阅读说明：本技术 一种含吩噻嗪和酰胺结构的二胺及其聚酰亚胺 (Diamine containing phenothiazine and amide structures and polyimide thereof ) 是由 谭井华 刘亦武 李禹慧 张祥 于 2019-12-15 设计创作，主要内容包括：本发明公开了一种含吩噻嗪和酰胺结构的二胺及其制备的聚酰亚胺。本发明将二卤代的吩噻嗪的原子转化为氰基,水解得到二羧酸单体,接着酰氯化,再通过酰胺反应接枝含硝基的基团,最后还原获得二胺单体,获得含吩噻嗪和酰胺结构的二胺单体,然后将制备的二胺单体与二酐聚合,得到含吩噻嗪和酰胺结构的聚酰亚胺。本发明创造性地将吩噻嗪的平面刚性结构和酰胺极性基团引入聚酰亚胺主链,平面刚性结构有利于分子链规整堆砌,诱导聚合物结晶,极性基团可以增强分子链的氢键作用,促进分子链紧密堆砌,从而使聚酰亚胺具有优异的阻隔性能,较高的玻璃化转变温度和热稳定性,较低的热膨胀系数以及抗菌性。(The invention discloses diamine containing phenothiazine and amide structures and polyimide prepared from the diamine. The method comprises the steps of converting atoms of dihalogenated phenothiazine into cyano groups, hydrolyzing to obtain dicarboxylic acid monomers, then performing acyl chlorination, grafting groups containing nitro groups through amide reaction, finally reducing to obtain diamine monomers containing phenothiazine and amide structures, and then polymerizing the prepared diamine monomers with dianhydride to obtain polyimide containing phenothiazine and amide structures. The invention creatively introduces the planar rigid structure of phenothiazine and amide polar groups into the polyimide main chain, the planar rigid structure is beneficial to regular stacking of molecular chains and induces the crystallization of polymers, and the polar groups can enhance the hydrogen bond effect of the molecular chains and promote the tight stacking of the molecular chains, so that the polyimide has excellent barrier property, higher glass transition temperature and thermal stability, lower thermal expansion coefficient and antibacterial property.)

1. A diamine containing phenothiazine and amide structures is characterized in that the diamine has the following structural general formula:

Ar₁any one selected from the following structural formulas:

wherein n is 0-6, m is 0-6, and n and m in the same structural formula are not 0 at the same time.

2. Diamine containing phenothiazine and amide structures according to claim 1, characterized in that said Ar is Ar₂And Ar₃Any one selected from the following structural formulas:

3. a process according to claim 1 for the preparation of a diamine containing phenothiazine and amide structures, characterized in that it comprises:

s1, phenothiazine monomer substituted by two halogen atoms

s2, adding the monomer 1, the monomer 2 or the monomer 3 in the S1 into a solvent, adding alkali, performing hydrolysis reaction under the atmosphere of protective gas, purifying, and drying to obtain a monomer 4, a monomer 5 or a monomer 6 in the dicarboxylic acid S2;

s3, dissolving the monomer 4, the monomer 5 or the monomer 6 in the S2 in the step S2 into a solvent, adding N, N-dimethylformamide as a catalyst, slowly dropwise adding thionyl chloride under an ice bath condition, and performing acyl chlorination reaction, purification and drying to obtain a diacid chloride monomer 7, a monomer 8 or a monomer 9;

s4, adding the monomer 7, the monomer 8 or the monomer 9 in the step S3 and Ar1 containing an amino group and a nitro group for substitution into a solvent, performing amidation reaction under a protective gas atmosphere, purifying, and drying to obtain a dinitromonomer 10, a monomer 11 or a monomer 12;

s5, adding the monomer 10, the monomer 11 or the monomer 12 in the step S4 into a solvent, introducing protective gas, adding a reducing agent, carrying out reduction reaction, purifying and drying to obtain a diamine monomer containing a phenothiazine structure shown in the structural general formulas I-III;

the monomer 1, the monomer 2 or the monomer 3 in the step S1, the monomer 4, the monomer 5 or the monomer 6 in the step S2, the monomer 7, the monomer 8 and the monomer 9 in the step S3, and the monomer 10, the monomer 11 and the monomer 12 in the step S4 respectively have the following structural characteristics:

Technical Field

The invention relates to the technical field of material science, in particular to diamine containing phenothiazine and amide structures and polyimide thereof.

Background

Organic light-emitting diodes (OL ED) are one of the important products for Organic materials to enter the field of information materials. The flexible organic electroluminescent device (FOLED) made by packaging the OLED by adopting the flexible polymer material has the characteristics of bending, folding, even being wearable and the like, and is an important development direction of the future display technology of the OLED. However, FOLED has problems of insufficient stability and life span, limiting its popularization and application. The key to improving the lifetime of flexible display devices is the selection and development of flexible substrates. First, electrode materials are susceptible to oxidation, and light emitting materials are very sensitive to impurities, water, oxygen, etc., so one of the keys to developing FOLEDs is to reduce the permeation of water vapor and oxygen into the interior of the device.

Polyimide is one of organic polymer materials with the best comprehensive performance, has extremely strong heat resistance, good mechanical property and dimensional stability, and is one of the best choices of flexible OLED substrates or packaging materials. At present, most of commercial polyimide is used as a packaging material and can meet the requirement of packaging of articles with low barrier property, and the diffusion path of water vapor in a base material is effectively prolonged by adding layered nano particles and utilizing the distribution of a flaky nano layer among molecular chains, so that the barrier property of the polyimide is improved. However, for high-barrier requirements such as flexible packaging, although the barrier property of polyimide is improved by using multilayer high-barrier film composite films, thin film plating layers, inorganic nano modification and the like, the high standard of the packaging material on the barrier property cannot be met. In addition, polyimide has heat resistance, stability, flame retardancy and nontoxicity which satisfy the requirements of packaging materials, and polyimide has insufficient antibacterial properties, and it is difficult to ensure that the contents are not contaminated under the condition of high water oxygen transmission rate. Polyimide has stronger molecular structure designability, and if an intrinsic polyimide material with excellent barrier property and certain antibacterial property can be directly prepared through reasonable molecular structure design and chemical synthesis, the application of the polyimide in a high-performance packaging material can be improved. .

Disclosure of Invention

The invention aims to solve the technical problem of providing a diamine containing phenothiazine and amide structures, which is high-temperature resistant and has high barrier property, aiming at the defects of heat resistance and barrier property of the existing polyimide.

Another technical problem to be solved by the invention is to provide a preparation method of the polyimide containing phenothiazine and amide structures.

The invention also solves the technical problem of providing the application of the polyimide containing phenothiazine and amide structures in multiple fields.

The purpose of the invention is realized by the following technical scheme:

a diamine containing phenothiazine and amide structures, wherein the diamine has a general structural formula shown as the following:

Ar₁any one selected from the following structural formulas:

wherein n is 0-6, m is 0-6, and n and m in the same structural formula are not 0 at the same time.

Further, said Ar₂And Ar₃Any one selected from the following structural formulas:

preferably, Ar is₂Is composed ofAndar3 is one or more ofAnd

one or more of (a).

The preparation method of the diamine containing phenothiazine and amide structures comprises the following steps:

s1, phenothiazine monomer substituted by two halogen atomsOrAdding cyanide into a solvent for reaction, purifying and drying to obtain a monomer 1, a monomer 2 or a monomer 3;

s2, adding the monomer 1, the monomer 2 or the monomer 3 in the S1 into a solvent, adding alkali, performing hydrolysis reaction in a protective gas atmosphere, purifying, and drying to obtain a dicarboxylic acid monomer 4, a monomer 5 or a monomer 6;

s3, dissolving the monomer 4, the monomer 5 or the monomer 6 in the step S2 into a solvent, adding N, N-dimethylformamide as a catalyst, slowly dropwise adding thionyl chloride under an ice bath condition, and performing acyl chlorination reaction, purification and drying to obtain a diacid chloride monomer 7, a monomer 8 or a monomer 9;

s4, adding the monomer 7, the monomer 8 or the monomer 9 in the step S3 and Ar1 containing an amino group and a nitro group for substitution into a solvent, performing amidation reaction under a protective gas atmosphere, purifying, and drying to obtain a dinitromonomer 10, a monomer 11 or a monomer 12;

s5, adding the monomer 10, the monomer 11 or the monomer 12 in the step S4 into a solvent, introducing protective gas, adding a reducing agent, carrying out reduction reaction, purifying and drying to obtain a diamine monomer containing a phenothiazine structure shown in the structural general formulas I-III;

the monomer 1, the monomer 2 or the monomer 3 in the step S1, the monomer 4, the monomer 5 or the monomer 6 in the step S2, the monomer 7, the monomer 8 and the monomer 9 in the step S3, and the monomer 10, the monomer 11 and the monomer 12 in the step S4 respectively have the following structural characteristics:

further, the ratio of the amounts of the two halogen atom-substituted phenothiazine monomers in S1 and the cyano group-containing substance in the cyanide is 1: 2-8; preferably, the ratio of the amounts of the two halogen atom-substituted acridone monomers to the amount of the cyano species in the cyanide compound in S1 is 1: 5.

Further, the ratio of the amount of the monomer 1, the monomer 2 or the monomer 3 to the amount of the added alkali in the S2 is 1: 10-50; preferably, the mass ratio of the monomer 1, the monomer 2 or the monomer 3 to the added base in S2 is 1: 30-40.

Further, the molar ratio of the monomer 4, the monomer 5 or the monomer 6 to the thionyl chloride in S3 is 1: 2-4; preferably, the molar ratio of monomer 4, monomer 5 or monomer to thionyl chloride in S3 is 1: 3.

Further, the mass ratio of the monomer 7, the monomer 8 or the monomer 9 to the substance containing an amino group-and nitro group-substituted Ar1 monomer in S4 is 1:2 to 1: 4; preferably, the mass ratio of the monomer 7, the monomer 8 or the monomer 9 to the substance containing an amino group-and a nitro group-substituted Ar1 monomer in S4 is 1: 2.5.

Further, the mass ratio of the monomer 10, the monomer 11 or the monomer 12 to the reducing agent in S5 is 1: 2-1: 32. Preferably, the mass ratio of the monomer 10, the monomer 11 or the monomer 12 to the reducing agent in S5 is 1: 15-25.

Further, the protective gas from S1 to S5 is one or more of nitrogen, helium, neon, argon, krypton, xenon and radon; further, the solvent of S3 is dichloromethane;

further, S1 the cyanide is NaCN, KCN, Zn (CN)₂And one or more of CuCN; the reducing agent is one or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder and zinc powder; in S1The solvent is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene and xylene.

Further, the base in S2 is one or more of sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium fluoride, n-butyl lithium, potassium tert-butoxide, sodium tert-butoxide, and hexamethyldisilazane-based aminolithium; the solvent in S2 is one or more of dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane, toluene, xylene, acetone, acetonitrile and water.

Further, the solvent in S4 is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene, and xylene;

further, the solvent in S5 is one or more selected from ethanol, methanol, N-propanol, tert-butanol, tert-amyl alcohol, ethanol, hexanol, tetrahydrofuran, 1,4 dioxane, dimethyl sulfoxide, N-dimethylformamide, ethyl acetate, and toluene.

Further, the diamine monomer containing the phenothiazine structure is used for synthesizing polyamide, polyimide, polyamide imide or polyester imide polymers.

According to the diamine monomer containing the phenothiazine structure obtained by the preparation method, the polyimide which is good in heat resistance, high in barrier property and suitable for FOLED materials is prepared, and the structural general formula of the polyimide is as follows:

wherein y is 1-10000. X is selected from any one of the following structures:

the preparation method of the polyimide containing phenothiazine and amide structures comprises the following steps: in an argon protective atmosphere, diamine containing an acridone structure and dianhydride containing an X structure are dissolved in a strong polar aprotic solvent according to a molar ratio of 1: 0.95-1.05, are stirred and react for 2-48 hours at a temperature of-15-30 ℃ to obtain homogeneous polyamic acid glue solution, and then the polyamic acid glue solution is subjected to thermal imidization or chemical imidization and dehydration to obtain polyimide.

Compared with the prior art, the beneficial effects are:

the invention designs and synthesizes an angle through a molecular structure, creatively introduces phenothiazine, amide structures and polar groups into a diamine monomer at the same time, and prepares the high-planarity diamine monomer containing the polar groups. Phenothiazine and amide are good electron donors with aromaticity, easily form a D-pi-D or S-pi-S system, and have high electron density and good rigid structure. Meanwhile, part of the medicines containing phenothiazine have certain antibacterial effect, and the diamine disclosed by the invention takes a phenothiazine structure as a core, so that the prepared diamine has certain antibacterial performance, and the functional diversity of diamine monomers is enriched to a great extent.

The plane rigid structure of the phenothiazine and the amide polar group are introduced into the polyimide main chain, the plane rigid structure is beneficial to regular stacking of molecular chains and induction of polymer crystallization, and the polar group can enhance the hydrogen bonding effect of molecular chain bonds and promote the tight stacking of the molecular chains, so that the phenothiazine polyimide has excellent barrier property, higher glass transition temperature and thermal stability and lower thermal expansion coefficient. And after the antibacterial diamine containing a phenothiazine structure is synthesized, the polyimide has certain antibacterial performance.

Detailed Description

The following examples are further explained and illustrated, but the present invention is not limited in any way by the specific examples. Unless otherwise indicated, the methods and equipment used in the examples are conventional in the art and all materials used are conventional commercially available materials.