrated, and applied at a volume ratio of 6: 1 petroleum ether and ethyl acetate as eluent, purifying by column chromatography to obtain 4- [ 9-dodecyl-6- (3-hydroxy-3-methyl-but-1-ynyl) -carbazol-3-yl]-2-methyl-but-3-yn-2-ol as a pale yellow oil.

Preferably, in the second step, the molar ratio of the 3, 7-dibromo-10-dodecyl-phenothiazine to the CuI is 8-12: 1; the 3, 7-dibromo-10-dodecyl-phenothiazine and PdCl₂(PPh₃)₂The molar ratio of (A) to (B) is 18-22: 1; the 3, 7-dibromo-10-dodecyl-phenothiazine and PPh₃The molar ratio of (A) to (B) is 1: 80-120; the molar ratio of the 3, 7-dibromo-10-dodecyl-phenothiazine to the 1, 1-dimethyl-2-butyne-1-ol is 1: 2.5-4; the mass-volume ratio of the 3, 7-dibromo-10-dodecyl-phenothiazine to triethylamine is 1g: 13-17 mL;

in the second step, the molar ratio of the 3, 6-dibromo-9-dodecyl-carbazole to the CuI is 8-12: 1; the 3, 6-dibromo-9-dodecyl-carbazole and PdCl₂(PPh₃)₂The molar ratio of (A) to (B) is 18-22: 1; the 3, 6-dibromo-9-dodecyl-carbazole and PPh₃The molar ratio of (A) to (B) is 1: 80-120; the 3, 6-dibromoThe molar ratio of the-9-dodecyl-carbazole to the 1, 1-dimethyl-2-butyn-1-ol is 1: 2.5-4; the mass-volume ratio of the 3, 6-dibromo-9-dodecyl-carbazole to the triethylamine is 1g: 13-17 mL;

preferably, the process in step three is as follows: adding potassium hydroxide to an isopropanol solution containing 4- [ 10-dodecyl-7- (3-hydroxy-3-) (methyl-but-1-ynyl) -phenothiazin-3-yl ] -2-methyl-but-3-yn-2-ol, refluxing the resulting mixture at 85 to 90 ℃ for 2.5 to 4 hours under Ar protection, cooling while keeping argon gas under reflux after completion of the reaction, concentrating, dissolving in ethyl acetate, extracting 3 times with saturated saline solution, 50mL each time, drying over anhydrous magnesium sulfate and concentrating, purifying a dark brown residue by column chromatography using a volume ratio of 20: 1, and taking petroleum ether and ethyl acetate as eluent to obtain 10-dodecyl-3, 7-diacetylene-phenothiazine as light yellow oily matter;

or the process in the third step is as follows: adding potassium hydroxide into an isopropanol solution containing 4- [ 9-dodecyl-6- (3-hydroxy-3-methyl-but-1-alkynyl) -carbazol-3-yl ] -2-methyl-but-3-yn-2-ol, refluxing the obtained mixture at 85-90 ℃ for 2.5-4 hours under the protection of Ar, cooling while keeping introducing argon after the reaction is completed, concentrating, dissolving in ethyl acetate, extracting for 3 times with saturated saline solution, 50mL each time, drying with anhydrous magnesium sulfate and concentrating, purifying a dark brown residue by column chromatography, and purifying with a solvent with a volume ratio of 20: 1 with petroleum ether and ethyl acetate as eluent, to give 9-dodecyl-3, 6-diacetylene-carbazole as a pale yellow oil.

Preferably, the molar ratio of the 4- [ 10-dodecyl-7- (3-hydroxy-3-) (methyl-but-1-alkynyl) -phenothiazin-3-yl ] -2-methyl-but-3-alkyne-2-alcohol to the potassium hydroxide is 1: 5-7; the molar volume ratio of the 4- [ 10-dodecyl-7- (3-hydroxy-3-) (methyl-butyl-1-alkynyl) -phenothiazin-3-yl ] -2-methyl-butyl-3-alkyne-2-alcohol to isopropanol is 5mmol: 40-60 mL;

the molar ratio of the 4- [ 9-dodecyl-6- (3-hydroxy-3-methyl-butyl-1-alkynyl) -carbazole-3-yl ] -2-methyl-butyl-3-alkyne-2-alcohol to potassium hydroxide is 1: 5-7; the molar volume ratio of the 4- [ 10-dodecyl-7- (3-hydroxy-3-) (methyl-butyl-1-alkynyl) -phenothiazin-3-yl ] -2-methyl-butyl-3-alkyne-2-alcohol to isopropanol is 5mmol: 40-60 mL.

Preferably, the process of step four is as follows: adding 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole into a reactor, and then adding PdCl₂(PPh₃)₂、PPh₃5-bromo-thiophene-2-carbaldehyde, triethylamine and DMF, and degassed with Ar for 10-15 minutes, refluxing the resulting mixture for 8 hours, cooling, removing the solvent, pouring the residue into saturated brine and extracting with ethyl acetate 3 times 30mL each, combining the organic layers, MgSO 2₄Drying, concentrating and purifying by column chromatography to obtain products of molecular structural formula (I) and molecular structural formula (III);

or the process of the fourth step is as follows: adding 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole into a reactor, and then adding PdCl₂(PPh₃)₂、PPh₃6-bromo-quinoline, triethylamine and DMF, degassed with Ar for 10-15 min, refluxing the resulting mixture for 8 h, cooling, removing the solvent, pouring the residue into saturated brine and extracting with ethyl acetate 3 times 30mL each, combining the organic layers, MgSO 2₄Drying, concentrating and purifying by column chromatography to obtain the products of molecular structural formula (II) and molecular structural formula (IV).

Preferably, in the fourth step: the molar ratio of the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole to the CuI is 8-12: 1; the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole and PdCl₂(PPh₃)₂The molar ratio of (A) to (B) is 18-22: 1; the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole and PPh₃The molar ratio of (A) to (B) is 1: 80-120; the molar ratio of the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole to the 5-bromo-thiophene-2-formaldehyde is 1: 2-4; the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetyleneThe molar volume ratio of carbazole to triethylamine is 1mmol:200 mL; the molar volume ratio of the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole to DMF is 1mmol:100 mL;

the molar ratio of the 10-dodecyl-3, 7-diacetylene-phenothiazine or 9-dodecyl-3, 6-diacetylene-carbazole to the 6-bromo-quinoline is 1: 2-4.

The invention at least comprises the following beneficial effects:

(1) the heterocyclic modified phenothiazine and carbazole derivative two-photon initiator prepared by the invention has good stability, solubility and two-photon polymerization activity, and the scanning rate of the two-photon polymerization reaction processing by using the heterocyclic modified phenothiazine and carbazole derivative two-photon initiator is high, and the microstructure precision is good.

(2) The preparation method of the phenothiazine and carbazolyl two-photon initiator is simple and convenient, simple in purification, short in required time and high in purity of the obtained product.

(3) The optical property and the two-photon polymerization performance of the initiator are researched, and the result shows that the cross section of TPA (terephthalic acid) of the initiator with the best performance can reach 1315GM, and the scanning speed in the polymerization process can reach 14000 mu m/s.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

Description of the drawings:

FIG. 1 is a chemical reaction formula of step one to step four in examples 1, 2, 5 and 6 of the present invention;

FIG. 2 is a chemical reaction formula of step five in examples 1 and 5 of the present invention;

FIG. 3 is a chemical reaction formula of step five in examples 2 and 6 of the present invention;

FIG. 4 is a chemical reaction formula of step one to step four in examples 3, 4, 7 and 8 of the present invention;

FIG. 5 is a chemical reaction formula of step five in examples 3 and 7 of the present invention;

FIG. 6 is a chemical reaction formula of step five in examples 4 and 8 of the present invention;

FIG. 7 is a nuclear magnetic hydrogen spectrum of the product of examples 1 and 5 of the present invention;

FIG. 8 is a nuclear magnetic hydrogen spectrum of the products of examples 2 and 6 of the present invention;

FIG. 9 is a nuclear magnetic hydrogen spectrum of the products of examples 3 and 7 of the present invention;

FIG. 10 is a nuclear magnetic hydrogen spectrum of the products of examples 4 and 8 of the present invention;

FIG. 11 is a scanning electron microscope image of a structure formed by polymerization initiated by the products of examples 1 and 5.

The specific implementation mode is as follows:

the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.

It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.