阅读说明：本技术 一种含n-苯基咔唑二酐类化合物及其合成方法 (N-phenyl carbazole dianhydride-containing compound and synthesis method thereof ) 是由 刘煜阳 张晓晨 刘瑞文 吕勇达 修江善 于 2021-02-08 设计创作，主要内容包括：本发明公开了一种含N-苯基咔唑结构的二酐化合物及其制备方法,该化合物的结构为：,将N-苯基咔唑-2,2’,3,3’-四羧酸溶于乙酸、乙酸酐等有机溶剂中,在硅基固体脱水剂SH-01催化下,于无氧环境下,加热至回流保温5～10h,得到相应的N-苯基咔唑结构的二酐化合物N-苯基咔唑-2,2’,3,3’-二酐,反应完后,经过滤、重结晶,其经纯化ωⅡ＞99%,反应收率大于70%。该类化合物可用于聚酰亚胺材料的合成。(The invention discloses a dianhydride compound containing an N-phenylcarbazole structure and a preparation method thereof, wherein the structure of the compound is as follows:)

1. An N-phenyl carbazole dianhydride-containing compound is characterized in that the structure of the compound is as follows:

the compound can be used for synthesizing polyimide materials.

2. A synthetic method of the compound containing N-phenyl carbazole dianhydride in claim 1 is characterized by adopting the following synthetic route:

the method comprises the steps of taking N-phenylcarbazole-2, 2', 3, 3' -tetracarboxylic acid shown in a structure I as a raw material, taking an organic solvent as a reaction medium, heating to reflux and preserving heat for 5-10 hours in an oxygen-free environment under the catalysis of a silicon-based solid dehydrating agent SH-01 to obtain the corresponding dianhydride containing N-phenylcarbazoleAfter the reaction of the compound IIN-phenylcarbazole-2, 2', 3, 3' -dianhydride is finished, the compound is filtered and recrystallized, the purified omega II is more than 99 percent, and the reaction yield is more than 70 percent.

3. The method for synthesizing the compound containing N-phenylcarbazole dianhydride according to claim 2, wherein the organic solvent is one or more of acetic acid, acetic anhydride, trifluoroacetic anhydride, xylene and tetrahydrofuran.

4. The method for synthesizing the compound containing N-phenylcarbazole dianhydride according to claim 2, wherein the reaction temperature is 30-150 ℃ and the reaction time is 5-10 hours.

5. The use of a compound containing N-phenylcarbazole dianhydride according to claim 1 in the field of polyimides.

Technical Field

The invention belongs to the technical field of polyimide materials, and particularly relates to an N-phenylcarbazole dianhydride-containing compound and a synthesis method thereof.

Background

The N-phenylcarbazole-2, 2', 3, 3' -dianhydride is a novel dianhydride compound containing an N-phenylcarbazole group, has a good electron donor, and can be polymerized with various amine compounds to produce polyimide. Polyimide has excellent properties such as high strength, low dielectric, high modulus, high temperature resistance, radiation resistance and the like, is concerned, and has wide application prospect and great commercial value in a plurality of high and new technical fields such as aerospace, aviation, space, microelectronics, precise machinery, medical appliances, organic light-emitting and electricity-generating materials, optical storage and the like.

Polyimide is generally prepared from dianhydride and diamine through binary copolymerization, and different monomer structures determine various properties of polyimide materials, so the research and development of polyimide monomer raw materials are a prerequisite condition for developing novel polyimide materials. At present, polyimides with single performance are very common, and how to develop a polyimide with multiple functional properties at the same time is an important subject of polyimide research at present.

N-phenylcarbazole is a good electron donor with aromaticity, is easy to form a D-pi-A system, and has high electron density and a good rigid structure. According to the invention, N-phenyl carbazole group is used for constructing the dianhydride compound, and then the dianhydride compound and diamine monomer are used for preparing the polyimide, so that the electron-donating capability of a dianhydride structure can be enhanced, the molecular delocalization is increased, and the polyimide has excellent storage performance and photoelectric performance.

Disclosure of Invention

The invention aims to improve the performance of a polyimide material, and provides a dianhydride compound containing an N-phenylcarbazole structure and having high planarity and a synthesis method thereof.

The invention aims to realize the purpose, and the compound containing N-phenylcarbazole dianhydride is characterized in that the structure of the compound is as follows:

the compound is used for synthesizing polyimide materials.

In order to achieve the purpose of the invention, the compound containing N-phenyl carbazole dianhydride uses the following synthetic route:the method comprises the steps of taking N-phenylcarbazole-2, 2', 3, 3' -tetracarboxylic acid shown in a structure I as a raw material, taking acetic acid, acid anhydride and other organic solvents as reaction media, heating to reflux and preserving heat for 5-10 hours in an oxygen-free environment under the catalysis of a silicon-based solid dehydrating agent SH-01 to obtain a corresponding N-phenylcarbazole dianhydride-containing compound IIN-phenylcarbazole-2, 2', 3, 3' -dianhydride, filtering and recrystallizing after the reaction is finished, wherein omega II is purified to be more than 99%, and the reaction yield is more than 70%.

In order to further achieve the purpose of the invention, the organic solvent may be one or more of acetic acid, acetic anhydride, trifluoroacetic anhydride, xylene and tetrahydrofuran.

In order to further realize the purpose of the invention, the reaction temperature can be 30-150 ℃, and the reaction time can be 5-10 h.

When the structure of the compound is designed, the dianhydride compound containing N-phenylcarbazole is designed and synthesized, and the dianhydride is used for preparing polyimide containing N-phenylcarbazole, so that the polyimide has excellent storage performance and good photoelectric performance. The invention has the following beneficial effects:

1. according to the invention, an N-phenylcarbazole group containing strong intramolecular electron transfer is introduced into the dianhydride compound, and after polyimide is synthesized, the electron transfer capacity is greatly improved.

2. The dianhydride compound synthesized by the invention and the diamine monomer are polymerized to generate polyimide, and the polyimide has good light transmittance.

3. The data for the compounds of the invention compared to BPDA are shown in the following table:

name of Compound	Molecular weight	Boiling point/. degree.C	Melting Point/. degree.C
				BPDA	294.22	609	199
Ⅱ	383.31	705	502

Detailed Description

The present invention is further illustrated by the following examples, which are included merely for the purpose of clarity and are not intended to limit the invention.

An N-phenyl carbazole dianhydride-containing compound has the following structure:

，

the synthetic route is as follows:

the method comprises the following steps of sequentially adding 30g of N-phenylcarbazole-2, 2', 3, 3' -tetracarboxylic acid, SH-010.15 g of a silicon-based solid dehydrating agent, 100mL of tetrahydrofuran, 90mL of acetic acid and 110mL of acetic anhydride into a 500mL three-neck reaction flask provided with a mechanical stirring device, a reflux condenser tube, a nitrogen protection device and an addition funnel, starting stirring and heating until the mixture flows back, reacting for 6 hours, sampling and analyzing, determining the reaction termination according to a GC analysis result, cooling, filtering, adding dichloromethane for recrystallization, purifying, and recovering mother liquor to obtain 30.25g of a product. Purity ω: 99.3 percent and the yield is 71.88 percent.

The electron withdrawing effect of the dianhydride group and the electron donating effect of the diamine group form an electron transfer complex effect (CTC), and the charge transfer effect in molecules or between molecules causes the film to show brown yellow in a visible light range. The introduction of the group containing carbazole dianhydride can inhibit the formation of CTC and improve various properties of the PI material;

the copolymerization type fluorine-containing Polyimide (PI) film is synthesized by N-phenylcarbazole-2, 2', 3, 3' -dianhydride monomer and 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl monomer according to a certain proportion, has good photoelectric property, and the light transmittance in a visible light region can reach more than 85 percent, while the light transmittance of the copolymerization type fluorine-containing Polyimide (PI) film synthesized by the traditional biphenyl dianhydride monomer and the 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl monomer according to the same proportion is only 65 percent; the PI material prepared from dianhydride and diamine can be used for display devices such as mobile phones and computers, and the photoelectric property of the PI material is improved;

and (3) product structure confirmation: the elemental analysis measured values were w (c) = 63.04%, w (h) = 3.10%, w (n) =3.30%, w (o) = 30.56%; theoretical values w (c) = 63.02%, w (h) = 3.12%, w (n) =3.34%, w (o) = 30.52%; melting Point>470℃；MS：m/s= 419.06（M⁺)。