阅读说明：本技术 一种具有抗菌和高阻隔性能的聚酰亚胺及其制备方法和应用 (Polyimide with antibacterial and high-barrier properties, and preparation method and application thereof ) 是由 谭井华 刘亦武 张祥 李禹慧 于 2019-12-15 设计创作，主要内容包括：本发明公开了一种具有抗菌和高阻隔性能的聚酰亚胺及其制备方法和应用。本发明以卤代吖啶酮结构制备得到含吖啶酮结构和酰胺结构的二胺,然后利用制备的二胺单体与二酐聚合得到聚酰亚胺。本发明制备具有抗菌和高阻隔性能的聚酰亚胺的主链具有吖啶酮平面刚性结构和极性酰胺基团,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键的氢键作用,促进分子链紧密堆砌,提高其阻隔性能。并且,所述聚酰亚胺在吖啶酮结构和酰胺结构的结合下具有了良好的抗菌效果。(The invention discloses polyimide with antibacterial and high-barrier properties, and a preparation method and application thereof. The invention prepares diamine containing acridone structure and amide structure by using halogenated acridone structure, and then polymerizes the prepared diamine monomer and dianhydride to obtain polyimide. The main chain of the polyimide with antibacterial and high barrier properties provided by the invention has an acridone plane rigid structure and polar amide groups, the plane rigid structure is beneficial to regular stacking of molecular chains and induction of polymer crystallization, and the polar groups can enhance the hydrogen bond effect of molecular chain bonds, promote the tight stacking of the molecular chains and improve the barrier properties of the molecular chains. In addition, the polyimide has a good antibacterial effect under the combination of an acridone structure and an amide structure.)

1. The polyimide with antibacterial and high-barrier properties is characterized by being prepared by polymerizing diamine and dianhydride containing acridone structures and amide groups, and the structural general formula of the polyimide is shown as follows:

Ar₁any one selected from the following structural formulas:

wherein y is 1-10000; 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. The polyimide having antibacterial and high barrier properties according to claim 1,

ar2 and Ar3 are selected from any one of the following structural formulas:

x is selected from any one of the following structures:

3. the polyimide with antibacterial and high barrier properties according to claim 1, wherein said Ar is selected from the group consisting of₂Is composed of

4. The polyimide having antibacterial and high barrier properties according to claim 1 or 2, provided with a preparation method, comprising the steps of: 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 a homogeneous polyamic acid glue solution, and then the polyamic acid glue solution is subjected to thermal imidization or chemical imidization dehydration to obtain polyimide.

5. The method for preparing polyimide having antibacterial and high barrier properties according to claim 3, wherein the method for preparing diamine containing acridone structure comprises:

s1, preparing acridone 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, and performing hydrolysis reaction under the atmosphere of protective gas 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 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, and performing amidation reaction under a protective gas atmosphere 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, and carrying out reduction reaction to obtain a diamine monomer containing acridone and shown in structural general formulas I-III;

the monomer 1, the monomer 2 and the monomer 3 in the step S1, the monomer 4, the monomer 5 and 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:

6. the method for preparing polyimide with antibacterial and high barrier properties according to claim 5, wherein the ratio of the amounts of the two halogen atom-substituted acridone monomers in S1 to the amount of cyano groups in cyanide is 1:2 to 8; the mass ratio of the monomer 1, the monomer 2 or the monomer 3 to the added alkali in S2 is 1: 10-50; the molar ratio of the monomer 4, the monomer 5 or the monomer 6 to the thionyl chloride in S3 is 1: 2-4; the mass ratio of the monomer 7, the monomer 8 or the monomer 9 to the substance containing an amino group-and nitro-substituted Ar1 monomer in S4 is 1: 2-1: 4; 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.

7. The method for preparing polyimide with antibacterial and high-barrier properties according to claim 5, wherein the protective gas from S1 to S5 is one or more of nitrogen, helium, neon, argon, krypton, xenon, and radon; 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; s2, the alkali 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 lithium; the solvent in S1 is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene and xylene; the solvent in S2 is one or more of dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane, toluene, xylene, acetone, acetonitrile and water; the solvent of step S3 is dichloromethane; the solvent in S4 is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene and xylene; the solvent in S5 is one or more of ethanol, methanol, N-propanol, tert-butanol, tert-amyl alcohol, ethanol, hexanol, tetrahydrofuran, 1,4 dioxane, dimethyl sulfoxide, N-dimethylformamide, ethyl acetate and toluene.

8. The preparation method of the polyimide with antibacterial and high-barrier properties according to claim 5, wherein the reaction temperature is 50-170 ℃ and the reaction time is 10-48 h; the drying temperature is 40-120 ℃, and the drying time is 6-30 h.

9. The polyimide having antibacterial and high barrier properties according to claim 1 or 2, which is applied to microelectronics, military industry, aerospace, packaging and protection, and electronic device packaging.

Technical Field

The invention relates to the technical field of material science, in particular to polyimide with antibacterial and high-barrier properties, and a preparation method and application thereof.

Background

Polyimide is one of organic polymer materials with the best comprehensive performance, has the performances of high and low temperature resistance, excellent mechanical property, good stability, flame retardance, no toxicity and the like, and has great application prospect fully recognized no matter being used as a structural material or a functional material. Polyimide is used as a polymer material with a great development prospect, and the application of polyimide in insulating materials and structural materials is continuously expanding. The potential of exposing the corners in functional materials is still under development. Polyimide is used as a packaging material, and the heat resistance, stability, flame retardance and nontoxicity of the polyimide all meet the requirements of the packaging material. However, polyimide has disadvantages of low barrier performance and high water oxygen permeability, and polyimide has insufficient antibacterial properties, and it is difficult to ensure that the contents are not contaminated when the water oxygen permeability is high.

Disclosure of Invention

The invention aims to solve the technical problem of providing polyimide with high barrier property, excellent antibacterial property and high barrier property aiming at the defects of barrier property and antibacterial effect of polyimide.

The invention also provides a diamine monomer containing an acridone structure and a preparation method of polyimide.

The invention also solves the technical problem of providing the application of the polyimide with antibacterial and high-barrier properties in various fields.

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

the polyimide with antibacterial and high-barrier properties has a structural general formula as follows:

Ar₁any one selected from the following structural formulas:

wherein y is 1-10000; 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:

further, X is selected from any one of the following structures:

further, said Ar₂Preferably, it isAr3 is one or more of

One or more of (a); said X is preferably

The preparation method of the polyimide with antibacterial and high-barrier properties 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, stirred and reacted for 2-48 h 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.

The preparation method of the diamine containing the acridone structure comprises the following steps:

s1, preparing acridone monomer substituted by two halogen atoms

Adding cyanide into a solvent 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, and performing hydrolysis reaction under the atmosphere of protective gas 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 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, and performing amidation reaction under a protective gas atmosphere 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, and carrying out reduction reaction to obtain a diamine monomer containing acridone and shown in structural general formulas I-III;

the monomer 1, the monomer 2 and the monomer 3 in the step S1, the monomer 4, the monomer 5 and 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 two halogen atom-substituted acridone monomers in S1 to the amount of cyano-group-containing substances in the cyanide is 1: 2-8; the mass ratio of the monomer 7, the monomer 8 or the monomer 9 to the added alkali in the S2 is 1: 10-50; the molar ratio of the monomer 10, the monomer 11 or the monomer 12 to the thionyl chloride in S3 is 1: 2-4; the mass ratio of the monomer 13, the monomer 14 or the monomer 15 to the substance containing an amino group-and nitro-substituted Ar1 monomer in S4 is 1: 2-1: 4; the mass ratio of the monomer 16, the monomer 17 or the monomer 18 to the reducing agent in S5 is 1: 2-1: 32.

Further, the protective gas in S1-S5 is one or more of nitrogen, helium, neon, argon, krypton, xenon and radon;

further, in S1, the cyanide is NaCN, KCN, Zn (CN)₂And one or more of CuCN;

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;

further, the reducing agent in S5 is one or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder, and zinc powder;

further, the solvent in S1 is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene, and xylene; the solvent in S2 is one or more of dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane, toluene, xylene, acetone, acetonitrile and water; the solvent in S3 is dichloromethane; the solvent in S4 is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene and xylene; the solvent in S5 is one or more of 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 reaction temperature is 50-170 ℃, and the reaction time is 10-48 h; the drying temperature is 40-120 ℃, and the drying time is 6-30 h. Preferably, in the step S1, the reaction temperature is 140 ℃, the reaction time is 24 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in the S2, the drying temperature is 80 ℃, and the drying time is 24 h; in the S3, the reaction temperature is 75 ℃, the reaction time is 12 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in the S4, the reaction temperature is 100 ℃, the reaction time is 12 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in S5, the reaction temperature is 80 ℃, the reaction time is 24h, the drying temperature is 80 ℃, and the drying time is 24 h.

The obtained polyimide with antibacterial and high-barrier properties is applied to microelectronics, military industry, aviation and aerospace, packaging and protection and electronic device packaging.

Compared with the prior art, the beneficial effects are:

according to the invention, through molecular structure design, an acridone structure and an imide polar group are creatively introduced into a diamine monomer at the same time, so that the diamine monomer containing acridone with high planarity is prepared, and the diamine monomer has high electron density and good rigidity structure. The diamine monomer containing the acridone structure has high planarity and stronger rigidity, and contains polar groups, and the prepared polyimide has regular molecular chain arrangement, strong intermolecular force and tight molecular chain stacking, thereby having excellent barrier property, higher glass transition temperature and thermal stability, and lower thermal expansion coefficient.

After the diamine monomer and the dianhydride monomer are polymerized, a plane rigid structure and a polar group are introduced into a polyimide main chain, the plane rigid structure is favorable for regular stacking of molecular chains and induces crystallization of polymers, and the polar group can enhance the hydrogen bond effect of molecular chain bonds and promote tight stacking of the molecular chains. The synergy of the effects can lead the molecular chains to be regularly arranged and tightly piled, and obviously improve the barrier property of the polyimide. In addition, the polyimide has a good antibacterial effect under the combination of an acridone structure and an amide structure.

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.