CN111018850A - Diamine containing phenoxazine structure and polymer thereof with antibacterial effect - Google Patents

Diamine containing phenoxazine structure and polymer thereof with antibacterial effect Download PDF

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CN111018850A
CN111018850A CN201911288086.1A CN201911288086A CN111018850A CN 111018850 A CN111018850 A CN 111018850A CN 201911288086 A CN201911288086 A CN 201911288086A CN 111018850 A CN111018850 A CN 111018850A
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phenoxazine
diamine
antibacterial effect
polyimide
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谭井华
刘亦武
贺盼
赵先清
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Guangdong Gaoyi Packaging Technology Co ltd
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Hunan University of Technology
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Abstract

The invention discloses diamine containing a phenoxazine structure and a polymer thereof with an antibacterial effect. The invention utilizes the reaction of the intermediate containing phenoxazine substituted by two halogen atoms and ammonia water to convert the halogen atoms into amino; grafting a nitro-containing group through Ullmann coupling reaction and reducing to obtain a diamine monomer containing a phenoxazine structure, and polymerizing the prepared diamine monomer and dianhydride to obtain the polyimide containing the phenoxazine structure. The invention creatively introduces the planar rigid structure and the polar group of the phenoxazine into the polyimide main chain, the planar rigid structure is beneficial to regular stacking of molecular chains and induces polymer crystallization, and the polar group 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.

Description

Diamine containing phenoxazine structure and polymer thereof with antibacterial effect
Technical Field
The invention relates to the technical field of material science, in particular to diamine containing a phenoxazine structure and a polymer thereof with an antibacterial effect.
Background
Aromatic Polyimide (PI) is a high temperature resistant material with excellent performance, contains strong rigid benzene ring and imide ring, has excellent characteristics of high glass transition temperature (Tg), high strength, low Coefficient of Thermal Expansion (CTE) and the like, and has a great application prospect as a structural material or a functional material. Meanwhile, the polyimide also has excellent flame retardant property and non-toxic property, and can be widely applied to material packaging.
The FOLED is one of the technologies with great development prospect, can realize flexible display, can prepare foldable and bendable displays, and is thinner, lighter and more impact-resistant than an OLED display screen made of rigid glass. Polyimide 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, while the barrier property of the traditional commercial polyimide film can not meet the packaging requirement of a flexible display device, the improvement of the barrier property by the currently adopted means of multilayer compounding, plating, inorganic nano modification and the like still has some defects, and the high-barrier layer film used by multilayer compounding has poor heat resistance and low stability; the flexibility of the coating film is influenced, and the surface is not smooth and easy to break and fall off; inorganic nano-modification is the most commonly used method, which effectively extends the diffusion path of water vapor and oxygen molecules in the substrate through the sheet-like nano-layer, thereby improving the barrier property thereof, however, the method is based on the property difference of the matrix, and the improvement of the barrier property is limited. In addition, polyimide has the defects of low barrier property and high water oxygen transmission rate, and the antibacterial property of polyimide is insufficient, so that the content is difficult to be prevented from being polluted under the condition of high water oxygen transmission rate, and the wide application of polyimide in the aspect of packaging is greatly limited. Therefore, the preparation of the polymer substrate material with high barrier property and antibacterial function accelerates the application of polyimide.
Disclosure of Invention
The invention aims to solve the technical problem of providing a diamine monomer containing a phenoxazine structure, which has good planarity and antibacterial property, aiming at the defects of heat resistance and barrier property of the existing polyimide.
The invention also aims to solve the technical problem of preparing polyimide with high barrier property, good thermal stability and high planarity by using the diamine monomer.
The purpose of the invention is realized by the following technical scheme:
diamine containing a phenoxazine structure and having an antibacterial effect has a structural general formula as follows:
Figure BDA0002318592620000021
Ar1any one selected from the following structural formulas:
Figure BDA0002318592620000022
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:
Figure BDA0002318592620000031
further, said Ar2Preferably, it is
Figure BDA0002318592620000032
Ar3 is one or more of
Figure BDA0002318592620000033
One or more of (a).
According to the preparation method of the diamine containing the phenoxazine structure with the antibacterial effect, the preparation steps comprise:
s1, a phenoxazine monomer containing two halogen atom substitutions
Figure BDA0002318592620000034
Figure BDA0002318592620000035
Reacting with ammonia water under a protective atmosphere 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 step S1, an Ar1 monomer containing a halogen atom and a nitro substituent into a solvent, adding alkali in a protective gas atmosphere, and performing Ullmann coupling reaction to obtain a monomer 4, a monomer 5 or a monomer 6 containing two nitro groups;
s3, adding the monomer 4, the monomer 5 or the monomer 6 in the step S2 into a solvent, adding a reducing agent, and carrying out reduction reaction in an atmosphere of protective gas to obtain a diamine monomer containing a phenoxazine structure, wherein the diamine monomer is shown in a structural general formula I, II or III;
the monomer 1, the monomer 2 and the monomer 3 in the step S1, and the monomer 4, the monomer 5 and the monomer 6 in the step S2 respectively have the following structural characteristics:
Figure BDA0002318592620000041
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 lithium hexamethyldisilazide.
Further, in S2, the ratio of the amount of the monomer 1, the monomer 2 or the monomer 3 to the amount of the substance containing a halogen atom and a nitro-substituted Ar1 monomer is 1: 2-8, and the ratio of the amount of the added alkali to the amount of the substance containing the monomer 1, the monomer 2 or the monomer 3 is 1: 0.5-2.
Preferably, the ratio of the amount of monomer 1, monomer 2 or monomer 3 to the amount of a substance containing a halogen atom and a nitro-substituted Ar1 monomer in S2 is 1: 5, and the ratio of the amount of the base added to the amount of the substance of monomer 1, monomer 2 or monomer 3 is 1: 1.
Further, in S3, the reducing agent is one or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder, and zinc powder. The mass ratio of the monomer 4, the monomer 5 or the monomer 6 to the reducing agent in S3 is 1: 2-32; preferably, the amount of the substance of the monomer 4, the monomer 5 or the monomer 6 to the reducing agent in S3 is 1: 20.
Further, the protective gas from S1 to S3 is one or more of nitrogen, helium, neon, argon, krypton, xenon and radon;
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 diphenyl ether; the solvent in S3 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 of S1-S3 is 50-170 ℃, 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 100 ℃, the reaction time is 24 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in the S2, the reaction temperature is 150 ℃, the reaction time is 24 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in S3, the reaction temperature is 80 ℃, the reaction time is 24h, the drying temperature is 80 ℃, and the drying time is 24 h.
Further, the diamine obtained by the method is used for preparing polyimide suitable for microelectronics, military industry, aerospace, packaging and protection and electronic device packaging, and the polyimide has a structural general formula as follows:
Figure BDA0002318592620000051
wherein y is 1-10000. X is selected from any one of the following:
Figure BDA0002318592620000052
the preparation method of the polyimide containing the phenoxazine structure comprises the following steps: in an argon protective atmosphere, diamine containing a phenoxazine structure and dianhydride containing an X structure are dissolved in a strong-polarity aprotic solvent according to a molar ratio of 1: 0.95-1.05, the mixture is stirred and reacted 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.
Compared with the prior art, the beneficial effects are:
the invention designs and synthesizes an angle through a molecular structure, creatively introduces the phenoxazine structure and a polar group into a diamine monomer at the same time, and prepares the diamine monomer with high planarity containing the polar group. Phenoxazine is a good electron donor with aromaticity, easily forms a D-pi-D or S-pi-S system, and has high electron density and good rigid structure. Meanwhile, the diamine takes a phenothiazine structure as a core, so that the prepared diamine has certain antibacterial performance, and the functional diversity of the diamine monomer is greatly improved.
The invention introduces a plane rigid structure and a polar group into a polyimide main chain by utilizing the prepared diamine monomer, the plane rigid structure is beneficial to 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 ensures that the prepared polyimide molecular chains are regularly arranged, have strong intermolecular force and are tightly piled, thereby having excellent barrier property, higher glass transition temperature and thermal stability and lower thermal expansion coefficient. After the polyimide is synthesized by using the diamine monomer and the dianhydride monomer with antibacterial performance, the antibacterial performance is not lost, and the polyimide is endowed with 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.
Example 1
This example provides the synthesis of N1, N1' - (10H-phenoxazine-2,8-diyl) bis (bezene-1, 4-diamine):
Figure BDA0002318592620000061
s1, synthesizing an intermediate 10H-phenoxazine-2, 8-diamine:
adding 3.41g (0.01mol) of 2,8-dibromo-10H-phenoxazine, a proper amount of cuprous oxide, 50ml of NMP and 13ml of ammonia water (29%, 0.2mol) into a 200ml pressure-resistant bottle, carrying out argon protection, carrying out reaction at 100 ℃, after the reaction is finished, pouring the reaction liquid into ice water, extracting with dichloromethane, removing the solvent under reduced pressure, and mixing the product with dichloromethane to n-hexane to obtain a product of 2: 1 (volume ratio) is mobile phase silica gel as fixed phase, and the product is collected, dried by spinning, and dried in vacuum at 80 ℃ for 24h to obtain the intermediate. The intermediate has the following structure:
Figure BDA0002318592620000071
s2, synthesizing an intermediate N2, N8-bis (4-nitrophenyl) -10H-phenoxazine-2, 8-diamine:
2.13g (0.01mol) of 10H-phenoxazine-2,8-diamine, 7.50g (0.05mol) of p-fluoronitrobenzene and 13.8g (0.1mol) of potassium carbonate are added into a 250ml three-neck flask, 150ml of dimethyl sulfoxide is added, magnetic stirring is carried out, argon is introduced, the temperature is increased to 150 ℃ for reaction for 12 hours, then the reaction solution is poured into cold water, precipitates are filtered out, and hydrochloric acid and water are used for washing, thus obtaining an intermediate. The intermediate has the following structure:
Figure BDA0002318592620000072
s3, synthesizing N1, N1' - (10H-phenoxazine-2,8-diyl) bis (bezene-1, 4-diamine):
adding 4.55g (0.01mol) of N2, N8-bis (4-nitrophenyl) -10H-phenoxazine-2,8-diamine into a 500ml three-neck flask, adding 450ml of absolute ethyl alcohol, magnetically stirring and introducing argon, heating in an oil bath to 70 ℃, adding 0.1g of 10% wt palladium carbon, gradually dropwise adding 10ml of hydrazine hydrate, refluxing for 24 hours, filtering the reaction liquid by using a funnel, placing the filtrate in a refrigerator for 24 hours for crystallization, collecting off-white solid after suction filtration, and drying in a vacuum drying oven at 80 ℃ for 24 hours to obtain the product.
Example 2
The present embodiment provides
Synthesis of N2- (5-aminopyridin-2-yl) -N7- (6-aminopyridin-3-yl) -10H-phenoxazine-2, 7-diamine:
Figure BDA0002318592620000073
s1, synthesizing an intermediate 10H-phenoxazine-2, 7-diamine:
adding 3.41g (0.01mol) of 2,7-dibromo-10H-phenoxazine, a proper amount of cuprous oxide, 50ml of NMP and 13ml of ammonia water (29 percent and 0.2mol) into a 200ml pressure-resistant bottle, reacting at 100 ℃ under the protection of argon, after the reaction is finished, pouring the reaction liquid into ice water, extracting with dichloromethane, removing the solvent under reduced pressure, purifying the product by taking dichloromethane and n-hexane (volume ratio) as mobile phase silica gel as a stationary phase for column chromatography, collecting the product, spin-drying, and drying at 80 ℃ for 24 hours in vacuum to obtain an intermediate. The intermediate has the following structure:
Figure BDA0002318592620000081
s2, synthesizing an intermediate
N2-(5-nitropyridin-2-yl)-N7-(6-nitropyridin-3-yl)-10H-phenoxazine-2,7-diamine：
2.13g (0.01mol) of 10H-phenoxazine-2,7-diamine, 7.105g (0.05mol) of 2-fluoro-5-nitropyridine and 13.8g (0.1mol) of potassium carbonate were added to a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was carried out while introducing argon gas, the temperature was raised to 150 ℃ to react for 12 hours, the reaction solution was poured into cold water, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain a product intermediate. The intermediate has the following structure:
Figure BDA0002318592620000082
s3. synthesis
N2-(5-aminopyridin-2-yl)-N7-(6-aminopyridin-3-yl)-10H-phenoxazine-2,7-diamine:
4.57g (0.01mol) of N2- (5-nitropyridin-2-yl) -N7- (6-nitropyridin-3-yl) -10H-phenoxazine-2,7-diamine was added to a 500ml three-necked flask, 450ml of absolute ethanol was added, magnetic stirring was carried out and argon gas was introduced, after the oil bath was heated to 70 ℃, 0.1g of 10% wt palladium on carbon was added and 10ml of hydrazine hydrate was gradually added dropwise, after reflux reaction for 24 hours, the reaction solution was filtered by a funnel, the filtrate was placed in a refrigerator for 24 hours to crystallize, after which an off-white solid was collected by suction filtration and dried in a vacuum oven at 80 ℃ for 24 hours to obtain the product.
Example 3
This example provides the synthesis of N1, N1' - (dibenzo [ b, d ] furan-2,8-diyl) bis (bezene-1, 3-diamine):
Figure BDA0002318592620000091
s1, synthesizing an intermediate 10H-phenoxazine-3, 7-diamine:
adding 3.41g (0.01mol) of 3,7-dibromo-10H-phenoxazine, a proper amount of cuprous oxide, 50ml of NMP and 13ml of ammonia water (29 percent and 0.2mol) into a 200ml pressure resistant bottle, reacting at 100 ℃ under the protection of argon, after the reaction is finished, pouring the reaction liquid into ice water, extracting with dichloromethane, removing the solvent under reduced pressure, purifying the product by taking dichloromethane and n-hexane (volume ratio) as mobile phase silica gel as a stationary phase for column chromatography, collecting the product, spin-drying, and drying at 80 ℃ for 24 hours in vacuum to obtain the intermediate. The intermediate has the following structure:
Figure BDA0002318592620000092
s2, synthesizing an intermediate N3, N7-bis (3-nitrophenyl) -10H-phenoxazine-3, 7-diamine:
2.13g (0.01mol) of 10H-phenoxazine-3,7-diamine, 7.50g (0.05mol) of m-fluoronitrobenzene and 13.8g (0.1mol) of potassium carbonate are added into a 250ml three-neck flask, 150ml of dimethyl sulfoxide is added, magnetic stirring is carried out, argon is introduced, the temperature is increased to 150 ℃ for reaction for 12 hours, then the reaction solution is poured into cold water, precipitates are filtered out, and hydrochloric acid and water are used for washing, thus obtaining an intermediate. The intermediate has the following structure:
Figure BDA0002318592620000093
s3, synthesizing N1, N1' - (10H-phenoxazine-3,7-diyl) bis (bezene-1, 3-diamine):
adding 4.55g (0.01mol) of N3, N7-bis (3-nitrophenyl) -10H-phenoxazine-3,7-diamine into a 500ml three-neck flask, adding 450ml of absolute ethyl alcohol, magnetically stirring and introducing argon, heating in an oil bath to 70 ℃, adding 0.1g of 10% wt palladium carbon, gradually dropwise adding 10ml of hydrazine hydrate, refluxing for 24 hours, filtering the reaction liquid by using a funnel, placing the filtrate in a refrigerator for 24 hours for crystallization, collecting off-white solid after suction filtration, and drying in a vacuum drying oven at 80 ℃ for 24 hours to obtain the product.
Example 4
The present embodiment provides
N2,N2'-(10H-phenoxazine-2,7-diyl)bis(naphthalene-2,6-diamine)：
Figure BDA0002318592620000101
S1, synthesizing an intermediate
N2,N7-bis(6-nitronaphthalen-2-yl)-10H-phenoxazine-2,7-diamine：
2.13g (0.01mol) of 10H-phenoxazine-2,7-diamine, 9.56g (0.05mol) of 2-fluoro-6-nitro-naphthalene and 13.8g (0.1mol) of potassium carbonate were added to a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was carried out while introducing argon gas, the reaction solution was poured into cold water after warming to 150 ℃ for 12 hours, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
Figure BDA0002318592620000102
s2, synthesis of N2, N2' - (10H-phenoxazine-2,7-diyl) bis (naphthalene-2, 6-diamine):
adding 5.56g (0.01mol) of N2, N7-bis (6-nitro phenyl-2-yl) -10H-phenoxazine-2,7-diamine into a 500ml three-neck flask, adding 450ml of absolute ethyl alcohol, magnetically stirring and introducing argon, heating in an oil bath to 70 ℃, adding 0.1g of 10% wt palladium carbon, gradually dropwise adding 10ml of hydrazine hydrate, refluxing for 24H, filtering the reaction solution by using a funnel, placing the filtrate in a refrigerator for 24H for crystallization, collecting off-white solid after suction filtration, and drying in a vacuum drying oven at 80 ℃ for 24H to obtain the product.
Example 5
The present embodiment provides
Synthesis of N1, N1' - (10H-phenoxazine-3,7-diyl) bis (N4- (4-aminophenyl) bezene-1, 4-diamine):
Figure BDA0002318592620000103
s1, synthesizing an intermediate
N1,N1'-(10H-phenoxazine-3,7-diyl)bis(N4-(4-nitrophenyl)benzene-1,4-diamine)：
2.13g (0.01mol) of 10H-phenoxazine-3,7-diamine, 11.61g (0.05mol) of 4-fluoro-N- (4-nitrophenyl) aniline and 13.8g (0.1mol) of potassium carbonate were added to a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was carried out while introducing argon gas, the reaction solution was poured into cold water after heating to 150 ℃ for 12 hours, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
Figure BDA0002318592620000111
s2. synthesis
N1,N1'-(10H-phenoxazine-3,7-diyl)bis(N4-(4-aminophenyl)benzene-1,4-diamine)：
6.38g (0.01mol) of N1, N1' - (10H-phenoxazine-3,7-diyl) bis (N4- (4-nitrophenyl) benzene-1,4-diamine) is added into a 500ml three-necked flask, 450ml of absolute ethyl alcohol is added, magnetic stirring is carried out, argon is introduced, after an oil bath is heated to 70 ℃, 0.1g of 10% wt palladium carbon is added, 10ml of hydrazine hydrate is gradually added dropwise, after reflux reaction is carried out for 24 hours, the reaction liquid is filtered by a funnel, the filtrate is placed in a refrigerator for 24 hours for crystallization, after suction filtration, off-white solid is collected, and the off-white solid is dried in a vacuum drying oven at 80 ℃ for 24 hours, so that the product is obtained.
Example 6
The present embodiment provides
Synthesis of 4,4' - ((10H-phenoxazine-2,8-diyl) bis (azanediyl)) bis (N- (4-aminophenyl) benzamide):
Figure BDA0002318592620000112
s1, synthesizing an intermediate
4,4'-((10H-phenoxazine-2,8-diyl)bis(azanediyl))bis(N-(4-nitrophenyl)benzamide)：
2.13g (0.01mol) of 10H-phenoxazine-2,8-diamine, 13.01g (0.05mol) of 4-fluoro-N- (4-nitrophenyl) benzamide and 13.8g (0.1mol) of potassium carbonate were added to a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was conducted while introducing argon gas, the temperature was raised to 150 ℃ to react for 12 hours, the reaction solution was poured into cold water, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
Figure BDA0002318592620000121
s2. synthesis
4,4'-((10H-phenoxazine-2,8-diyl)bis(azanediyl))bis(N-(4-aminophenyl)benzamide)：
6.94g (0.01mol) of 4,4' - ((10H-phenoxazine-2,8-diyl) bis (azanediyl)) bis (N- (4-nitrophenyl) benzamide) is added into a 500ml three-necked flask, 450ml of absolute ethyl alcohol is added, magnetic stirring is carried out, argon is introduced, after an oil bath is heated to 70 ℃, 0.1g of 10% wt palladium carbon is added, 10ml of hydrazine hydrate is gradually dripped, after reflux reaction is carried out for 24 hours, reaction liquid is filtered by a funnel, filtrate is placed in a refrigerator for 24 hours for crystallization, and after suction filtration, off-white solid is collected and dried in a vacuum drying oven at 80 ℃ for 24 hours, so that the product is obtained.
Example 7
This example provides the preparation of a polyimide by a thermal imidization process, comprising the steps of:
dissolving diamine containing a phenoxazine structure and dianhydride containing an X structure in a strong polar aprotic solvent according to a molar ratio of 1: 0.95-1.05 in an argon protective atmosphere, stirring and reacting at-15-30 ℃ for 2-48 h to obtain a homogeneous polyamic acid glue solution, scraping the polyamic acid glue solution on a glass plate to form a thin layer with the thickness of 1-3 mm, placing the glass plate in a vacuum oven, vacuumizing, and heating, wherein the heating process is as follows: and heating to 100 ℃ and keeping the temperature for 0.5-1 h, heating from 100 ℃ to 200 ℃ and keeping the temperature for 0.5-1 h, heating from 200 ℃ to 300 ℃ and keeping the temperature for 0.5-1 h, finally heating from 300 ℃ to 420 ℃ and keeping the temperature for 1.0-2.0 h, and cooling to obtain the high-planarity polyimide film containing the phenoxazine structure.
The diamine monomers prepared in examples 1 to 4 were tested for antibacterial activity against escherichia coli according to QB/T25912003, and were respectively tested for antibacterial activity against polyimides prepared by polymerizing with pyromellitic dianhydride in examples 7 to 12, where p-phenylenediamine and polyimides synthesized with pyromellitic dianhydride were used as control groups, and the test results are shown in table 1:
TABLE 1
Figure BDA0002318592620000122
Figure BDA0002318592620000131
The diamines prepared in examples 1 to 6 were polymerized with pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, 4 '-diphenyl ether dianhydride, 1,4,5, 8-naphthalene tetracarboxylic anhydride, 4' - (hexafluoroisopropylene) diphthalic anhydride, and 3,3', 4' -benzophenone tetracarboxylic dianhydride to form high-plane polyimides containing phenoxazine structures, and the synthesized polyimides were tested for barrier properties, glass transition temperature, thermal stability, and thermal expansion coefficient, 1 to 6 groups of diamines prepared in examples 1 to 6 were used, and the data range of the polyimide tests for each group was determined, and the test results are shown in table 2:
wherein the dianhydrides are all commercially available on the commercial scale from the reagent Aladdin. The barrier property is detected according to GB/T1038-2000 differential pressure method for testing gas permeability of plastic films and sheets and GB/T19789-2005 coulometer detection method for testing oxygen permeability of plastic films and sheets of packaging materials, and the thermal expansion coefficient and the proud transition temperature are detected according to GB/T36800.2-2018 thermo-mechanical analysis method for plastics.
TABLE 2
Figure BDA0002318592620000132
As shown in tables 1-2, the invention introduces the phenoxazine structure and the polar group into the diamine monomer at the same time to prepare the diamine monomer with high planarity and containing the polar group, and has high electron density and good rigid structure. A plane rigid structure and a polar group are introduced into a polyimide main chain, the plane rigid structure is beneficial to regular stacking of molecular chains and induces polymer crystallization, and the polar group can enhance the hydrogen bond effect of molecular chain bonds and promote the tight stacking of the molecular chains. The synergy of the effects can ensure that molecular chains are regularly arranged and tightly stacked, and the barrier property of the polyimide is obviously improved, so that the polyimide has excellent barrier property, higher glass transition temperature and thermal stability and lower thermal expansion coefficient. The diamine monomer containing the phenoxazine structure has good antibacterial activity of escherichia coli, and polyimide prepared from the diamine also has good antibacterial activity.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The diamine containing the phenoxazine structure and having the antibacterial effect is characterized by having the following structural general formula:
Figure FDA0002318592610000011
Ar1any one selected from the following structural formulas:
Figure FDA0002318592610000012
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. Phenoxazine structure-containing diamine according to claim 1 with antibacterial effect, characterized in that Ar is as defined above2And Ar3Any one selected from the following structural formulas:
Figure FDA0002318592610000021
3. phenoxazine structure-containing diamine according to claim 1 with antibacterial effect, characterized in that Ar is as defined above2Is composed of
Figure FDA0002318592610000022
Ar3 is one or more of
Figure FDA0002318592610000023
Figure FDA0002318592610000024
One or more of (a).
4. The phenoxazine structure-containing diamine of any one of claims 1 to 3, which has an antibacterial effect, characterized in that the preparation method of the phenoxazine structure-containing diamine comprises:
s1, a phenoxazine monomer containing two halogen atom substitutions
Figure FDA0002318592610000025
Figure FDA0002318592610000026
Reacting with ammonia water under a protective atmosphere 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 step S1, an Ar1 monomer containing a halogen atom and a nitro substituent into a solvent, adding alkali in a protective gas atmosphere, and performing Ullmann coupling reaction to obtain a monomer 4, a monomer 5 or a monomer 6 containing two nitro groups;
s3, adding the monomer 4, the monomer 5 or the monomer 6 in the step S2 into a solvent, adding a reducing agent, and carrying out reduction reaction in an atmosphere of protective gas to obtain a diamine monomer containing a phenoxazine structure, wherein the diamine monomer is shown in a general structural formula I, II or III;
the monomer 1, the monomer 2 and the monomer 3 in the step S1, and the monomer 4, the monomer 5 and the monomer 6 in the step S2 respectively have the following structural characteristics:
Figure FDA0002318592610000031
5. a phenoxazine structure-containing diamine according to claim 4, which has an antibacterial effect, wherein the ratio of the amount of monomer 1, monomer 2 or monomer 3 to the amount of a substance containing a halogen atom and a nitro group-substituted Ar1 monomer in S2 is 1:2 to 4, and the ratio of the amount of the base added to the amount of the substance of monomer 1, monomer 2 or monomer 3 is 1: 0.5 to 2; the mass ratio of the monomer 4, the monomer 5 or the monomer 6 to the reducing agent in S3 is 1: 2-32; the ratio of the two halogen atom substituted phenoxazine monomers in B1 to the amount of cyano-group in cyanide is 1: 2-8.
6. A phenoxazine structure-containing diamine of claim 4 which has antibacterial effect, and is characterized in that 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, lithium hexamethyldisilazide; the reducing agent in S3 is one or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder and zinc powder.
7. A phenoxazine structure-containing diamine of claim 4 which has antibacterial effect, and is characterized in that the solvent in S1 is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene, xylene; the solvent in S2 is one or more of dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane, toluene, xylene, acetone, acetonitrile and diphenyl ether; the solvent in S3 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. A diamine containing a phenoxazine structure with antibacterial effect according to claim 4, characterized in that the reaction temperature in S1-S3 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 use of the diamine containing a phenoxazine structure with an antibacterial effect according to any one of claims 1 to 8 for the synthesis of polyimide, characterized in that the structural formula of the polyimide is as follows:
Figure FDA0002318592610000041
wherein y is 1-10000. X is selected from any one of the following structures:
Figure FDA0002318592610000042
10. the use of a diamine monomer containing a phenoxazine structure according to claim 9 in the synthesis of a polyimide, where the polyimide is used in microelectronics, military industry, aerospace, packaging and protection, and electronics packaging.
CN201911288086.1A 2019-12-15 2019-12-15 Diamine containing phenoxazine structure and polymer thereof with antibacterial effect Pending CN111018850A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105237462A (en) * 2015-09-08 2016-01-13 湖南工业大学 Diamine monomer containing carbazole structure and having high planarity, synthetic method and application thereof
CN105440286A (en) * 2016-01-12 2016-03-30 湖南工业大学 Polyimide of fluorene-containing or fluorenone-containing structure as well as preparation method and application of polyimide
CN105461925A (en) * 2016-01-04 2016-04-06 湖南工业大学 Polyimide containing carbazole structure, preparation method thereof and application thereof
CN108863981A (en) * 2018-07-31 2018-11-23 湖南工业大学 A kind of Triamine monomer and its preparation method and application containing benzothiazole structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105237462A (en) * 2015-09-08 2016-01-13 湖南工业大学 Diamine monomer containing carbazole structure and having high planarity, synthetic method and application thereof
CN105461925A (en) * 2016-01-04 2016-04-06 湖南工业大学 Polyimide containing carbazole structure, preparation method thereof and application thereof
CN105440286A (en) * 2016-01-12 2016-03-30 湖南工业大学 Polyimide of fluorene-containing or fluorenone-containing structure as well as preparation method and application of polyimide
CN108863981A (en) * 2018-07-31 2018-11-23 湖南工业大学 A kind of Triamine monomer and its preparation method and application containing benzothiazole structure

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