Organic polyspirogrid nano polymer material and preparation method therefor

Abstract

The invention relates to an organic polyspiralgrid nanopolymer material and a preparation method thereof, and belongs to the field of nanotechnology and organic electronics. The structure of the organic polyspiralgrid nanopolymer material is composed of grids containing a spiro ring that serves as a repeat unit to form a special nano polymer, and the structure shares the spiro ring structure. A synthetic method thereof relates to a synthon containing the spiro ring, and by means of a Friedel-Crafts reaction, an organic spirogrid and a nano polymer thereof are built. By means of reasonable molecular design and the Friedel-Crafts reaction with the advantages of being mild in reaction condition, high in yield, high in selectivity, simple in posttreatment, green, free of toxicity and the like, the problems that a traditional polymer molecule is complex in synthesis step, toxic in posttreatment, large in pollution and the like are solved.

Claims

1. An organic polyspiralgrid nanopolymer material represented by the following structure formula: ##STR00021## wherein, R.sub.1 and R.sub.2 are identical or different, and are selected from the following groups: ##STR00022## wherein, m is a natural number ranging from 1 to 10, ##STR00023## are identical or different and the specific structures thereof are as follows: ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## are identical or different and are one of the following structures: ##STR00029##

2. A method for preparing the organic polyspiralgrid nanopolymer material of claim 1, comprising forming an organic nanopolymer by connecting rigid organic mono-spiralgrids through common spiral rings, wherein the polymer comprises at least two types of fluorene-like groups, wherein one type of the fluorene-like groups is a 9-phenylfluorenol derivative and the other type of the fluorene-like groups is a spiral ring structure with a geometric configuration similar to that of spirobifluorene; a synthesis method of the organic nanopolymer is to make A2B2-type spiral ring-containing synthon have Friedel-Crafts reaction in a dry organic solvent at room temperature under the catalysis of an acid as the catalyst to get the organic polyspiralgrid nanopolymer through common spiral rings, and then make A1B1-type spiral ring-containing synthon have Friedel-Crafts reaction to seal the terminals of the organic polyspiralgrid nanopolymer to get the final structure, the structural formula of the organic polyspiralgrid nanopolymer as well as reaction formula of the organic polyspiralgrid nanopolymer are as follows: ##STR00030##

3. The method for preparing the organic polyspiralgrid nanopolymer material of claim 2, wherein the acid includes Lewis acids and protonic acids, and an amount of acid catalyst added is 2-5 times that of A2B2-type synthon according to reactivity of different substrates; and a reaction concentration of A2B2-type synthon is between 1 mmol/L-10 mmol/L according to the reactivity of different substrates.

4. The method for preparing the organic polyspiralgrid nanopolymer material of claim 3, wherein the Lewis acids and protonic acids are one or a combination of several of the following acids: acetic acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, methanesulfonic acid, fluoromethylsulfonic acid, trifluoromethanesulfonic acid, concentrated sulfuric acid, trifluoroacetic acid and hydrofluoric acid-antimony pentafluoride.

5. The method for preparing the organic polyspiralgrid nanopolymer material of claim 2, wherein the dry organic solvent is one of the following solvents: dichlorobenzene, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane, nitrobenzene, acetone, tetrahydrofuran and 1,4-dioxane.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1a. Proton spectrum of organic bispiralgrid 4a;

(2) FIG. 1b. Mass spectrum of organic bispiralgrid 4a,

(3) FIG. 2a. Proton spectrum of organic polyspiralgrid nanopolymer 5a;

(4) FIG. 2b. Gel chromatogram of organic polyspiralgrid nanopolymer 5a,

(5) FIG. 3. TEM spectrum of organic polyspiralgrid nanopolymer 5a,

(6) FIG. 4a. Ultraviolet absorption and fluorescence emission spectra of organic bispiralgrid 4a and organic polyspiralgrid nanopolymer 5a solutions:

(7) FIG. 4b. Absorption emission spectra of thin films of organic bispiralgrid 4a and organic polyspiralgrid nanopolymer 5a,

(8) FIG. 5a. TG spectrum of organic polyspiralgrid nanopolymer 5a:

(9) FIG. 5b. DSC spectrum of organic polyspiralgrid nanopolymer 5a,

(10) FIG. 6a. CV spectrum of organic bispiralgrid 4a;

(11) FIG. 6b. CV spectrum of organic polyspiralgrid nanopolymer 5a.

DETAILED DESCRIPTION OF THE INVENTION

(12) The present invention relates to a type of organic mono-spiralgrid as well as its nanopolymer materials, in which the specific structural formula and reaction route of organic mono-spiralgrid are as follows:

(13) ##STR00008##

(14) Wherein: R.sub.1 is a common alkyl chain, including: 1) straight chains: a hydrogen atom, alkane chains, alkoxy chains, or alkane chains introducing halogen atoms onto the terminals, such as fluorine, chlorine and bromine; 2) branched chains: tert-butyl chains and branched alkyl chains with oxygen atoms; wherein, m is a natural number ranging from 1 to 10. Their specific structures are as follows:

(15) ##STR00009##
are common fluorene-like spiral ring compounds. Their specific structures are as follows:

(16) ##STR00010##

(17) wherein, the related alkyl chain R′ can also be introduced on the nitrogen atom, and n′ is a natural number ranging from 1 to 10. Their specific structures are as follows:

(18) ##STR00011##
is one of the following structures:

(19) ##STR00012##

(20) The acid includes Lewis acids and protonic acids. It is the combination of one or several of the following acids: acetic acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, methanesulfonic acid, fluoromethylsulfonic acid, trifluoromethanesulfonic acid, concentrated sulfuric acid, trifluoroacetic acid or hydrofluoric acid-antimony pentafluoride. The amount of acid catalyst added in the reaction is 2-5 times that of A1B1-type synthon according to the reactivity of different substrates.

(21) The solvent is a dry organic solvent, which is specifically one of the following solvents: dichlorobenzene, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane, nitrobenzene, acetone, tetrahydrofuran and 1,4-dioxane. The reaction concentration of A1B1-type synthon is between 1 mmol/L-10 mmol/L according to the reactivity of different substrates.

(22) The specific synthesis steps of the above-mentioned organic mono-spiralgrid are as follows: Take a fixed amount of acid and add it into a round bottom flask containing a fixed amount of dry organic solvent; fully dissolve the spiral ring-containing A1B1-type synthon-1 in another part of dry organic solvent and add it dropwise into the round bottom flask at a rate of 1 drop per second; stir the reaction for 24 h until the reaction substrate is completely reacted, and then add water to quench the neutralization reaction. Extract the resulted mixture solution with dichloromethane, put dichloromethane extracts in the organic phase together, dry them with anhydrous magnesium sulfate, filter off the desiccant, and remove the solvent with vacuum distillation. Separate the crude product through a silica gel chromatography column to obtain the corresponding target product: organic mono-spiralgrid-2.

(23) Its organic bispiralgrid structure as well as its reaction route are as follows:

(24) ##STR00013##

(25) Wherein, R.sub.1 and R.sub.2 are identical or different, and they are common alkyl chains, including 1) straight chains: a hydrogen atom, alkane chains, alkoxy chains, or alkane chains introducing halogen atoms onto the terminals, such as fluorine, chlorine and bromine; 2) branched chains: tert-butyl chains and branched alkyl chains with oxygen atoms; wherein, m is a natural number ranging from 1 to 10. Their specific structures are as follows:

(26) ##STR00014##
are identical or different and are common fluorene-like spiral ring compounds. Their specific structures are as follows:

(27) ##STR00015##

(28) wherein, the related alkyl chain R′ can also be introduced on the nitrogen atom, and n′ is a natural number ranging from 1 to 10. Their specific structures are as follows:

(29) ##STR00016##
identical or different and are one of the following structures:

(30) ##STR00017##

(31) The acid includes Lewis acids and protonic acids. It is the combination of one or several of the following acids: acetic acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, methanesulfonic acid, fluoromethylsulfonic acid, trifluoromethanesulfonic acid, concentrated sulfuric acid, trifluoroacetic acid or hydrofluoric acid-antimony pentafluoride. The amount of acid catalyst added in the reaction is 2-5 times that of A1B1-type synthon according to the reactivity of different substrates.

(32) The solvent is a dry organic solvent, which is specifically one of the following solvents: dichlorobenzene, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane, nitrobenzene, acetone, tetrahydrofuran and 1,4-dioxane. The reaction concentration of A1B1-type synthon is between 1 mmol/L-10 mmol/L according to the reactivity of different substrates.

(33) The specific synthesis steps of the above-mentioned organic polyspiralgrid are as follows: Take a fixed amount of acid and add it into a round bottom flask containing a fixed amount of dry organic solvent; fully dissolve the spiral ring-containing A2B2-type synthon-3 in another part of dry organic solvent and add it dropwise into the round bottom flask at a rate of 1 drop per second, and stir the reaction for 1 h-4 h; fully dissolve the spiral ring-containing A1B1-type synthon-1 in another part of dry organic solvent and add it dropwise into the round bottom flask at a rate of 1 drop per second, and stir the reaction for 24 h; then treat the resulted solution with vacuum distillation to remove the solvent until the solution is left to 5 ml, precipitate the remaining solution with methanol, and then extract it with acetone; and take out the solid portion from the mixture and dry it to obtain the corresponding target product: organic polyspiralgrid nanopolymer-5.

(34) The technical solution of the present invention is further described below with reference to the embodiment cases, but these embodiment cases are not limited to the embodiment mode of the present invention. The present invention has several different embodiment modes and is not limited to what is described in this specification. Without departure from the spirit of the present invention, all the schemes devised by technicians in the field should be within the scope of the present invention.

Embodiment Case 1: Preparation of Organic Mono-Spiralgrid-2a

(35) ##STR00018##

(36) Add boron trifluoride ether solution (1 ml) and 400 ml 1,2-dichloroethane to a 1000 ml reaction flask, and stir the mixture evenly; add 1a (0.353 g, 0.5 mmol, 1 equiv) into a constant-pressure dropping funnel containing 100 ml 1,2-dichloroethane, and then add the resulted solution dropwise to the reaction bottle at a rate of one drop per second. After the dropwise addition, the reaction goes on for 5-10 hours. After the reaction is completed, water is added into the reaction solution to quench the reaction. Extract the resulted mixture solution with dichloromethane, put dichloromethane extracts in the organic phase together, dry them with anhydrous magnesium sulfate, filter off the desiccant, and remove the solvent with vacuum distillation. Separate and purify the crude product through a silica gel chromatography column to obtain white solid powder 2a (0.151 g, 43.9%).

(37) .sup.1H NMR (400 MHz, CDCl.sub.3) δ7.77-7.73; (t, J=7.8 Hz, 4H), 7.66-7.64; (d, J=7.6 Hz, 4H), 7.57-7.52; (t, J=8.0 Hz, 4H), 7.48-7.46; (d, J=8.0 Hz, 2H), 7.42-7.40; (d, J=7.6 Hz, 2H), 7.37-7.36; (m, 5H), 7.34-7.28; (m, 6H), 7.24-7.21; (m, 5H), 7.14-7.10; (t, J=7.2 Hz, 2H), 7.02-6.98; (t, J=7.4, 2H), 6.89-6.87; (d, J=7.6 Hz, 2H), 6.79-6.72; (d, J=8.8 Hz, 4H), 6.65-6.62; (d, J=8.0 Hz, 4H), 3.89-3.86; (t, J=6.5 Hz, 4H), 1.80-1.73; (m, 4H), 1.46-1.42; (t, J=6.0 Hz, 4H), 1.30-1.27; (m, 16 H), 0.91-0.89; (t, J=4.4 Hz, 6H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 158.3, 154.8, 152.0, 151.3, 150.8, 148.6, 147.6, 147.3, 145.9, 141.3, 141.1, 140.8, 140.2, 139.3, 139.3, 138.6, 137.8, 128.3, 128.1, 127.9, 127.8, 127.6, 127.4, 126.9, 126.8, 126.1, 125.7, 124.6, 124.4, 123.4, 122.5, 120.2, 120.1, 120.0, 119.2, 117.7, 114.2, 67.9, 64.0, 62.1, 31.9, 31.5, 31.5, 30.3, 30.2, 30.2, 29.7, 29.7, 29.4, 29.3, 26.2, 22.7, 14.2. MALDI-TOF-MS (m/z): 1377.70/1377.55 [M.sup.+].

Embodiment Case 2: Preparation of Organic Bispiralgrid-4a

(38) ##STR00019##

(39) wherein, R=OC.sub.8H.sub.17.

(40) Add boron trifluoride ether solution (1 ml) and 400 ml 1,2-dichloroethane (DCE) to a 1000 ml reaction flask, and stir the mixture evenly; add 1a (0.353 g, 0.5 mmol, 1 equiv) and 3a (0.274 g, 0.25 mmol, 0.5 equiv) into a constant-pressure dropping funnel containing 100 ml 1,2-dichloroethane and mix them evenly until they are completely dissolved, and then add the resulted solution dropwise to the reaction bottle at a rate of one drop per second. After the dropwise addition, the reaction goes on for 5-10 hours. After the reaction is completed, water is added into the reaction solution to quench the reaction. Extract the resulted mixture solution with dichloromethane, put dichloromethane extracts in the organic phase together, dry them with anhydrous magnesium sulfate, filter off the desiccant, and remove the solvent with vacuum distillation. Separate and purify the crude product through a silica gel chromatography column to obtain yellowish solid powder 4a (0.040 g, 6.54%).

(41) .sup.1H NMR (400 MHz, CDCl.sub.3) δ7.74-7.72; (d, J=8.0 Hz, 2H), 7.70-7.68; (d, J=7.6 Hz, 2H), 7.67-7.64; (d, J=8.0 Hz, 4H), 7.63-7.61; (d, J=8.0 Hz, 2H), 7.59-7.57; (m, 6H), 7.56-7.54; (m, 6H), 7.54-7.51; (d, J=6.4 Hz, 4H), 7.50-7.46; (m, 6H), 7.42-7.40; (d, J=8.8 Hz, 4H), 7.36-7.35; (d, J=2.8 Hz, 2H), 7.32-7.30; (d, J=6.8 Hz, 4H), 7.29-7.28; (m, 4H), 7.16-7.14; (d, J=7.2 Hz, 2H), 7.13; (s, 2H), 7.10-7.07; (d, J=8.4, 2.8 Hz, 4H), 7.06-7.04; (d, J=8.0 Hz, 2H), 6.97 (s, 2H), 6.93-6.89 (m, 8H), 6.83-6.81 (d, J=7.6 Hz, 4H), 6.79-6.77 (d, J=9.2 Hz, 4H), 6.59-6.57; (d, J=8.8 Hz, 2H), 3.91-3.88; (t, J=5.8 Hz, 8H), 2.31-2.21; (m, 4H), 2.06-1.97; (m, 4H), 1.79-1.70; (m, 8H), 1.30-1.29; (m, 32H), 0.86-0.83; (m, 12H). MALDI-TOF-MS (m/z): 2438.99/2439.00 [M.sup.+].

Embodiment Case 3: Preparation of Organic Polyspiralgrid Nanopolymer-5a

(42) ##STR00020##

(43) wherein, R=OC.sub.8H.sub.17.”

(44) At room temperature, take a certain amount of 3a (0.329 g, 0.3 mmol) and dissolve it in 20 ml DCE and then add it dropwise to 40 ml DCE dissolved with boron trifluoride ether solution (0.78 ml, 3 mmol) at a dropping rate of 1 drop per second. After the dropwise addition is completed, the reaction system is stirred for 1-4 hours. Subsequently, 10 ml DCE solution dissolved with 1a (0.021 g, 0.03 mmol) is added dropwise to the reaction system at a dropping rate of 1 drop per second. After the addition is complete, the reaction goes on for 24 hours. After the reaction is completed, the solvent is directly removed with rotary evaporation until 5 ml of the reaction solution is left. The remaining solution is then settled with methanol and filtered. The residue is extracted with acetone in a Soxhlet extractor to obtain a brown product (0.304 g, yield rate 89.8% (the theoretical yield 0.3386 g)).

Embodiment Case 4: Test the Basic Optical, Electrical and Thermal Properties of Organic Mono-Spiralgrid (2a), Organic Bispiralgrid (4a) and Organic Polyspiralgrid Nanopolymer (5a)

(45) A certain amount of sample is taken from each of the three materials and dissolved into a certain amount of dichloromethane (DCM) to form a 10.sup.−5 mg/mL DCM dilute solution. Shimadzu UV-3150 UV-visible spectrometer and RF-530XPC fluorescence spectrometer are used to measure the absorption spectrum and emission spectrum of the solution. The photoluminescence spectrum of the solution is measured at the ultraviolet (UV) wavelength at which the solution has the maximum UV absorption. The solid film is prepared with the solution spin-coating film forming technology, and the spin-coating solution is a 10 mg/mL chloroform solution. Shimadzu DTG-60H is used for thermogravimetric analysis, and Shimadzu DSC-60A is used for differential scanning thermal analysis. Electrochemical tests are performed with the cyclic voltammetry (CV) through the CHI660E system at room temperature. The typical three-electrode system composed of a working electrode, a platinum wire electrode and a silver nitrate electrode is used in the tests. All the electrochemical tests are performed in a nitrogen atmosphere. The sample is dropped on a glassy carbon electrode to form film on the electrode. After the film is air-dried, the electrode is inserted into tetrabutylammonium hexafluorophosphate (0.1 mol/L)/acetonitrile for testing. The scanning rate is 0.1 V/s. According to the redox starting potential of the CV measurement, the highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) ratio of the materials is calculated based on the reference energy level of ferrocene (4.8 eV lower than vacuum): HOMO/LUMO=−(E.sub.ox/red−0.03 V)−4.8 eV, where 0.03 V is the standard potential difference of ferrocene relative to Ag/Ag.sup.+.