Preparation method of non-conjugated dehydrated polymer and polymer prepared thereby

Abstract

The invention discloses a preparation method of a non-conjugated dehydrated polymer and a polymer prepared by the preparation method. Comprising the following steps: mixing polycarboxylic acid and polyamine, reacting, and drying to obtain the non-conjugated dehydrated polymer, the polycarboxylic acid is selected from at least one of oxalic acid, tricarboxylic acid, succinic acid, 1, 2, 4-butane tricarboxylic acid, 1, 2, 3.4-butane tetracarboxylic acid, glutaric acid, adipic acid and 1, 2, 4, 5-cyclohexane tetracarboxylic acid; the polyamine is selected from at least one of ethylenediamine, propane triamine, 1, 3-propane diamine and phenylenediamine; the reaction temperature is 80-260 DEG C; the atmosphere is an inert gas atmosphere. By using an inert gas purging melt polymerization method, side reactions induced by water or other low-molecular-weight intermediate products generated in a polycondensation process can be inhibited, and by-products in a final product are greatly reduced. The preparation process difficulty can be greatly reduced and the yield of the product can be effectively improved by utilizing a dispersion-precipitation method.

Description

Technical Field

[0001] The present application relates to a method for preparing a non-conjugated dehydrated polymer and the polymer prepared therefrom, and belongs to the field of functional polymers. Background Art

[0002] Self-assembly refers to the phenomenon and process in which building blocks such as small organic molecules, polymers, biomacromolecules and nanoparticles spontaneously form ordered structures under non-covalent interactions. The blocks are connected in order through non-covalent bonds to form assemblies with specific structures or functions. It is an important means to create new substances and generate new functions. It follows the principle of minimum energy, and for open, highly active systems far from equilibrium, it may obey the principle of dissipative structure. The synergistic effect of the weak interaction forces of countless non-covalent bonds on the spontaneous formation of molecules is the key to self-assembly. Not all molecules can undergo the self-assembly process, and its generation requires two conditions: the power of self-assembly and the guiding role. The application in nanotechnology is mainly concentrated in the preparation of nano-mesoporous materials, nanotubes, and nanoparticles. These new materials play an important role in biology, physics, chemistry, materials, medicine, information and other fields. Therefore, the development of new self-assembly functional elementary materials has received more and more attention from researchers in various countries.

[0003] Conventional organic fluorescent self-assembly materials are mostly based on the self-assembly process driven by different intermolecular forces between primitives with conjugated structures, but the presence of conjugated structures will greatly enhance the π-π stacking effect and induce fluorescence quenching. Based on the presence of non-conjugated structures, it is difficult to produce fluorescence or the fluorescence is weak. Summary of the invention

[0004] The inventors utilized the weak fluorescence phenomenon generated by the electron delocalization of the excited state of rigid oligoamide or oligoimide, and designed hydrogen bonding to achieve self-assembly of non-conjugated oligoamide / imide driven by intermolecular forces such as hydrogen bonding. The oligoamide / imide prepared based on the scheme of the present invention has the characteristics of high product yield, concentration-adjusted self-assembly size and fluorescence properties, and has good application prospects.

[0005] According to one aspect of the present application, a method for preparing a non-conjugated dehydrated polymer is provided, comprising the following steps:

[0006] Mixing polycarboxylic acid and polyamine, reacting, and drying to obtain the non-conjugated dehydrated polymer;

[0007] The polycarboxylic acid is selected from at least one of oxalic acid, trisaccharic acid, succinic acid, 1,2,4-butanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, glutaric acid, adipic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid;

[0008] The polyamine is selected from at least one of ethylenediamine, propanetriamine, 1,3-propylenediamine and phenylenediamine;

[0009] The reaction temperature is 80-260°C;

[0010] The reaction atmosphere is an inert gas atmosphere.

[0011] The molar ratio of the polycarboxylic acid to the polyamine is 1:10 to 10:1.

[0012] The reaction is a melt polymerization reaction.

[0013] The reaction time is 0.5 to 6 hours.

[0014] The inert gas atmosphere is selected from at least one of nitrogen, helium and argon.

[0015] Specifically,

[0016] (1) Alkane polycarboxylic acid benzene and polyamino compound are mixed and reacted by melt polymerization under the condition of inert gas purge.

[0017] (2) By controlling the reaction time, a polyamide or polyimide product with a low molecular weight is generated.

[0018] (3) After the reaction is completed, the unreacted precursor or impurities in the product are removed by a dispersion-reprecipitation method, and the product is filtered and dried to obtain a low molecular weight dehydrated polymer with self-assembled fluorescence enhancement properties.

[0019] The solvent used in the dispersion-reprecipitation method is selected from at least one of dimethyl sulfoxide-water, dimethyl sulfoxide-ethanol, methanol-trichloroform, ethanol-toluene, and acetone-n-hexane.

[0020] The yield of the above method is 60-95%.

[0021] According to another aspect of the present application, a non-conjugated dehydrated polymer prepared by the above-mentioned preparation method is provided, wherein the molecular weight of the non-conjugated dehydrated polymer is 1000-15000 Da.

[0022] The beneficial effects of this application include:

[0023] (1) The melt polymerization method using inert gas purge can inhibit the side reactions induced by water or other low molecular weight intermediates produced during the polycondensation process, thereby significantly reducing the by-products in the final product.

[0024] (2) The use of the dispersion-precipitation method can greatly reduce the difficulty of the preparation process and effectively improve the yield of the product.

[0025] (3) The fluorescence intensity and particle size of the prepared product can be regulated by the concentration in the dispersed system.

[0026] (4) The fluorescence behavior of the product can be controlled by adjusting the precursor ratio. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is the 1H-NMR spectrum of the product in Example 2.

[0028] Figure 2 The ESI mass spectrum of the product in Example 1.

[0029] Figure 3 This is the concentration-dependent fluorescence spectrum of the product in Example 1.

[0030] Figure 4 a, b, c, and d are transmission electron micrographs of the product in Example 1, wherein the scales of a and c are 50 nm, the scale of b is 10 nm, and the scale of d is 20 nm.

[0031] Figure 5 This is a scanning transmission electron microscope image of the product in Example 1, with a scale of 50 nm. DETAILED DESCRIPTION

[0032] The present invention will be further described below in conjunction with embodiments so that those skilled in the art can better understand the present invention, but the present invention is not limited thereto.

[0033] Example 1

[0034] At room temperature, 1 mol of oxalic acid and 1 mol of 1,3-propylenediamine were weighed and mixed and transferred to a muffle furnace, heated to 180°C under the condition of passing inert gas, and cooled to room temperature after 3 hours of reaction. The obtained product was dispersed in 10 mL of methanol, and then 50 mL of chloroform was added. The obtained precipitate was filtered and dried to obtain a low molecular weight non-conjugated dehydrated polymer with self-assembled fluorescence enhancement properties, and the solid powder yield was 75%.

[0035] Figure 3 : This is the concentration-dependent fluorescence spectrum of the product in Example 1. It can be seen from the figure that the fluorescence intensity increases with the increase of polymer concentration.

[0036] Figure 4 a, b, c, and d are transmission electron micrographs of the product in Example 1, wherein the scales of a and c are 50 nm, the scale of b is 10 nm, and the scale of d is 20 nm. It can be seen from the figure that the sizes of nanoparticles formed by the oligomers at different concentrations are different, indicating that the oligomers have self-assembly properties.

[0037] Figure 5This is a scanning transmission electron microscope image of the product in Example 1, with a scale of 50 nm. It can be seen from the figure that the nanoparticles are relatively uniformly dispersed at 5 mg / mL, and the average particle size is similar to that of TEM. Figure 4 c, d are similar.

[0038] Example 2

[0039] At room temperature, 1.0 mol of trisaccharide and 1.2 mol of phenylenediamine were weighed and mixed and transferred to a muffle furnace, heated to 200°C under the condition of passing inert gas, reacted for 2 hours and then cooled to room temperature. The obtained product was dispersed in 10 mL of dimethyl sulfoxide, and then 50 mL of ethanol was added. The obtained precipitate was filtered and dried to obtain a low molecular weight non-conjugated dehydrated polymer with self-assembled fluorescence enhancement characteristics, and the solid powder yield was 85%.

[0040] Figure 1 This is the 1H-NMR spectrum of the product in Example 2. It can be seen from the figure that the product has an amide structure

[0041] Figure 2 This is the ESI mass spectrum of the product in Example 1. It can be seen from the figure that the product is a polymer, and the ion fragment peak shows that the cyclic unit is C 12 H 12 N2O4.

[0042] Example 3

[0043] At room temperature, 1.2 mol of glutaric acid and 1.0 mol of phenylenediamine were weighed and mixed and transferred to a muffle furnace, heated to 230°C under the condition of passing inert gas, reacted for 3 hours and then cooled to room temperature. The obtained product was dispersed in 3 mL of dimethyl sulfoxide, and then 30 mL of ethanol was added. The obtained precipitate was filtered and dried to obtain a low molecular weight non-conjugated dehydrated polymer with self-assembled fluorescence enhancement properties, and the solid powder yield was 80%.

[0044] Example 4

[0045] At room temperature, 1.0 mol of succinic acid and 1.0 mol of ethylenediamine were weighed and mixed and transferred to a muffle furnace, heated to 250°C under the condition of passing inert gas, reacted for 2.5 hours, and then cooled to room temperature. The obtained product was dispersed in 10 mL of ethanol, and then 50 mL of toluene was added. The obtained precipitate was filtered and dried to obtain a low molecular weight non-conjugated dehydrated polymer with self-assembled fluorescence enhancement characteristics, and the solid powder yield was 82%.

[0046] Example 5

[0047] At room temperature, 1.0 mol of 1,2,4-butanetricarboxylic acid and 1.5 mol of phenylenediamine were weighed and mixed and transferred to a muffle furnace, heated to 230°C under the condition of passing inert gas, reacted for 2 hours and then cooled to room temperature. The obtained product was dispersed in 5 mL of dimethyl sulfoxide, and then 30 mL of water was added. The obtained precipitate was filtered and dried to obtain a low molecular weight non-conjugated dehydrated polymer with self-assembled fluorescence enhancement properties, and the solid powder yield was 78%.

[0048] Example 6

[0049] 1.0 mol of 1,2,3.4-butanetetracarboxylic acid and 1.2 mol of propanetriamine were weighed and mixed at room temperature and transferred to a muffle furnace. The mixture was heated to 200°C under the condition of passing inert gas, and cooled to room temperature after reacting for 3 hours. The obtained product was dispersed in 5 mL of acetone, and then 30 mL of n-hexane was added. The obtained precipitate was filtered and dried to obtain a low molecular weight non-conjugated dehydrated polymer with self-assembled fluorescence enhancement characteristics, and the solid powder yield was 73%.

[0050] Example 7

[0051] At room temperature, 1.0 mol of adipic acid and 1.0 mol of ethylenediamine were weighed and mixed and transferred to a muffle furnace, heated to 180°C under the condition of passing inert gas, reacted for 3 hours and then cooled to room temperature. The obtained product was dispersed in 5 mL of dimethyl sulfoxide, and then 30 mL of water was added. The obtained precipitate was filtered and dried to obtain a low molecular weight non-conjugated dehydrated polymer with self-assembled fluorescence enhancement properties.

[0052] Example 8

[0053] At room temperature, 1.0 mol of 1,2,4,5-cyclohexanetetracarboxylic acid and 1.0 mol of phenylenediamine were weighed and mixed and transferred to a muffle furnace, heated to 200°C under the condition of passing inert gas, reacted for 2.5 hours and then cooled to room temperature. The obtained product was dispersed in 5 mL of dimethyl sulfoxide, and then 50 mL of ethanol was added. The obtained precipitate was filtered and dried to obtain a low molecular weight non-conjugated dehydrated polymer with self-assembled fluorescence enhancement characteristics, and the solid powder yield was 83%.

[0054] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing a non-conjugated dehydrated polymer, characterized in that: The following steps are involved: Mixing polycarboxylic acid and polyamine, reacting, and drying to obtain the non-conjugated dehydrated polymer; The polycarboxylic acid is selected from at least one of oxalic acid, trisaccharic acid, succinic acid, 1,2,4-butanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, glutaric acid, adipic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid; The polyamine is selected from at least one of ethylenediamine, propanetriamine, 1,3-propylenediamine and phenylenediamine; The reaction temperature is 80-260°C; The reaction atmosphere is an inert gas atmosphere.

2. The preparation method according to claim 1, characterized in that: The molar ratio of the polycarboxylic acid to the polyamine is 1:10 to 10:

1.

3. The preparation method according to claim 1, characterized in that: The reaction is a melt polymerization reaction.

4. The preparation method according to claim 1, characterized in that: The reaction time is 0.5 to 6 hours.

5. The preparation method according to claim 1, characterized in that: The inert gas atmosphere is selected from at least one of nitrogen, helium and argon.

6. A non-conjugated dehydrated polymer prepared by the preparation method according to any one of claims 1 to 5, characterized in that: The molecular weight of the non-conjugated dehydrated polymer is 1000-15000 Da.

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