CN112048049A - Luminescent polymer and preparation method and application thereof - Google Patents

Abstract

A nitrogen hydroxyl/amino based polyureaurethane prepared from the reaction of at least one nitrogen hydroxyl/amino compound, at least one aliphatic polyisocyanate, and at least one aliphatic polyamine. The molecular structure of the nitrogen hydroxyl/amino-based polyureaurethane is an aliphatic chain, and the rigidity is improved compared with the existing luminous polymer. In addition, the film prepared by the polymer has good transparency; the polymer has photoluminescence performance, and the fluorescence quantum yield is 40-60%. The film prepared by the polymer can effectively block light below 450nm and has the transmittance equivalent to that of glass at other wavelengths. This indicates that the film has the potential to be a high transmission uv resistant coating. Finally, the polymers of the invention also have thermoreversible properties, and can be reversibly decomposed under heating to give the starting materials.

Description

A kind of light-emitting polymer and its preparation method and application

technical field

The invention belongs to the technical field of polymer material preparation, and particularly relates to a light-emitting polymer and a preparation method and application thereof.

Background technique

Optoelectronic functional polymers are a vibrant and important branch in the field of polymer science research. Among them, light-emitting polymer materials have application value in many fields such as LED light diffusion materials, white light LED materials, anti-counterfeiting materials, fluorescent inks, fluorescent dyes, solar cell light conversion films, and biological detection. According to the structure and luminescence characteristics of organic compounds, the above-mentioned luminescent polymer materials can be divided into two categories: aggregated fluorescence quenching (ACQ) and aggregation-induced emission (AIE). Both traditional organic fluorescent compounds and typical AIE organic fluorescent compounds contain large conjugated structures such as aromatic rings or aromatic heterocycles in their molecules, and these conjugated structures are necessary conditions for their fluorescence emission. However, such fluorescent compounds are difficult to prepare in large quantities, poor in material transparency, and high in rigidity. The poor optical properties limit the application of such materials in many fields.

SUMMARY OF THE INVENTION

In order to improve the problems in the prior art, the present invention provides a nitroxyl/amino-based polyurea urethane, the nitroxyl/amino-based polyurea urethane is composed of at least one nitrox/amino compound, at least one Prepared by the reaction of an aliphatic polyisocyanate and at least one aliphatic polyamine.

According to an embodiment of the present invention, the nitrogen hydroxyl/amino compound is selected from the following compounds:

According to an embodiment of the present invention, the aliphatic polyisocyanate has the structure shown in formula I:

Wherein, A represents the core part of aliphatic polyisocyanate, selected from substituted or unsubstituted C _1-12 alkylene, substituted or unsubstituted C _3-20 cycloalkylene, and the substitution is an inert substitution; y is 2 An integer between ~10.

Preferably, y is an integer between 2-8; also preferably, y is an integer between 2-6.

Preferably, A is selected from the following groups: substituted or unsubstituted C _1-10 alkylene, substituted or unsubstituted C _3-12 cycloalkylene; the substitution is an inert substitution.

More preferably, the aliphatic polyisocyanate is selected from 1,6-hexamethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, isophorone diisocyanate (IPDI), 1,4-cyclic diisocyanate At least one of hexane diisocyanate, cyclohexane dimethylene diisocyanate, norbornane diisocyanate, hexamethylene diisocyanate trimer, and isophorone diisocyanate trimer.

According to an embodiment of the present invention, the aliphatic polyamine is selected from difunctional and/or trifunctional organic amines.

According to an embodiment of the present invention, the bifunctional organic amine is selected from ethylenediamine, diaminodicyclohexylmethane, 1,4-butanediamine, dimethylthiodiamine or bifunctional polyetheramine.

According to an embodiment of the present invention, the molecular weight of the bifunctional polyetheramine is 50-20000, such as 500-15000, 1000-10000, 1200-8000, 3000-5000.

Preferably, the bifunctional polyetheramine is selected from at least one of polyetheramine D230, polyetheramine D400, and polyetheramine D2000.

According to an embodiment of the present invention, the trifunctional organic amine is selected from the group consisting of amine terminated trifunctional polyether D230, amine terminated trifunctional polyether D400, amine terminated trifunctional polyether D1000, amine terminated trifunctional polyether Ether D2000.

The nitroxyl/amino-based polyureaurethane of the present invention has thermal reversibility, is relatively stable at room temperature, and can spontaneously dissociate into raw materials when the temperature rises above 90°C.

According to an embodiment of the present invention, the molar ratio of the nitrogen hydroxyl/amino compound, the aliphatic polyisocyanate and the aliphatic polyamine is 1:(8-12):(0.1-9), preferably 1:(9 -11): (0.1 to 9).

According to an embodiment of the present invention, the solid content of the nitroxyl/amino-based polyureaurethane is 10-50 wt %, preferably 20-40 wt %.

According to an embodiment of the present invention, the number average molecular weight of the nitroxyl/amino-based polyureaurethane is 1×10 ⁴ -5×10 ⁶ g/mol, preferably 2×10 ⁴ -1×10 ⁵ g/ mol.

Preferably, the nitroxyl/amino-based polyureaurethane is a random copolymer or a block copolymer.

Preferably, the nitroxyl/amino-based polyurea urethane is composed of polyetheramine (eg, at least one of polyetheramine D230, polyetheramine D400, polyetheramine D2000, trifunctional polyether D230), 4 - ANOP and IPDI polymers prepared by polymerization.

Preferably, the nitroxyl/amino-based polyureaurethane is a thermoplastic or thermosetting polyureaurethane.

According to an embodiment of the present invention, the nitroxyl/amino-based polyureaurethane has photoluminescence properties.

Further, the solution and solid of the nitroxyl/amino-based polyureaurethane of the present invention both have photoluminescence properties.

Further, the solution and solid fluorescence quantum yield of the nitroxyl/amino-based polyurea urethane of the present invention is 40-60%.

The present invention also provides the above-mentioned preparation method of the polyurea urethane based on nitroxyl/amino group, comprising the following steps:

The polymerization is carried out by mixing at least one nitroxyl/amino compound, at least one aliphatic polyisocyanate and at least one aliphatic polyamine in a solvent.

According to an embodiment of the present invention, the molar ratio of the nitrogen hydroxyl/amino compound, the aliphatic polyisocyanate and the aliphatic polyamine is 1:(8-12):(0.1-9), preferably 1:(9 -11): (0.1 to 9).

According to a preferred embodiment of the present invention, the polymer is prepared by uniformly dispersing a polyisocyanate, a nitroxyl/amino compound, a diamine compound and/or a triamine compound in an organic solvent , stir evenly, and obtain polymer solution after full reaction.

As an example, 4-ANOP, dipolyetheramine (polyetheramine D230, or polyetheramine D400, or polyetheramine D2000), and IPDI are uniformly dispersed in the organic solvent DMAc, stirred uniformly, and fully reacted to obtain a polymer solution.

As an example, the molar ratios are 180:3:15.7:180, 172:4.5:15.7:172, 164:14.75:15.7:164, 360:5.75:20:100, 320:11.7:20:100, 280:17.5 : 20:100 dibasic polyetheramine (polyetheramine D230, or polyetheramine D400, or polyetheramine D2000), three-terminal amino ether, 4-ANOP and IPDI are evenly dispersed in the organic solvent DMAc, stir evenly, After sufficient reaction, a polymer solution was obtained.

As an example, three-terminal amino ethers (amine-terminated trifunctional polyether D230, amine-terminated trifunctional polyether D400, amine-terminated trifunctional polyether D1000, amine-terminated trifunctional polyether D2000), 4-ANOP and IPDI are uniformly dispersed in the organic solvent DMAc, stirred uniformly, and fully reacted to obtain a polymer solution.

According to an embodiment of the present invention, the solvent used in the above reaction is selected from alcohol-based solvents, halogenated alkane-based solvents, ketone-based solvents, ester-based solvents, ether-based solvents, amide-based solvents, sulfone-based solvents, aromatic hydrocarbon-based solvents or sulfur-containing solvents Solvent; for example, the solvent is selected from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, n-octanol, acetone, methyl ethyl ketone, chloroform, dichloromethane, diethyl ether, butyl ether , carbon disulfide, 1-methyl-2-pyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, DMAc, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, dioxygen One, two or more of hexacyclic, acetonitrile, benzene, toluene, or xylene.

According to an embodiment of the present invention, the temperature of the reaction is 0-80°C.

According to an embodiment of the present invention, the reaction time is 10 minutes to 24 hours.

Further, the present invention also provides a method for recycling and reusing the above-mentioned nitroxyl/amino-based thermosetting polyurea urethane, comprising: crushing the nitroxyl/amino-based thermosetting polyurea urethane, and heating and decomposing to obtain Raw materials for the preparation of polymers.

According to an embodiment of the present invention, the method of breaking up may be cutting the polyureaurethane into pieces.

According to an embodiment of the present invention, the heating temperature is above 80°C, for example, 80°C to 120°C, such as 90°C.

According to an embodiment of the present invention, the heating may be carried out at the same time as pressurization, and the pressure of the pressurization is 1-20 MPa, for example, 1-10 MPa, such as 5 MPa.

The present invention also provides the nitroxyl/amino-based polyureaurethane prepared by the above method.

The present invention also provides the use of the nitroxyl/amino-based polyurea urethane for preparing waterproof materials, anti-corrosion materials, medical appliances, anti-wear coatings and surface decoration materials, pipeline anti-corrosion coatings, and steel structure anti-corrosion coatings Layers, elastic anti-collision materials, automotive connectors (such as universal connectors), gastroscope hoses, medical hoses, fluorescent additives, fluorescent coatings, anti-ultraviolet coatings, solar cell packaging coatings, packaging adhesives, etc.

beneficial effect

(1) The molecular structure of the nitroxyl/amino group-based polyureaurethane of the present invention is an aliphatic chain, and the rigidity is improved compared to the existing light-emitting polymers. At the same time, the molecular structure of the polyurea urethane based on nitroxyl/amino group of the present invention also has thermal reversibility, and under heating conditions, the polymer can be decomposed reversibly to obtain raw materials.

(2) The polymer of the present invention has excellent photoluminescence properties, and its fluorescence does not change with the concentration; the fluorescence quantum yield is 40-60%. The film prepared by using the polymer of the present invention has good transparency, can effectively block light below 450 nm, and has a transmittance equivalent to that of glass at other wavelengths. This shows the potential of this film as a highly transparent UV-resistant coating.

(3) The preparation method of the polymer of the present invention is simple, and the raw materials can be reacted at room temperature to obtain a product without using a catalyst. Therefore, it is easy to prepare in large quantities and has broad application prospects.

(4) The thermosetting polymer of the present invention has better mechanical properties.

Definition and Explanation of Terms

Unless otherwise indicated, the numerical ranges recited in this specification and claims are equivalent to at least reciting each specific integer value therein. For example, the numerical range "2-6" corresponds to the description of each integer value in the numerical range "2-6", ie, 2, 3, 4, 5, and 6. It is to be understood that in the context of one, two or more used herein in describing a substituent, "more" shall refer to an integer > 3, such as 3, 4, 5, 6, 7, 8, 9 or 10 .

In this application, "multiple" or "multiple" means containing two or more functional groups.

The term "inert substitution" means that under the conditions of manufacture and storage, the substituent does not render the substituted group reactive with other components of the polyurethane reaction materials of the present invention. For example, the inertly substituted substituent may be selected from C _1-12 alkyl, C _3-20 cycloalkyl, alkyl carboxylate, carboxyl, hydroxyl, amino, and the like.

The term "C _1-12 alkylene" is to be understood as preferably denoting a straight-chain or branched saturated hydrocarbylene group having 1 to 12 carbon atoms, preferably a C _1-10 alkylene. "C _1-10 alkylene" is to be understood to preferably mean a straight-chain or branched saturated hydrocarbylene radical having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The alkylene groups are, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, isopropylidene, isobutylene, sec-butylene, tert-butylene, isopentyl. In particular, the group has 1, 2, 3, 4, 5, 6 carbon atoms ("C _1-6 alkylene"), eg methylene, ethylene, propylene, butylene.

The term "C _3-20 cycloalkylene" should be understood to mean a saturated monocyclic, bicyclic hydrocarbon ring or bridged ring having 3 to 20 carbon atoms, preferably "C _3-10 cycloalkylene". The term "C _3-10 cycloalkylene" is understood to mean a saturated monocyclic or bicyclic hydrocarbon ring having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The C _3-10 cycloalkylene group may be a monocyclic hydrocarbon group, such as cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene Or cyclodecyl, or a bicyclic hydrocarbon group such as a decalin ring.

Description of drawings

Fig. 1 is the process of preparing linear polyureaurethane in Example 1.

Figure 2 shows the infrared characterization results of polyurea urethane SL-0 and polymer SL-4 (polynitrocarbamate).

Figure 3 shows the NMR characterization results of polymer SL-4.

Figure 4 is a photo of SL-4 solutions with different concentrations under visible light and fluorescence.

Figure 5 is a photo of the SL-4 film and a fluorescence photo of the film.

Figure 6 shows the results of fluorescence spectrum characterization of the SL-4 thin film.

Figure 7 shows the UV-Vis spectral transmittance characterization results of SL-4 film (polynitrocarbamate), glass, and polyureaurethane.

Figure 8 shows the tensile properties test results of SC-4 and SC-8.

specific implementation

The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following examples are only for illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the intended protection scope of the present invention.

Unless otherwise stated, the starting materials and reagents used in the following examples are commercially available or can be prepared by known methods.

Preparation Example 1 Synthesis of Nitroxyl Compound 4-ANOP

Add 4-nitrophthalic anhydride (25g, 0.13mol) and isopropanol (250mL) to a 500mL two-necked flask, stir and dissolve, add hydroxylamine hydrochloride (8.9g, 0.13mol) and triethylamine (13g, 0.13mol), stirred and refluxed for 2 hours, the reaction solution was red, cooled to room temperature, a large amount of solid was precipitated, concentrated under reduced pressure, added 300 mL of water, stirred well, filtered, washed with water, and dried to obtain a white powder 4-nitro-N-hydroxyl Phthalamide (22.5 g, 84% yield);

Add 4-nitro-N-hydroxyphthalamide (5g, 24mmol) and 150mL anhydrous methanol into a 250mL single-necked flask, stir and dissolve, add 10% palladium carbon (0.5g), under a hydrogen pressure of 2atm , stirred at room temperature for 5 hours, the reaction system became dark green, the reaction solution was filtered to remove the palladium carbon, and the product adsorbed on the palladium carbon was eluted with hot tetrahydrofuran, the solvent was removed under reduced pressure to obtain a yellow solid, after the yellow solid was recrystallized ( It was dissolved in methanol under reflux, cooled to room temperature, and a large amount of yellow solid was precipitated, which was filtered to obtain yellow powder, which was dried) to obtain the target product 4-ANOP yellow powder (3.3 g, 78% yield).

Example 1: Preparation of Linear Polyureaurethane

The reaction process of linear polyureaurethane is shown in Figure 1. The specific operation steps are as follows: adding an appropriate amount of polyetheramine, 4-ANOP and solvent DMAc to a three-necked round-bottomed flask equipped with a mechanical stirrer, a condenser tube and a nitrogen passage. The reaction was carried out in a water bath maintained at 0°C. After the above-mentioned raw materials were thoroughly mixed, IPDI was added dropwise to the mixture to react for 30 minutes. The solid content of the final product solution was adjusted to be 30 wt% (the number average molecular weight and molecular weight distribution data of the raw materials and products used are shown in the table below).

For comparison, polyureaurethane (SL-0) was also prepared using the same protocol but without the addition of 4-ANOP starting material. The specific operation steps are as follows: adding an appropriate amount of polyetheramine and solvent DMAc into a three-necked round-bottomed flask equipped with a mechanical stirrer, a condenser tube and a nitrogen passage. The reaction was carried out in a water bath maintained at 0°C. After the above-mentioned raw materials were thoroughly mixed, IPDI was added dropwise to the mixture to react for 30 minutes. The solid content of the final product solution was adjusted to be 30 wt% (the number average molecular weight and molecular weight distribution data of the raw materials and products used are shown in the table below).

Example 2: Preparation of cross-linked polyurea urethane

The specific operation steps for preparing the cross-linked polyurea urethane are as follows: add an appropriate amount of polyetheramine, 4-ANOP, and amine-terminated trifunctional polyether to a three-necked round-bottomed flask equipped with a mechanical stirrer, a condenser tube and a nitrogen passage. D400 and solvent DMAc. The reaction was carried out in a water bath maintained at 0°C. After the above-mentioned raw materials were thoroughly mixed, IPDI was added dropwise to the mixture to react for 30 minutes. The solid content of the product solution was adjusted to 30 wt% (the data of the raw materials used are shown in the table below).

For comparison, cross-linked polyureaurethanes (SC-1 and SC-5) were also prepared using the same protocol but without the addition of 4-ANOP. The specific operation steps are as follows: adding an appropriate amount of polyetheramine, amine-terminated trifunctional polyether D400 and solvent DMAc into a three-necked round-bottomed flask equipped with a mechanical stirrer, a condenser tube and a nitrogen passage. The reaction was carried out in a water bath maintained at 0°C. After the above-mentioned raw materials were thoroughly mixed, IPDI was added dropwise to the mixture to react for 30 minutes. The solid content of the product solution was adjusted to 30 wt% (the data of the raw materials used are shown in the table below).

Example 3

In order to verify whether the polymers prepared in the above examples have dynamic reversibility, we designed and synthesized a polymer model prepared by the small molecule nitroxyl compound 4-ANOP and isocyanate IPDI for verification. The specific operation process is as follows: use the small molecule product obtained by the reaction of 4-ANOP and IPDI at room temperature, and then perform a temperature-variable nuclear magnetic test on the product in deuterated DMSO, from 25℃-50℃-70℃-80℃-90℃- 100°C-105°C-110°C-115°C-120°C was gradually heated up. From the analysis of the temperature-variable NMR results, we can know that the characteristic peaks of the raw materials appear obviously when the product is heated to about 90°C, which means that 4-ANOP and isocyanate IPDI are at room temperature. The product obtained by the following reaction can be reversibly returned to obtain the raw material 4-ANOP and isocyanate IPDI under the condition of increasing temperature. Therefore, it is proved that the polymers prepared in the above examples have thermal reversibility.

Test case 1:

Infrared Spectroscopy Test: The product polymers SL-4 and SL-0 were characterized using Perkin-Elmer 2000 FT-IR Fourier Transform Infrared Spectroscopy (FTIR). The resolution of the infrared detection instrument was 4 cm ^-1 , and the number of sample scans was 32 times. The samples were prepared by KBr (potassium bromide) pellet method for transmission infrared (TR) test. The detection result is as shown in Figure 2, and it can be seen from Figure 2 that the obtained product is the polyurea urethane based on the nitrogen hydroxyl group (the polynitroxide in Figure 2 is the detection result of SL-4, and the polyurea urethane is the detection of SL-0. result).

¹ HNMR test: Take the sample (polymer SL-4) in an amount of about 10 mg and dissolve it in d ₆ -DMSO. The instrument is Bruker's nuclear magnetic resonance spectrometer AV400, and the ¹ HNMR test is carried out. The test results are shown in Figure 3, which proves that The resulting product is a nitroxyl-based polyurea urethane.

Test case 2

Nitroxyl-based polyureaurethane (Polymer SL-4) polymer solutions were formulated at different concentrations ranging from 0.1 mg/mL to 100 mg/mL. The nitroxyl-based polyurea urethane polymer solution has fluorescence emission with a maximum excitation wavelength of 460 nm and a maximum emission wavelength of 500 nm. The detection results are shown in Figure 4. The color of the upper sample solutions in Figure 4 is light yellow. The color of the solution from left to right gradually becomes darker; the solutions in the lower row all emit green fluorescence, but the fluorescence color is not strong or weak. Different from other light-emitting polymers reported in the prior art, the polymer SL-4 solution is fluorescent at different concentrations and has a rather high quantum yield (>60%). In addition, Figure 4 also shows that the luminescence brightness of the polymer SL-4 solution is independent of the polymer concentration under the irradiation of a 365 nm UV lamp.

Test Example 3: Performance Test of Polynitroxide Film

The above-mentioned polymer sample SL-4 was prepared into a thin film, and the preparation process was film coating. Then the transparency and fluorescence properties of the film were tested, and the test results were shown in Figure 5 (the upper picture in Figure 5 is a transparent film, the pattern under the film can be seen, and the lower picture emits green fluorescence). It can be seen from FIG. 5 that the SL-4 prepared in the above-mentioned embodiment can be prepared into a transparent film, and the film emits green fluorescence when irradiated with light of 365 nm.

To test whether the above film has the ability to convert blue-violet light below 300nm-450nm into green light of 500nm, directly test the fluorescence spectrum of the film. The detection results are shown in FIG. 6 , and it can be seen from FIG. 6 that the above-mentioned thin film has the ability to convert blue-violet light below 300 nm to 450 nm into green light of 500 nm.

In order to evaluate the light transmittance of the above-mentioned films, we evaluated the films by UV-Vis absorption spectroscopy. The test process was carried out using ordinary glass, SL-0 and SL-4. It can be seen from FIG. 7 that the polymer sample SL-0 without the addition of the nitroxyl compound has the same transmittance curve as the glass. In contrast, the nitroxyl compound-based polyurea urethane film SL-4 can effectively block light below 450 nm, and has comparable transmittance to glass at other wavelengths. This shows the potential of this film as a highly transparent UV-resistant coating.

In order to test the mechanical properties of the cross-linked polyurea urethane prepared in Example 2, the tensile properties were tested in the following manner: an Instron3300 universal tensile testing machine was used, equipped with a 100kN sensor, a rectangular sample was used, and the effective gauge length was 20mm long × wide 3mm, the thickness is about 0.4-0.6mm, the stretching rate is 50mm·min ^-1 , and the temperature is 26°C. Extruded splines are cut by a pneumatic punch. Each group of experiments was repeated at least three times, and the average value was taken. The detection results of SC-4 and SC-8 are shown in Figure 8 (the upper part of the picture is the detection result of SC-4, and the lower part is the detection result of SC-8). It can be seen from Figure 8 that the two materials have good tensile properties.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. a polyurea urethane based on nitroxyl/amino is characterized in that, the polyurea urethane based on nitrox/amino is composed of at least one nitrox/amino compound, at least one aliphatic polyisocyanate and at least one An aliphatic polyamine is prepared by reaction. 2. The polyurea urethane based on nitroxyl/amino group according to claim 1, wherein the nitroxyl/amino compound is selected from the following compounds:

Preferably, the aliphatic polyisocyanate has the structure shown in formula I:

Wherein, A represents the core part of aliphatic polyisocyanate, selected from substituted or unsubstituted C _1-12 alkylene, substituted or unsubstituted C _3-20 cycloalkylene, and the substitution is an inert substitution; y is 2 an integer between ~10; More preferably, the aliphatic polyisocyanate is selected from 1,6-hexamethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, isophorone diisocyanate (IPDI), 1,4-cyclic diisocyanate At least one of hexane diisocyanate, cyclohexane dimethylene diisocyanate, norbornane diisocyanate, hexamethylene diisocyanate trimer, and isophorone diisocyanate trimer. 3. The nitroxyl/amino-based polyureaurethane of claim 1 or 2, wherein the aliphatic polyamine is selected from bifunctional and/or trifunctional organic amines; Preferably, the bifunctional organic amine is selected from ethylenediamine, diaminodicyclohexylmethane, 1,4-butanediamine, dimethylthiodiamine or bifunctional polyetheramine; Preferably, the molecular weight of the bifunctional polyetheramine is 50-20000, such as 500-15000, 1000-10000, 1200-8000, 3000-5000; Preferably, the bifunctional polyetheramine is selected from at least one of polyetheramine D230, polyetheramine D400, and polyetheramine D2000; Preferably, the trifunctional organic amine is selected from amine terminated trifunctional polyether D230, amine terminated trifunctional polyether D400, amine terminated trifunctional polyether D1000, and amine terminated trifunctional polyether D2000. 4. The nitroxyl/amino-based polyurea urethane according to any one of claims 1-3, wherein the solid content of the nitroxyl/amino-based polyurea urethane is 10-50 wt%; Preferably, the number-average molecular weight of the nitroxyl/amino-based polyureaurethane is 1×10 ⁴ to 5×10 ⁶ g/mol. Preferably, the nitroxyl/amino-based polyureaurethane is a random copolymer or a block copolymer. 5. the preparation method of the polyurea urethane based on nitroxyl/amino described in any one of claim 1-4, is characterized in that, comprises the steps: The polymerization is carried out by mixing at least one nitroxyl/amino compound, at least one aliphatic polyisocyanate and at least one aliphatic polyamine in a solvent. 6. preparation method according to claim 5 is characterized in that, comprises the steps: the mol ratio of described nitrogen hydroxyl/amino compound, aliphatic polyisocyanate and aliphatic polyamine is 1: (8-12) : (0.1 to 9). 7. preparation method according to claim 5 or 6 is characterized in that, adopts following method to prepare polymer: a kind of polyisocyanate, a kind of nitrogen hydroxyl/amino compound, a kind of diamine compound and/or a kind of The ternary amine compound is uniformly dispersed in the organic solvent, stirred uniformly, and fully reacted to obtain a polymer solution. 8. a method based on nitroxyl/amino-based thermosetting polyurea urethane for recycling and reuse, is characterized in that, comprising: the nitro-hydroxy/amino-based thermosetting polyurea urethane described in any one of claims 1-5 It is crushed and decomposed by heating to obtain raw materials for preparing polymers. 9. The polyurea urethane based on nitrogen hydroxyl/amino group that the preparation method described in claim 5-7 obtains. 10. Use of the nitroxyl/amino-based polyurea urethane described in any one of claims 1-5, for the preparation of waterproof materials, anti-corrosion materials, medical appliances, anti-wear coatings and surface decoration materials, pipeline anti-corrosion coatings Layers, anti-corrosion coatings for steel structures, elastic anti-collision materials, automotive connectors (such as universal connectors), gastroscope hoses, medical hoses, fluorescent additives, fluorescent coatings, anti-ultraviolet coatings, solar cell encapsulation coatings, encapsulants adhesive.

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