CN113754598A - Diamine containing cyclopeptide structure, polyimide and preparation method thereof - Google Patents

Diamine containing cyclopeptide structure, polyimide and preparation method thereof Download PDF

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CN113754598A
CN113754598A CN202111154107.8A CN202111154107A CN113754598A CN 113754598 A CN113754598 A CN 113754598A CN 202111154107 A CN202111154107 A CN 202111154107A CN 113754598 A CN113754598 A CN 113754598A
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monomer
cyclopeptide
compound
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diamine
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CN113754598B (en
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杨刚
蒲渝
曾科
胡江淮
何弦
谢换鑫
谭伟
洪金浪
朱正柱
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Sichuan University
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    • C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
    • C07D241/08—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
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    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties

Abstract

The invention discloses diamine containing a cyclopeptide structure, which has a structural general formula as follows: h2N‑R2‑RR1‑NH2Or
Figure DDA0003287989070000011
The invention also discloses a preparation method of diamine containing a cyclopeptide structure, polyimide containing the cyclopeptide structure and a preparation method of the polyimide. The polyimide has a cyclic peptide structure, so that the polyimide has high thermal stability, excellent mechanical property and solvent resistance, and the characteristics of reproducibility and environmental protection.

Description

Diamine containing cyclopeptide structure, polyimide and preparation method thereof
Technical Field
The invention belongs to the technical field of polyimide materials, and relates to diamine containing a cyclopeptide structure for preparing polyimide, polyimide prepared by taking the diamine containing the cyclopeptide structure as a raw material and a preparation method thereof.
Background
Since the 20 th century, the oil industry has been rapidly developing, promoting the development of science and technology and the progress of human society. However, the development of the petroleum industry also brings about problems such as greenhouse effect, environmental pollution, and the like. It has been reported that by 1998, the carbon dioxide content in the atmosphere exceeded thirty percent of the time before the industrial revolution. In addition, petroleum is a non-renewable resource, and has a problem that the reserves are not infinite. Under the pressure of environment and resources, the greening of polymer materials is becoming the main melody of the present material research and development. Therefore, the development of renewable, green and high-performance materials is a research focus today.
Polyimide is a high temperature resistant high performance polymer with imide ring. The high-performance thermoplastic elastomer has excellent mechanical properties, excellent heat resistance and low-temperature resistance, excellent electrical properties and excellent dimensional stability, is widely applied to the fields of films, fibers, building materials, composite materials, paints, microelectronics and the like, and is one of the most widely applied engineering plastics in the market at present. However, diamines conventionally used for the preparation of polyimides are mostly derived from petroleum, and therefore, it is imperative to develop bio-based diamine monomers of green raw material origin.
Cyclic peptide structures are a class of cyclic compounds with specific shapes and specific properties that are ubiquitous in nature, and are composed of amino acid units. The content and the variety of amino acids in organisms are various, and various amino acids have numerous active sites, so that a large number of bio-based monomers can be derived, and the polymer prepared by taking the bio-based monomers as the raw material meets the requirements of green and sustainable development.
Therefore, based on the cyclic peptide structure, a novel diamine monomer is provided, and the preparation method has very important significance for preparing reproducible and environment-friendly polyimide.
Disclosure of Invention
The invention aims to provide diamine containing a cyclopeptide structure and a preparation method thereof, and the diamine can be used as a candidate raw material for preparing renewable and green polyimide in view of the contained cyclopeptide structure and a bio-based derivative.
The invention also aims to provide the polyimide containing the cyclic peptide structure and the preparation method thereof, and the prepared polyimide has excellent thermal stability and mechanical property, is not only green and renewable in raw material source, but also is a renewable, green and environment-friendly high-performance material due to the cyclic peptide structure contained in the polyimide.
The diamine containing the cyclopeptide structure has the structural general formula as follows:
Figure BDA0003287989050000021
wherein R is produced by the reaction of L-tyrosine cyclic dipeptide, L-histidine cyclic dipeptide, L-tryptophan cyclic dipeptide or 5-hydroxy-tryptophan cyclic dipeptide and can be represented as:
Figure BDA0003287989050000022
R1and R2Is generated by the reaction of corresponding aromatic compounds containing aromatic substituted halogen and nitro or aromatic compounds containing acyl halide and nitro, and is determined by the structure of the selected aromatic compounds containing halogen and nitro or aromatic compounds containing acyl halide and nitro, wherein R is1And R2Are the same or different in structure, R1、R2The structural formula of (a) may be one of the following:
Figure BDA0003287989050000023
ortho positionMeta or para;
Figure BDA0003287989050000024
ortho, meta or para, R0is-CH3、-CF3or-OCH3；
Figure BDA0003287989050000025
1,4, 1,5, 1,6, 2,6 or 2, 7;
Figure BDA0003287989050000026
Figure BDA0003287989050000027
4,3 'or 4, 4', wherein X is O, S, CO, SO2、CH2、C(CH3)2Or C (CF)3)2；
Halogen (represented by F) as defined above means a fluorine, chlorine, bromine or iodine atom, preferably a fluorine, chlorine atom, particularly preferably a fluorine atom; the acyl halide as mentioned above means acyl fluoride, acyl chloride, acyl bromide or acyl iodide, preferably acyl fluoride, acyl chloride or acyl bromide, particularly preferably acyl chloride.
Further, the diamine containing a cyclic peptide structure is preferably a diamine having the general structural formula (I) because it is more soluble and easy to purify. The diamine containing a cyclopeptide structure described by the above general structural formula (I) may specifically be any one of the following structures:
(1) first kind monomer (same double head)
The first monomer is R1And R2Diamine containing cyclopeptide structure with the same structure comprises a monomer 1-X, a monomer 2-X and a monomer 3-X, wherein,
r in monomer 1-X1And R2And is also one of the following structural formulas:
Figure BDA0003287989050000031
ortho, meta or para;
Figure BDA0003287989050000032
ortho, meta or para, R0is-CH3、-CF3or-OCH3；
R in monomer 2-X1And R2And is also one of the following structural formulas:
Figure BDA0003287989050000033
1,4, 1,5, 1,6, 2,6 or 2, 7;
r in monomer 3-X1And R2And is also one of the following structural formulas:
Figure BDA0003287989050000034
4,3 'or 4, 4', wherein X is O, S, CO, SO2、CH2、C(CH3)2Or C (CF)3)2；
(2) Second type monomer (different double heads)
The second monomer is R1And R2Diamine containing cyclopeptide structures with different structures comprises a monomer 4-X, a monomer 5-X and a monomer 6-X, wherein,
r in monomer 4-X1And R2Respectively is phenyl and naphthalene in the following structural formula: (i.e., one is phenyl and the other is naphthalene)
Phenyl group:
Figure BDA0003287989050000035
ortho, meta or para;
Figure BDA0003287989050000036
ortho, meta or para, R0is-CH3、-CF3or-OCH3；
Naphthalene:
Figure BDA0003287989050000037
1,4, 1,5, 1,6, 2,6 or 2, 7;
r in monomer 5-X1And R2Respectively is phenyl and diphenyl in the following structural formula: (i.e., one is phenyl and the other is diphenyl)
Phenyl group:
Figure BDA0003287989050000041
ortho, meta or para;
Figure BDA0003287989050000042
ortho, meta or para, R0is-CH3、-CF3or-OCH3；
Diphenyl group:
Figure BDA0003287989050000043
4,3 'or 4, 4', wherein X is O, S, CO, SO2、CH2、C(CH3)2Or C (CF)3)2；
R in monomer 6-X1And R2Respectively, a naphthalene and a diphenyl in the following structural formulas: (i.e., one is diphenyl and the other is naphthalene)
Naphthalene:
Figure BDA0003287989050000044
1,4, 1,5, 1,6, 2,6 or 2, 7;
diphenyl group:
Figure BDA0003287989050000045
4,3 'or 4, 4', wherein X is O, S, CO, SO2、CH2、C(CH3)2Or C (CF)3)2。
The invention further provides a preparation method of the diamine containing the cyclopeptide structure.
The preparation method of diamine containing cyclopeptide structure with the general structural formula (I) comprises the following steps according to monomer classification:
the synthetic route of the first monomer is as follows:
Figure BDA0003287989050000046
Figure BDA0003287989050000051
the preparation method of the first monomer comprises the following steps:
(11) mixing a compound containing a cyclopeptide structure, a compound A and a catalyst A in a solvent A, and reacting the obtained mixed system for 8-12h at 50-70 ℃ under the protection of inert gas; precipitating, filtering, washing and drying the obtained reaction solution to obtain an intermediate 1; the compound containing a cyclopeptide structure, the compound A and the catalyst A are in a molar ratio of 1: 2.2-3: 1.5-2; the total concentration of the compound containing the cyclopeptide structure and the compound A in the mixed system is 0.2-0.3g/mL (namely the ratio of the mass of the raw material to the volume of the solvent in the mixed system, which is the same as the following); the compound A is an aromatic compound containing halogen and nitro, or an aromatic compound containing acyl halide and nitro;
(12) mixing the intermediate 1 and stannous chloride dihydrate in a solvent B, and reacting the obtained mixed system at 50-70 ℃ for 20-24 h; precipitating, extracting, washing and drying the obtained reaction liquid to obtain a product 1 which is a first type of monomer; the molar ratio of the intermediate 1 to the stannous chloride dihydrate is 1: 8-12; the solvent B is obtained by uniformly mixing the solvent A and ethanol according to the volume ratio of 1: 0.5-2; in the step, the total concentration of the intermediate 1 and stannous chloride dihydrate in a mixed system is 0.07-0.1 g/mL.
(II) the synthetic route of the second monomer is as follows:
Figure BDA0003287989050000061
Figure BDA0003287989050000071
the preparation method of the second monomer comprises the following steps:
(21) mixing a compound containing a cyclopeptide structure, a compound A and a catalyst A in a solvent A, and reacting the obtained mixed system for 8-12h at 50-70 ℃ under the protection of inert gas; precipitating, filtering, washing and drying the obtained reaction solution to obtain an intermediate 2-1; the molar ratio of the compound containing the cyclopeptide structure, the compound A and the catalyst A is 1: 1.1-1.2: 0.75-1; the total concentration of the compound containing the cyclopeptide structure and the compound A in a mixed system is 0.2-0.3 g/mL; the compound A is an aromatic compound containing halogen and nitro, or an aromatic compound containing acyl halide and nitro;
(22) mixing the intermediate 2-1, the compound B and the catalyst A in a solvent A, and reacting the obtained mixed system for 8-12h at 50-70 ℃ under the protection of inert gas; precipitating, filtering, washing and drying the obtained reaction solution to obtain an intermediate 2-2; the molar ratio of the intermediate 2-1 to the compound B to the catalyst A is 1: 1.1-1.2: 0.75-1; the total concentration of the intermediate 2-1 and the compound B in a mixed system is 0.2-0.3 g/mL; the compound B is an aromatic compound containing halogen and nitro, or an aromatic compound containing acyl halide and nitro;
(23) mixing the intermediate 2-2 and stannous chloride dihydrate in a solvent B, and reacting the obtained mixed system at 50-70 ℃ for 20-24 h; precipitating, extracting, washing and drying the obtained reaction liquid to obtain a product 2, namely a second monomer; the molar ratio of the intermediate 2-2 to the stannous chloride dihydrate is 1: 8-12; the solvent B is obtained by uniformly mixing the solvent A and ethanol according to the volume ratio of 1: 0.5-2; the total concentration of the intermediate 2-2 and stannous chloride dihydrate in a mixed system is 0.07-0.1 g/mL.
The synthetic route of the diamine containing the cyclopeptide structure with the general structural formula (II) is as follows:
Figure BDA0003287989050000072
the preparation method of the diamine containing the cyclopeptide structure with the general structural formula (II) comprises the following steps:
(31) mixing L-tyrosine cyclic peptide and nitric acid in a solvent A, and reacting the obtained mixed system at 30-50 ℃ for 6-8 h; precipitating, filtering, washing and drying the obtained reaction solution to obtain an intermediate 3; the molar ratio of the L-tyrosine cyclic peptide to the nitric acid is 1: 10; the mass-volume ratio of the L-tyrosine cyclic peptide to the solvent A in the mixed system is 0.2-0.3, the mass unit of the L-tyrosine cyclic peptide is g, and the volume unit of the solvent A is mL;
(32) mixing the intermediate 3 and stannous chloride dihydrate in a solvent B, and reacting the obtained mixed system at 50-70 ℃ for 20-24 h; precipitating, extracting, washing and drying the obtained reaction solution to obtain a product 3, namely diamine containing a cyclopeptide structure determined by the general structural formula (II); the molar ratio of the intermediate 3 to the stannous chloride dihydrate is 1: 8-12; the solvent B is obtained by uniformly mixing the solvent A and ethanol according to the volume ratio of 1: 0.5-2; in the step, the total concentration of the intermediate 3 and stannous chloride dihydrate in a mixed system is 0.07-0.1 g/mL.
The purpose of the precipitation and washing in the above steps (11), (21), (22) and (31) is to remove unreacted raw materials or by-product impurities formed. The reaction solution in steps (11), (21), (22), and (31) is precipitated using water (deionized water, distilled water, or the like) until no more precipitate is generated. After filtering, further washing the obtained filter cake for multiple times by using water (deionized water or distilled water and the like), wherein the washing times are at least 2 times; for step (31), washing is generally carried out until the pH of the wash liquor is 7 to 8; the number of washing times for steps (11), (21) and (22) is preferably 3 to 5, and after washing with water (deionized water or distilled water, etc.), further washing with ethanol may be performed again 1 to 2 times. And (3) after the washing in the steps (11), (21) and (31) is finished, further drying for 10-12h in vacuum at the temperature of 80-100 ℃.
The purpose of precipitation, extraction and washing in the above steps (12), (23) and (32) is to remove unreacted raw materials or by-product impurities formed. And (4) precipitating the reaction liquid in the steps (12), (22) and (33) by using distilled water until no precipitate is generated. And then further extracting the precipitated product, wherein the specific implementation mode is as follows: adjusting pH of the mixed solution containing precipitate to 7-8 with 5-10% sodium carbonate aqueous solution, extracting with ethyl acetate, and washing the extractive solution with saturated saline solution for at least 2 times. And finally, carrying out rotary evaporation on the washed product to obtain a final product 1, a product 2 or a product 3.
In the above method for preparing diamine containing cyclopeptide structure, compound a and compound B are aromatic compounds containing halogen and nitro, or aromatic compounds substituted by acyl halide and nitro, wherein the halogen refers to fluorine, chlorine, bromine or iodine atom, preferably fluorine and chlorine atom, and particularly preferably fluorine atom; the acyl halide refers to acyl fluoride, acyl chloride, acyl bromide or acyl iodide, preferably acyl fluoride, acyl chloride or acyl bromide, and particularly preferably acyl chloride. The structural general formula of the compound A is Y-R1-NO2The structural general formula of the compound B is Y-R2-NO2(ii) a Y represents halogen or acyl halide, R1、R2With R given above1、R2The structure is the same.
In the above method for preparing diamine containing cyclopeptide structure, the solvent a is a high boiling point solvent, and may be one of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and the like.
In the preparation method of the diamine containing the cyclopeptide structure, the inert gas is nitrogen or argon.
In the above method for preparing diamine containing cyclic peptide structure, the catalyst a is lewis base, and may be one of anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, sodium hydride, calcium hydride, and the like, and is preferably anhydrous sodium carbonate or anhydrous potassium carbonate, and particularly preferably anhydrous potassium carbonate.
The invention further provides polyimide containing a cyclopeptide structure, which is prepared from diamine and aromatic dianhydride compounds containing the cyclopeptide structure synthesized by the invention, and the structural formula of the polyimide is as follows:
Figure BDA0003287989050000091
n is 10 to 500;
r is as defined above1And R2The same or different, the structure thereof is any one of the following structures:
Figure BDA0003287989050000092
ortho, meta or para;
Figure BDA0003287989050000093
ortho, meta or para, R0is-CH3、-CF3or-OCH3；
Figure BDA0003287989050000094
1,4, 1,5, 1,6, 2,6 or 2, 7;
Figure BDA0003287989050000095
Figure BDA0003287989050000096
4,3 'or 4, 4', wherein X is O, S, CO, SO2、CH2、C(CH3)2Or C (CF)3)2。
The invention further provides a preparation method of the polyimide containing the cyclopeptide structure, and the polyimide containing the cyclopeptide structure is prepared from the diamine containing the cyclopeptide structure and the aromatic dianhydride compound synthesized by the invention.
The synthetic route for preparing polyimide by the diamine containing the cyclic peptide structure and the aromatic dianhydride compound synthesized by the invention is as follows:
Figure BDA0003287989050000101
the preparation method of the polyimide containing the cyclopeptide structure comprises the following steps:
(i) under the protection of inert gas, dissolving a diamine monomer containing a cyclopeptide structure in a polar solvent, stirring until the diamine monomer containing the cyclopeptide structure is completely dissolved, adding an aromatic dianhydride compound with the same molar weight as that of the diamine monomer containing the cyclopeptide structure, and stirring at room temperature for 12-15 hours to obtain a polyamic acid solution;
(ii) and (3) carrying out gradient heating and ring closure on the polyamic acid solution at 80-320 ℃ under a vacuum condition to obtain the polyimide containing the cyclopeptide structure.
The aromatic dianhydride compound is one of pyromellitic dianhydride (PMDA), biphenyl dianhydride (BPDA), diphenyl ether dianhydride (ODPA), Benzophenone Tetracarboxylic Dianhydride (BTDA), and 4,4- (hexafluoroisopropyl) diphthalic anhydride (6 FDA).
In the step (i), the polar solvent is one of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), and the like. The amount of the polar solvent is that the total concentration of the diamine monomer containing the cyclic peptide structure and the aromatic dianhydride compound is 0.15-0.2 g/mL.
In the step (ii), a polyamic acid solution is generally coated on the substrate to form a film, and the film is subjected to gradient heating at 80-320 ℃ under a vacuum condition to close the ring, so as to obtain the polyimide film containing the cyclic peptide structure, so that the polyimide film can be conveniently tested and applied. The substrate may be of conventional choice in the art, such as glass, PTFE sheet, and the like.
In the step (ii), the gradient heating closed-loop procedure is as follows:
isothermal at 80-100 ℃ for 4-4.5 h,
isothermal at 115-120 ℃ for 2-2.5 h,
isothermal at 150-155 ℃ for 2.5-3 h,
isothermal at 200-210 ℃ for 2-4 h,
keeping the temperature constant for 1.5-2 h at 300-320 ℃.
The diamine and the polyimide containing the cyclopeptide structure and the preparation method thereof have the following beneficial effects:
(1) the diamine containing cyclopeptide structure provided by the invention has strong intermolecular supramolecular action among molecular chains due to perfect hydrogen bonds formed among amide groups, and can endow the material with good thermal property and mechanical property.
(2) The polyimide prepared by using diamine containing cyclic peptide structure and aromatic dianhydride compound as raw materials also contains cyclic peptide structure, so that the polyimide has excellent thermal stability and mechanical property.
(3) The diamine and the polyimide provided by the invention contain cyclic peptide structures, so that the diamine and the polyimide have the characteristics of reproducibility and environmental protection, and meet the requirements of green and sustainable development.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of intermediate N3-1 (i.e., cyclic peptide dinitro) prepared in example 3.
FIG. 2 is a nuclear magnetic hydrogen spectrum of diamine monomer N3 (i.e., cyclopeptide diamine) containing a cyclopeptide structure prepared in example 3.
FIG. 3 is an infrared spectrum of the polyimide PI-3 containing cyclic peptide structure prepared in example 3.
FIG. 4 is a TGA curve of the polyimide PI-3 containing the cyclic peptide structure prepared in example 3 under a nitrogen atmosphere.
FIG. 5 is a DSC curve of the polyimide PI-3 containing cyclic peptide structure prepared in example 3 under nitrogen atmosphere.
Detailed Description
The technical solution of the present invention is further described below by way of examples with reference to the accompanying drawings.
The preparation process of the amino acid cyclic dipeptide comprises the following steps:
45g of amino acid compound M and 180mL of ethylene glycol were added to a single-neck flask and purged with nitrogen 15 times. Heating is started, the heating temperature is set to be 197 ℃, and reflux reaction is carried out for 24 hours. The reaction solution was poured into 800mL of deionized water and precipitated. After filtration, the mixture was washed with 800mL of deionized water with stirring and repeated three times. The filter cake was washed 5 times with 500mL ethanol under reflux. Drying at 80 deg.C under vacuum to obtain the final product.
The compound M is: l-tyrosine, L-histidine, L-tryptophan or 5-hydroxy-tryptophan.
Example 1
1.1 Synthesis of diamine monomer N1 containing Cyclic peptide Structure
Figure BDA0003287989050000111
Combining the above synthetic route, the preparation method of diamine monomer N1 containing cyclic peptide structure comprises the following steps:
(11) 0.01mol of L-tyrosine cyclic dipeptide, 0.03mol of parafluoronitrobenzene, 0.02mol of anhydrous potassium carbonate and 40ml of DMF are added into a reactor, and stirring is started. Under the protection of nitrogen, the temperature is raised to 70 ℃ and the reaction lasts for 12 hours. And (3) post-treatment: and precipitating the obtained reaction solution by using 400mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 10 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N1-1.
(12) 0.005mol of intermediate N1-1, 0.04mol of stannous chloride dihydrate, 13mL of DMMF and 26mL of ethanol are sequentially added into a reactor, the temperature is raised to 70 ℃, and the reaction is carried out for 24 hours. And (3) post-treatment: the resulting reaction solution was precipitated with 80mL of deionized water, the pH was adjusted to 7-8 with 8% aqueous sodium carbonate (measured using pH paper, the same applies hereinafter), followed by extraction with ethyl acetate, washing the extract with saturated brine for 2 times, and rotary evaporation of the washed extract to give N1.
Warp beam1H-NMR test proves that the target product N1 has the following structure:
Figure BDA0003287989050000121
1.2 preparation of polyimide PI1 containing cyclopeptide Structure
Figure BDA0003287989050000122
Combining the synthesis route, the preparation of the polyimide film containing the cyclopeptide structure is carried out according to a two-step method, which specifically comprises the following steps:
(i) 1.0000g of monomer N1 is added into a three-neck flask which is protected by dry nitrogen, then a dry polar solvent DMAc (the total concentration of the monomer N1 and pyromellitic dianhydride PMDA in the polar solvent is 0.2g/mL) is added, the mixture is stirred until the monomer N1 is completely dissolved, an aromatic dianhydride compound pyromellitic dianhydride PMDA with the same molar amount as the monomer N1 is added, and the mixture is stirred for 12 hours at room temperature, so that a polyamic acid solution PI1 is obtained.
(ii) Coating a polyamic acid solution PI1 on a glass substrate to form a film with the thickness of 400 mu m, and then putting the film into a vacuum oven to perform isothermal treatment at 80 ℃ for 4.5h, 120 ℃ for 2h, 150 ℃ for 3h, 200 ℃ for 4h and 300 ℃ for 2h to obtain the polyimide film PI1 with a cyclopeptide structure.
Example 2
2.1 Synthesis of diamine monomer N2 containing Cyclic peptide Structure
Figure BDA0003287989050000131
Combining the above synthetic route, the preparation method of diamine monomer N2 containing cyclic peptide structure comprises the following steps:
(11) 0.01mol of L-histidine cyclic dipeptide, 0.03mol of p-fluoronitrobenzene, 0.02mol of anhydrous potassium carbonate and 40ml of DMF are added into a reactor, and stirring is started. Under the protection of nitrogen, the temperature is raised to 70 ℃ and the reaction lasts 8 h. And (3) post-treatment: and precipitating the obtained reaction solution by using 400mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 10 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N2-1.
(12) 0.005mol of intermediate N2-1, 0.06mol of stannous chloride dihydrate, 13mL of DMMF and 26mL of ethanol were added to the reactor in this order. The temperature is increased to 70 ℃ and the reaction is carried out for 24 h. And (3) post-treatment: precipitating the obtained reaction solution with 80mL of deionized water, adjusting the pH value to 7-8 with 8% sodium carbonate aqueous solution, extracting with ethyl acetate, washing the extract with saturated saline solution for 2 times, and performing rotary evaporation on the washed extract to obtain a product N2.
Warp beam1H-NMR test proves that the target product N2 has the following structure:
Figure BDA0003287989050000132
2.2 preparation of polyimide PI2 containing cyclopeptide Structure
Figure BDA0003287989050000133
Combining the synthesis route, the preparation of the polyimide film containing the cyclopeptide structure is carried out according to a two-step method, which specifically comprises the following steps:
(i) 1.0000g of monomer N2 is added into a three-neck flask which is protected by dry nitrogen, then a dry polar solvent DMAc (the total concentration of the monomer N2 and pyromellitic dianhydride PMDA in the polar solvent is 0.15g/mL) is added, the mixture is stirred until the monomer N2 is completely dissolved, an aromatic dianhydride compound pyromellitic dianhydride PMDA with the same molar amount as the monomer N2 is added, and the mixture is stirred for 12 hours at room temperature, so that a polyamic acid solution PI2 is obtained.
(ii) Coating a polyamic acid solution PI2 on a glass substrate to form a film with the thickness of 400 mu m, and then putting the film into a vacuum oven to perform isothermal treatment at 100 ℃ for 4h, 120 ℃ for 2h, 150 ℃ for 3h, 200 ℃ for 4h and 300 ℃ for 2h to obtain the polyimide film PI2 containing a cyclopeptide structure.
Example 3
3.1 Synthesis of diamine monomer N3 containing Cyclic peptide Structure
Figure BDA0003287989050000141
Combining the above synthetic route, the preparation method of diamine monomer N3 containing cyclic peptide structure comprises the following steps:
(11) 0.01mol of L-tyrosine cyclic dipeptide, 0.022mol of 2-fluoro-5-nitrobenzotrifluoride, 0.015mol of anhydrous potassium carbonate and 40mLDMAc are added into a reactor, and stirring is started. And under the protection of nitrogen, heating to 60 ℃ and reacting for 10 hours. And (3) post-treatment: and precipitating the obtained reaction solution by using 400mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N3-1.
(12) 0.005mol of intermediate N3-1, 0.05mol of stannous chloride dihydrate, 26mLDMAc and 13mL of ethanol are added into a reactor, the temperature is raised to 50 ℃, and the reaction is carried out for 20 h. And (3) post-treatment: precipitating the obtained reaction solution with 80mL of deionized water, adjusting the pH value to 7-8 with 10% sodium carbonate aqueous solution, extracting with ethyl acetate, washing the extract with saturated saline solution for 2 times, and performing rotary evaporation on the washed extract to obtain a product N3.
Warp beam1H-NMR test proves that the target product N3 has the following structure:
Figure BDA0003287989050000142
3.2 preparation of polyimide PI3 containing cyclopeptide Structure
Figure BDA0003287989050000151
Combining the synthesis route, the preparation of the polyimide film containing the cyclopeptide structure is carried out according to a two-step method, which specifically comprises the following steps:
(i) 1.0000g of monomer N3 was added into a three-necked flask which was purged with dry nitrogen, followed by adding dry polar solvent DMAc (total concentration of monomer N3 and biphenyl dianhydride BPDA in the polar solvent was 0.15g/mL), stirring until monomer N3 was completely dissolved, adding aromatic dianhydride compound biphenyl dianhydride BPDA in an amount equimolar to monomer N3, and stirring at room temperature for 12 hours to obtain polyamic acid solution PI 3.
(ii) Coating a polyamic acid solution PI3 on a glass substrate to form a film with the thickness of 400 mu m, and then putting the film into a vacuum oven to perform isothermal treatment at 100 ℃ for 4h, 120 ℃ for 2h, 150 ℃ for 3h, 200 ℃ for 4h and 300 ℃ for 2h to obtain the polyimide film PI3 containing a cyclopeptide structure.
FIG. 1 shows the results of nuclear magnetic testing of intermediate N3-1 prepared in this example, from which it can be seen that intermediate N3-1 was successfully synthesized.
FIG. 2 shows the results of nuclear magnetic tests on diamine monomer N3 containing cyclic peptide structure prepared in this example, and it can be seen that monomer N3 was successfully synthesized.
FIG. 3 shows a sample prepared in this exampleThe infrared test result of the polyimide PI3 film containing the cyclic peptide structure can be seen in the figure, 1776cm-1、1720cm-1、1375cm-1The peaks at the positions respectively correspond to in-plane and out-of-plane stretching vibration and carbon-nitrogen stretching vibration of carbonyl groups on the imide ring, and the successful synthesis of the polyimide PI3 structure is shown.
FIG. 4 shows the TGA (thermogravimetric analysis) test results of the polyimide PI3 film containing cyclic peptide structure prepared in this example under nitrogen atmosphere, and it can be seen that the temperature T at which 5% of the weight is lost is shown5％It was 431 ℃, indicating that it has excellent thermal stability.
Fig. 5 shows the result of DSC (thermal analysis) test of the polyimide PI3 film containing a cyclic peptide structure prepared in this example under nitrogen atmosphere, and it can be seen that the Tg of the PI film is 250 ℃, and the thermal performance is excellent.
Example 4
4.1 Synthesis of diamine monomer N4 containing Cyclic peptide Structure
Figure BDA0003287989050000161
Combining the above synthetic route, the preparation method of diamine monomer N4 containing cyclic peptide structure comprises the following steps:
(11) 0.01mol of L-histidine cyclic dipeptide, 0.022mol of 2-fluoro-5-nitrobenzotrifluoride, 0.015mol of anhydrous potassium carbonate and 40ml of TMAC were added to the reactor, and stirring was started. And under the protection of nitrogen, heating to 60 ℃ and reacting for 10 hours. And (3) post-treatment: and precipitating the obtained reaction solution by using 400mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N4-1.
(12) 0.005mol of intermediate N4-1, 0.05mol of stannous chloride dihydrate, 26mLDMAc and 13mL of ethanol are added into a reactor, the temperature is raised to 50 ℃, and the reaction is carried out for 20 h. And (3) post-treatment: the resulting reaction solution was precipitated with 80mL of deionized water, the pH was adjusted to 7-8 with 10% aqueous sodium carbonate, followed by extraction with ethyl acetate, washing the extract with saturated brine for 2 times, and rotary evaporation to give N4.
Warp beam1H-NMR test is carried out to determine the structure of the target product.
Figure BDA0003287989050000162
4.2 preparation of polyimide PI4 containing cyclopeptide Structure
Figure BDA0003287989050000163
Combining the synthesis route, the preparation of the polyimide film containing the cyclopeptide structure is carried out according to a two-step method, which specifically comprises the following steps:
(i) 1.0000g of monomer N4 was added into a three-necked flask which was purged with dry nitrogen, followed by adding dry polar solvent DMAc (total concentration of monomer N4 and biphenyl dianhydride BPDA in the polar solvent was 0.15g/mL), stirring until monomer N4 was completely dissolved, adding aromatic dianhydride compound biphenyl dianhydride BPDA in an amount equimolar to monomer N4, and stirring at room temperature for 12 hours to obtain polyamic acid solution PI 4.
(ii) Coating a polyamic acid solution PI4 on a glass substrate to form a film with the thickness of 400 mu m, and then putting the film into a vacuum oven to perform isothermal treatment at 100 ℃ for 4h, 115 ℃ for 2.5h, 155 ℃ for 2.5h, 200 ℃ for 4h and 300 ℃ for 2h to obtain the polyimide film PI4 with the cyclopeptide structure.
Example 5
5.1 Synthesis of diamine monomer N5 containing Cyclic peptide Structure
Figure BDA0003287989050000171
Combining the above synthetic route, the preparation method of diamine monomer N5 containing cyclic peptide structure comprises the following steps:
(11) 0.01mol of L-tyrosine cyclic dipeptide, 0.025mol of 1-chloro-4-nitronaphthalene, 0.015mol of anhydrous potassium carbonate and 50ml of NMMP are added into a reactor, and stirring is started. And under the protection of nitrogen, heating to 60 ℃ and reacting for 10 hours. And (3) post-treatment: and precipitating the obtained reaction solution by using 500mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 10 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N5-1.
(12) 0.005mol of intermediate N5-1, 0.05mol of stannous chloride dihydrate, 20mLNMP and 20mL of ethanol are added into a reactor, the temperature is raised to 60 ℃, and the reaction is carried out for 22 h. And (3) post-treatment: precipitating the obtained reaction solution with 80mL of deionized water, adjusting the pH value to 7-8 with 10% sodium carbonate aqueous solution, extracting with ethyl acetate, washing the extract with saturated saline solution for 2 times, and performing rotary evaporation on the washed extract to obtain a product N5.
Warp beam1H-NMR test proves that the target product N5 has the following structure:
Figure BDA0003287989050000172
5.2 preparation of polyimide PI5 containing cyclopeptide Structure
Figure BDA0003287989050000181
Combining the synthesis route, the preparation of the polyimide film containing the cyclopeptide structure is carried out according to a two-step method, which specifically comprises the following steps:
(i) 1.0000g of monomer N5 was added to a three-necked flask protected by dry nitrogen, followed by addition of a dry polar solvent DMAc (total concentration of monomer N5 and diphenyl ether dianhydride (ODPA) in the polar solvent was 0.15g/mL), stirring was carried out until the monomer N5 was completely dissolved, and then an aromatic dianhydride compound diphenyl ether dianhydride (ODPA) in an amount equimolar to the monomer N5 was added, and stirring was carried out at room temperature for 12 hours to obtain a polyamic acid solution PI 5.
(ii) Coating a polyamic acid solution PI5 on a glass substrate to form a film with the thickness of 400 mu m, and then putting the film into a vacuum oven to perform isothermal treatment at 100 ℃ for 4h, 120 ℃ for 2h, 150 ℃ for 3h, 200 ℃ for 4h and 300 ℃ for 2h to obtain the polyimide film PI5 containing a cyclopeptide structure.
Example 6
6.1 Synthesis of diamine monomer N6 containing Cyclic peptide Structure
Figure BDA0003287989050000182
Combining the above synthetic route, the preparation method of diamine monomer N6 containing cyclic peptide structure comprises the following steps:
(11) 0.01mol of L-histidine cyclic dipeptide, 0.024mol of 4-nitro-4' -chlorodiphenyl ether, 0.015mol of anhydrous potassium carbonate and 45mLDMSO are added into a reactor, and stirring is started. And under the protection of nitrogen, heating to 60 ℃ and reacting for 10 hours. And (3) post-treatment: precipitating the obtained reaction solution by using 450mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 10 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N6-1.
(12) 0.005mol of intermediate N6-1, 0.05mol of stannous chloride dihydrate, 20mLNMP and 20mL of ethanol are added into a reactor, the temperature is raised to 60 ℃, and the reaction is carried out for 22 h. And (3) post-treatment: precipitating the obtained reaction solution with 80mL of deionized water, adjusting the pH value to 7-8 with 10% sodium carbonate aqueous solution, extracting with ethyl acetate, washing the extract with saturated saline solution for 2 times, and performing rotary evaporation on the washed extract to obtain a product N6.
Warp beam1H-NMR test proves that the target product N6 has the following structure:
Figure BDA0003287989050000191
6.2 preparation of polyimide PI6 containing Cyclic peptide Structure
Figure BDA0003287989050000192
Combining the synthesis route, the preparation of the polyimide film containing the cyclopeptide structure is carried out according to a two-step method, which specifically comprises the following steps:
(i) 1.0000g of monomer N6 was added to a three-necked flask purged with dry nitrogen, followed by addition of dry polar solvent DMAc (total concentration of monomer N6 and 3,3 ', 4, 4' -diphenylsulfoxydetetracarboxylic dianhydride in the polar solvent was 0.2g/mL), stirring until monomer N6 was completely dissolved, addition of an aromatic dianhydride compound 3,3 ', 4, 4' -diphenylsulfoxydetetracarboxylic dianhydride in an amount equimolar to monomer N6, and stirring at room temperature for 12 hours to obtain polyamic acid solution PI 6.
(ii) Coating a polyamic acid solution PI6 on a glass substrate to form a film with the thickness of 400 mu m, and then putting the film into a vacuum oven to perform isothermal treatment at 100 ℃ for 4h, 120 ℃ for 2h, 150 ℃ for 3h, 210 ℃ for 2h and 300 ℃ for 2h to obtain the polyimide film PI6 containing a cyclopeptide structure.
Example 7
7.1 Synthesis of diamine monomer N7 containing Cyclic peptide Structure
Figure BDA0003287989050000193
Combining the above synthetic route, the preparation method of diamine monomer N7 containing cyclic peptide structure comprises the following steps:
(21) 0.01mol of L-tyrosine cyclic dipeptide, 0.012mol of m-chloronitrobenzene, 0.0075mol of anhydrous potassium carbonate and 40ml of DMMAc are added into a reactor, and stirring is started. And under the protection of nitrogen, heating to 50 ℃ and reacting for 10 hours. And (3) post-treatment: and precipitating the obtained reaction solution by using 400mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 10 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N7-1.
(22) 0.01mol of N7-1, 0.012mol of 1-nitro-5-chloronaphthalene, 0.01mol of anhydrous potassium carbonate and 40ml of TMAC are added into a reactor, and stirring is started. And under the protection of nitrogen, heating to 50 ℃ and reacting for 10 hours. And (3) post-treatment: and precipitating the obtained reaction solution by using 400mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 10 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N7-2.
(23) 0.005mol of intermediate N7-2, 0.05mol of stannous chloride dihydrate, 26mLDMAc and 13mL of ethanol are added into a reactor, the temperature is raised to 60 ℃, and the reaction is carried out for 24 h. And (3) post-treatment: precipitating the obtained reaction solution with 80mL of deionized water, adjusting the pH value to 7-8 with 5% sodium carbonate aqueous solution, extracting with ethyl acetate, washing the extract with saturated saline solution for 2 times, and performing rotary evaporation on the washed extract to obtain a product N7.
Warp beam1H-NMR test proves that the target product N7 has the following structure:
Figure BDA0003287989050000201
7.2 preparation of polyimide PI7 containing cyclopeptide Structure
Figure BDA0003287989050000202
Combining the synthesis route, the preparation of the polyimide film containing the cyclopeptide structure is carried out according to a two-step method, which specifically comprises the following steps:
(i) 1.0000g of monomer N7 was added to a three-necked flask purged with dry nitrogen, followed by addition of dry polar solvent DMAc (total concentration of monomer N7 and biphenyl dianhydride (BPDA) in the polar solvent was 0.15g/mL), stirring until monomer N7 was completely dissolved, addition of aromatic dianhydride compound biphenyl dianhydride (BPDA) in an amount equimolar to monomer N7, and stirring at room temperature for 12 hours to obtain polyamic acid solution PI 7.
(ii) Coating a polyamic acid solution PI7 on a glass substrate to form a film with the thickness of 400 mu m, and then putting the film into a vacuum oven to perform isothermal treatment at 100 ℃ for 4h, 120 ℃ for 2h, 150 ℃ for 3h, 200 ℃ for 4h and 300 ℃ for 2h to obtain the polyimide film PI7 containing a cyclopeptide structure.
Example 8
8.1 Synthesis of diamine monomer N8 containing Cyclic peptide Structure
Figure BDA0003287989050000211
Combining the above synthetic route, the preparation method of diamine monomer N8 containing cyclic peptide structure comprises the following steps:
(11) 0.01mol of 5-hydroxy-tryptophan cyclic dipeptide, 0.022mol of 1-nitro-5-chloronaphthalene, 0.015mol of anhydrous potassium carbonate and 50ml of DMMSO were added to the reactor, and stirring was started. Under the protection of nitrogen, the temperature is raised to 50 ℃ for reaction for 12 h. And (3) post-treatment: and precipitating the obtained reaction solution by using 500mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N8-1.
(12) 0.005mol of intermediate N8-1, 0.05mol of stannous chloride dihydrate, 30mLDMSO and 15mL of ethanol are added into a reactor, the temperature is raised to 50 ℃, and the reaction is carried out for 20 h. And (3) post-treatment: precipitating the obtained reaction solution by using 90mL of deionized water, adjusting the pH value to 7-8 by using a 5% sodium carbonate aqueous solution, extracting by using ethyl acetate, washing the extract by using saturated saline solution for 2 times, and carrying out rotary evaporation on the washed extract to obtain a product N8.
Warp beam1H-NMR test proves that the target product N8 has the following structure:
Figure BDA0003287989050000212
8.2 preparation of polyimide PI8 containing Cyclic peptide Structure
Figure BDA0003287989050000213
Combining the synthesis route, the preparation of the polyimide film containing the cyclopeptide structure is carried out according to a two-step method, which specifically comprises the following steps:
(i) 1.0000g of monomer N8 was added to a three-necked flask purged with dry nitrogen, followed by addition of a dry polar solvent DMAc (total concentration of monomer N8 and pyromellitic dianhydride (PMDA) in the polar solvent was 0.15g/mL), stirring was carried out until the monomer N8 was completely dissolved, and then an aromatic dianhydride compound, pyromellitic dianhydride (PMDA), in an amount equimolar to the monomer N8 was added, and stirring was carried out at room temperature for 12 hours to obtain a polyamic acid solution PI 8.
(ii) Coating a polyamic acid solution PI8 on a glass substrate to form a film with the thickness of 400 mu m, and then putting the film into a vacuum oven to perform isothermal treatment at 100 ℃ for 4h, 120 ℃ for 2h, 150 ℃ for 3h, 200 ℃ for 4h and 320 ℃ for 1.5h to obtain the polyimide film PI8 containing the cyclopeptide structure.
Example 9
9.1 Synthesis of diamine monomer N9 containing Cyclic peptide Structure
Figure BDA0003287989050000221
Combining the above synthetic route, the preparation method of diamine monomer N9 containing cyclic peptide structure comprises the following steps:
(21) 0.01mol of L-histidine cyclic dipeptide, 0.012mol of 2-nitro-6-chloronaphthalene, 0.0075mol of anhydrous potassium carbonate and 45mLDMSO are added into a reactor, and stirring is started. And under the protection of nitrogen, heating to 60 ℃ and reacting for 12 hours. And (3) post-treatment: precipitating the obtained reaction solution by using 450mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 10 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N9-1.
(22) 0.01mol of intermediate N9-1, 0.012mol of 4-nitro-4' -chlorobenzenethioether, 0.01mol of anhydrous potassium carbonate and 50ml of TMSO were added to the reactor, and stirring was started. And under the protection of nitrogen, heating to 60 ℃ and reacting for 12 hours. And (3) post-treatment: and precipitating the obtained reaction solution by using 500mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 10 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N9-2.
(23) 0.005mol of intermediate N9-2, 0.05mol of stannous chloride dihydrate, 30mLDMSO and 15mL of ethanol are added into a reactor, the temperature is raised to 60 ℃, and the reaction is carried out for 24 h. And (3) post-treatment: precipitating the obtained reaction solution by using 90mL of deionized water, adjusting the pH value to 7-8 by using a 5% sodium carbonate aqueous solution, extracting by using ethyl acetate, washing the extract by using saturated saline solution for 2 times, and carrying out rotary evaporation on the washed extract to obtain a product N9.
Warp beam1H-NMR test proves that the target product N9 has the following structure:
Figure BDA0003287989050000231
9.2 preparation of polyimide PI9 containing cyclopeptide Structure
Figure BDA0003287989050000232
Combining the synthesis route, the preparation of the polyimide film containing the cyclopeptide structure is carried out according to a two-step method, which specifically comprises the following steps:
(i) 1.0000g of monomer N9 was added to a three-necked flask purged with dry nitrogen, followed by addition of dry polar solvent DMAc (monomer N9 and 4,4- (hexafluoroisopropyl) diphthalic anhydride (6FDA) at a total concentration of 0.18g/mL in the polar solvent), stirring until monomer N9 was completely dissolved, addition of an aromatic dianhydride compound 4,4- (hexafluoroisopropyl) diphthalic anhydride (6FDA) in an amount equimolar to monomer N9, and stirring at room temperature for 15 hours to obtain polyamic acid solution PI 7.
(ii) Coating a polyamic acid solution PI7 on a glass substrate to form a film with the thickness of 400 mu m, and then putting the film into a vacuum oven to perform isothermal treatment at 100 ℃ for 4h, 120 ℃ for 2h, 150 ℃ for 3h, 200 ℃ for 4h and 300 ℃ for 2h to obtain the polyimide film PI9 containing a cyclopeptide structure.
Example 10
10.1 Synthesis of diamine monomer N10 containing Cyclic peptide Structure
Figure BDA0003287989050000233
Combining the above synthetic route, the preparation method of diamine monomer N10 containing cyclic peptide structure comprises the following steps:
(31) 0.01mol L-tyrosine cyclic dipeptide, 37mL of 17 wt% dilute nitric acid and 13mL of DMMF were added to the reactor, and the stirring was started. The temperature is increased to 30 ℃ and the reaction is carried out for 6 h. And (3) post-treatment: and precipitating the obtained reaction solution by using 300mL of distilled water, performing suction filtration after the precipitation is finished, collecting a filter cake, and washing the filter cake for 3 times by using the distilled water until the pH value of a washing liquid is 7-8. Finally, the filter cake is dried in a vacuum oven for 12h at 80 ℃ to obtain an intermediate N10-1.
(32) Adding 0.005mol of intermediate N10-1, 0.05mol of stannous chloride dihydrate, 30mL of DMMF and 15mL of ethanol into a reactor, heating to 60 ℃, and reacting for 24 hours. And (3) post-treatment: precipitating the obtained reaction solution by using 90mL of deionized water, adjusting the pH value to 7-8 by using a 5% sodium carbonate aqueous solution, extracting by using ethyl acetate, washing the extract by using saturated saline solution for 2 times, and carrying out rotary evaporation on the washed extract to obtain a product N10.
Warp beam1H-NMR test proves that the target product N10 has the following structure:
Figure BDA0003287989050000241
10.2 preparation of polyimide PI10 containing Cyclic peptide Structure
Figure BDA0003287989050000242
Combining the synthesis route, the preparation of the polyimide film containing the cyclopeptide structure is carried out according to a two-step method, which specifically comprises the following steps:
(i) 1.0000g of monomer N10 was added to a three-necked flask purged with dry nitrogen, followed by addition of a dry polar solvent DMAc (total concentration of monomer N10 and pyromellitic dianhydride (PMDA) in the polar solvent was 0.15g/mL), stirring was carried out until the monomer N10 was completely dissolved, and then an aromatic dianhydride compound, pyromellitic dianhydride (PMDA), in an amount equimolar to the monomer N10 was added, and stirring was carried out at room temperature for 12 hours to obtain a polyamic acid solution PI 7.
(ii) Coating a polyamic acid solution PI7 on a glass substrate to form a film with the thickness of 400 mu m, and then putting the film into a vacuum oven to perform isothermal treatment at 100 ℃ for 4h, 120 ℃ for 2h, 150 ℃ for 3h, 200 ℃ for 4h and 300 ℃ for 2h to obtain the polyimide film PI10 containing a cyclopeptide structure.
Example 11
11.1 Synthesis of diamine monomer N11 containing Cyclic peptide Structure
Figure BDA0003287989050000251
Combining the above synthetic route, the preparation method of diamine monomer N11 containing cyclic peptide structure comprises the following steps:
(11) 0.01mol of L-tryptophan cyclodipeptide, 0.025mol of parafluoronitrobenzene, 0.02mol of sodium hydride and 40ml of DMAC are added to the reactor, and the stirring is started. Under the protection of nitrogen, the temperature is raised to 70 ℃ and the reaction lasts for 12 hours. And (3) post-treatment: and precipitating the obtained reaction solution by using 400mL of deionized water, performing suction filtration after precipitation is finished, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, washing the filter cake for 1 time by using ethanol, and finally drying the filter cake for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain an intermediate N11-1.
(12) 0.005mol of intermediate N11-1, 0.05mol of stannous chloride dihydrate, 26mLDMAc and 13mL of ethanol are added into a reactor, the temperature is raised to 50 ℃, and the reaction is carried out for 20 h. And (3) post-treatment: precipitating the obtained reaction solution with 80mL of deionized water, adjusting the pH value to 7-8 with 10% sodium carbonate aqueous solution, extracting with ethyl acetate, washing the extract with saturated saline solution for 2 times, and performing rotary evaporation on the washed extract to obtain a product N11.
Warp beam1H-NMR test proves that the target product N11 has the following structure:
Figure BDA0003287989050000252
11.2 preparation of polyimide PI13 containing cyclopeptide Structure
Figure BDA0003287989050000253
Combining the synthesis route, the preparation of the polyimide film containing the cyclopeptide structure is carried out according to a two-step method, which specifically comprises the following steps:
(i) 1.0000g of monomer N11 was added to a three-necked flask purged with dry nitrogen, followed by addition of dry polar solvent DMAc (total concentration of monomer N11 and biphenyl dianhydride (BPDA) in the polar solvent was 0.15g/mL), stirring until monomer N11 was completely dissolved, addition of aromatic dianhydride compound biphenyl dianhydride (BPDA) in an amount equimolar to monomer N13, and stirring at room temperature for 15 hours to obtain polyamic acid solution PI 11.
(ii) Coating a polyamic acid solution PI11 on a glass substrate to form a film with the thickness of 400 mu m, and then putting the film into a vacuum oven to perform isothermal treatment at 100 ℃ for 4h, 120 ℃ for 2h, 150 ℃ for 3h, 200 ℃ for 4h and 300 ℃ for 2h to obtain the polyimide film PI11 containing a cyclopeptide structure.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.

Claims (10)

1. Diamine containing cyclopeptide structure is characterized by having a general structural formula:
Figure FDA0003287989040000011
wherein R is:
Figure FDA0003287989040000012
R1and R2Are the same or different in structure, R1、R2The structural formula of (a) is one of the following:
Figure FDA0003287989040000013
ortho, meta or para;
Figure FDA0003287989040000014
ortho, meta or para, R0is-CH3、-CF3or-OCH3；
Figure FDA0003287989040000015
1,4, 1,5, 1,6, 2,6 or 2, 7;
Figure FDA0003287989040000016
Figure FDA0003287989040000017
4,3 'or 4, 4', wherein X is O, S, CO, SO2、CH2、C(CH3)2Or C (CF)3)2。
2. Diamine containing a cyclic peptide structure according to claim 1, characterized in that the general structural formula (I) is any one of the following structures:
(1) monomers of the first type
The first monomer is R1And R2Diamine containing cyclopeptide structure with the same structure comprises a monomer 1-X, a monomer 2-X and a monomer 3-X, wherein,
r in monomer 1-X1And R2And is also one of the following structural formulas:
Figure FDA0003287989040000021
ortho, meta or para;
Figure FDA0003287989040000022
ortho, meta or para, R0is-CH3、-CF3or-OCH3；
R in monomer 2-X1And R2And is also one of the following structural formulas:
Figure FDA0003287989040000023
1,4, 1,5, 1,6, 2,6 or 2, 7;
r in monomer 3-X1And R2And is also one of the following structural formulas:
Figure FDA0003287989040000024
4,3 'or 4, 4', wherein X is O, S, CO, SO2、CH2、C(CH3)2Or C (CF)3)2；
(2) Monomers of the second type
The second monomer is R1And R2Diamine containing cyclopeptide structures with different structures comprises a monomer 4-X, a monomer 5-X and a monomer 6-X, wherein,
r in monomer 4-X1And R2Respectively is phenyl and naphthalene in the following structural formula:
Figure FDA0003287989040000025
ortho, meta or para;
Figure FDA0003287989040000026
ortho, meta or para, R0is-CH3、-CF3or-OCH3；
Figure FDA0003287989040000027
1,4, 1,5, 1,6, 2,6 or 2, 7;
r in monomer 5-X1And R2Respectively is phenyl and diphenyl in the following structural formula:
Figure FDA0003287989040000028
ortho, meta or para;
Figure FDA0003287989040000029
ortho, meta or para, R0is-CH3、-CF3or-OCH3；
Figure FDA00032879890400000210
4,3 'or 4, 4', wherein X is O, S, CO, SO2、CH2、C(CH3)2Or C (CF)3)2；
R in monomer 6-X1And R2Respectively, a naphthalene and a diphenyl in the following structural formulas:
Figure FDA0003287989040000031
1,4, 1,5, 1,6, 2,6 or 2, 7;
Figure FDA0003287989040000032
Figure FDA0003287989040000033
4,3 'or 4, 4', wherein X is O, S, CO, SO2、CH2、C(CH3)2Or C (CF)3)2。
3. The method of preparing a cyclic peptide structure-containing diamine of claim 2, wherein the first monomer is prepared by the steps of:
(11) mixing a compound containing a cyclopeptide structure, a compound A and a catalyst A in a solvent A, and reacting the obtained mixed system for 8-12h at 50-70 ℃ under the protection of inert gas; precipitating, filtering, washing and drying the obtained reaction solution to obtain an intermediate 1; the molar ratio of the compound containing the cyclopeptide structure, the compound A and the catalyst A is 1: 2.2-3: 1.5-2; the total concentration of the compound containing the cyclopeptide structure and the compound A in a mixed system is 0.2-0.3 g/mL; the compound A is an aromatic compound containing halogen and nitro, or an aromatic compound containing acyl halide and nitro;
(12) mixing the intermediate 1 and stannous chloride dihydrate in a solvent B, and reacting the obtained mixed system at 50-70 ℃ for 20-24 h; precipitating, extracting, washing and drying the obtained reaction liquid to obtain a product 1 which is a first type of monomer; the molar ratio of the intermediate 1 to the stannous chloride dihydrate is 1: 8-12; the solvent B is obtained by uniformly mixing the solvent A and ethanol according to the volume ratio of 1: 0.5-2; the total concentration of the intermediate 1 and stannous chloride dihydrate in a mixed system is 0.07-0.1 g/mL.
4. The method of preparing a cyclic peptide structure-containing diamine of claim 2, wherein the second monomer is prepared by the steps of:
(21) mixing a compound containing a cyclopeptide structure, a compound A and a catalyst A in a solvent A, and reacting the obtained mixed system for 8-12h at 50-70 ℃ under the protection of inert gas; precipitating, filtering, washing and drying the obtained reaction solution to obtain an intermediate 2-1; the molar ratio of the compound containing the cyclopeptide structure, the compound A and the catalyst A is 1: 1.1-1.2: 0.75-1; the total concentration of the compound containing the cyclopeptide structure and the compound A in a mixed system is 0.2-0.3 g/mL; the compound A is an aromatic compound containing halogen and nitro, or an aromatic compound containing acyl halide and nitro;
(22) mixing the intermediate 2-1, the compound B and the catalyst A in a solvent A, and reacting the obtained mixed system for 8-12h at 50-70 ℃ under the protection of inert gas; precipitating, filtering, washing and drying the obtained reaction solution to obtain an intermediate 2-2; the molar ratio of the intermediate 2-1 to the compound B to the catalyst A is 1: 1.1-1.2: 0.75-1; the total concentration of the intermediate 2-1 and the compound B in a mixed system is 0.2-0.3 g/mL; the compound B is an aromatic compound containing halogen and nitro, or an aromatic compound containing acyl halide and nitro;
(23) mixing the intermediate 2-2 and stannous chloride dihydrate in a solvent B, and reacting the obtained mixed system at 50-70 ℃ for 20-24 h; precipitating, extracting, washing and drying the obtained reaction liquid to obtain a product 2, namely a second monomer; the molar ratio of the intermediate 2-2 to the stannous chloride dihydrate is 1: 8-12; the solvent B is obtained by uniformly mixing the solvent A and ethanol according to the volume ratio of 1: 0.5-2; the total concentration of the intermediate 2-2 and stannous chloride dihydrate in a mixed system is 0.07-0.1 g/mL.
5. The method for preparing diamine containing cyclopeptide structure according to claim 1, wherein the diamine containing cyclopeptide structure with the general structural formula (II) is prepared by the following steps:
(31) mixing L-tyrosine cyclic peptide and nitric acid in a solvent A, and reacting the obtained mixed system at room temperature for 6-8 h; precipitating, filtering, washing and drying the obtained reaction solution to obtain an intermediate 3; the molar ratio of the L-tyrosine cyclic peptide to the nitric acid is 1: 20; the mass-volume ratio of the L-tyrosine cyclic peptide to the solvent A in the mixed system is 0.2-0.3, the mass unit of the L-tyrosine cyclic peptide is g, and the volume unit of the solvent A is mL;
(32) mixing the intermediate 3 and stannous chloride dihydrate in a solvent B, and reacting the obtained mixed system at 50-70 ℃ for 20-24 h; precipitating, extracting, washing and drying the obtained reaction solution to obtain a product 3, namely diamine containing a cyclopeptide structure determined by the general structural formula (II); the molar ratio of the intermediate 3 to the stannous chloride dihydrate is 1: 8-12; the solvent B is obtained by uniformly mixing the solvent A and ethanol according to the volume ratio of 1: 0.5-2; the total concentration of the intermediate 3 and stannous chloride dihydrate in a mixed system is 0.07-0.1 g/mL.
6. The method for preparing diamine containing cyclic peptide structure as claimed in claim 3, 4 or 5, wherein the solvent A is one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone.
7. Polyimide containing a cyclic peptide structure, characterized by being prepared from the diamine containing a cyclic peptide structure and the aromatic dianhydride compound according to claim 1 or 2, and having a structural formula:
Figure FDA0003287989040000041
n is 10 to 500;
r is as defined above1And R2The same or different, the structure thereof is any one of the following structures:
Figure FDA0003287989040000042
ortho, meta or para;
Figure FDA0003287989040000043
ortho, meta or para, R0is-CH3、-CF3or-OCH3；
Figure FDA0003287989040000051
1,4, 1,5, 1,6, 2,6 or 2, 7;
Figure FDA0003287989040000052
Figure FDA0003287989040000053
4,3 'or 4, 4', wherein X is O, S, CO, SO2、CH2、C(CH3)2Or C (CF)3)2。
8. The method for preparing a cyclic peptide structure-containing polyimide according to claim 7, comprising the steps of:
(i) under the protection of inert gas, dissolving a diamine monomer containing a cyclopeptide structure in a polar solvent, stirring until the diamine monomer containing the cyclopeptide structure is completely dissolved, adding an aromatic dianhydride compound with the same molar weight as that of the diamine monomer containing the cyclopeptide structure, and stirring at room temperature for 12-15 hours to obtain a polyamic acid solution;
(ii) and (3) carrying out gradient heating and ring closure on the polyamic acid solution at 80-320 ℃ under a vacuum condition to obtain the polyimide containing the cyclopeptide structure.
9. The method for preparing a cyclic peptide structure-containing polyimide according to claim 8, wherein in the step (ii), the gradient heating ring-closure procedure comprises:
isothermal at 80-100 ℃ for 4-4.5 h,
isothermal at 115-120 ℃ for 2-2.5 h,
isothermal at 150-155 ℃ for 2.5-3 h,
isothermal at 200-210 ℃ for 2-4 h,
keeping the temperature constant for 1.5-2 h at 300-320 ℃.
10. The method for preparing polyimide containing a cyclic peptide structure according to claim 8 or 9, wherein the polar solvent is one of N, N-dimethylacetamide, N-dimethylformamide, and N-methylpyrrolidone; the amount of the polar solvent is such that the total concentration of the diamine monomer containing a cyclic peptide structure and the aromatic dianhydride compound is 0.15-0.2 g/mL.
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