CN112048049A

CN112048049A - Luminescent polymer and preparation method and application thereof

Info

Publication number: CN112048049A
Application number: CN201910492699.0A
Authority: CN
Inventors: 徐坚; 阳珠生; 乔志; 赵宁
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 2019-06-06
Filing date: 2019-06-06
Publication date: 2020-12-08
Anticipated expiration: 2039-06-06
Also published as: CN112048049B

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

Luminescent polymer and preparation method and application thereof

Technical Field

The invention belongs to the technical field of high molecular material preparation, and particularly relates to a luminescent polymer, and a preparation method and application thereof.

Background

The photoelectric functional polymer is an important active branch in the field of polymer science research. The luminescent polymer material has application value in various fields such as LED light diffusion materials, white light LED materials, anti-counterfeiting materials, fluorescent ink, fluorescent dyes, solar cell light conversion films, biological detection and the like. The above-mentioned light-emitting polymer materials can be classified into two types, aggregate fluorescence quenching (ACQ) and Aggregate Induced Emission (AIE), according to the structure and light-emitting characteristics of organic compounds. The molecules of the traditional organic fluorescent compound and the typical AIE organic fluorescent compound contain large conjugated structures such as aromatic rings or aromatic heterocycles, and the conjugated structures are necessary conditions for fluorescent emission. However, the fluorescent compound has the defects of difficult macro preparation, poor material transparency, high material rigidity and the like, and the application of the material in various fields is limited due to poor optical performance.

Disclosure of Invention

In order to ameliorate the problems of the prior art, the present invention provides a N-hydroxy/amino-based polyureaurethane prepared from the reaction of at least one N-hydroxy/amino compound, at least one aliphatic polyisocyanate, and at least one aliphatic polyamine.

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

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

wherein A isRepresents an aliphatic polyisocyanate core moiety selected from substituted or unsubstituted C_1～12Alkylene of (a), substituted or unsubstituted C_3-20Cycloalkylene, said substitution being inert substitution; y is an integer of 2-10.

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

Preferably, a is selected from the following groups: substituted or unsubstituted C_1～10Alkylene of (a), substituted or unsubstituted C_3～12A cycloalkylene group; the substitution is an inert substitution.

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

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

According to an embodiment of the present invention, the difunctional organic amine is selected from the group consisting of ethylenediamine, diaminodicyclohexylmethane, 1, 4-butanediamine, dimethylthiodiamine or difunctional polyetheramines.

According to an embodiment of the present invention, the molecular weight of the difunctional polyetheramine is 50-20000, such as 500-.

Preferably, the difunctional 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, and amine-terminated trifunctional polyether D2000.

The nitrogen hydroxyl/amino based polyureaurethane of the present invention is thermally reversible, is stable at room temperature, and spontaneously dissociates into starting materials when the temperature is raised above 90 ℃.

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

According to an embodiment of the present invention, the nitrogen hydroxyl/amino based polyureaurethane can have a solids content of 10 to 50 wt.%, preferably 20 to 40 wt.%.

According to an embodiment of the invention, the number average molecular weight of the polyureaurethane based on hydroxyl/amino groups is 1X 10⁴-5×10⁶g/mol, preferably 2X 10⁴-1×10⁵g/mol。

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

Preferably, the N-hydroxy/amino based polyureaurethane is a polymer prepared from polyetheramine (e.g., at least one of polyetheramine D230, polyetheramine D400, polyetheramine D2000, trifunctional polyether D230), 4-ANOP, and IPDI by polymerization.

Preferably, the nitrogen hydroxyl/amino based polyureaurethane is a thermoplastic or thermoset polyureaurethane.

According to an embodiment of the present invention, the hydroxyl/amino nitrogen based polyureaurethane can have photoluminescent properties.

Further, the solutions and solids of the inventive hydroxyl/amino based polyureaurethane can have photoluminescent properties.

Further, the solution and solid fluorescence quantum yield of the nitrogen hydroxyl/amino based polyureaurethane of the present invention is 40-60%.

The invention also provides a preparation method of the polyureaurethane based on the N-hydroxyl/amino, which comprises the following steps:

mixing at least one nitrogen hydroxyl/amino compound, at least one aliphatic polyisocyanate and at least one aliphatic polyamine in a solvent for polymerization reaction.

According to a preferred embodiment of the invention, the polymer is prepared by the following method: uniformly dispersing a polyisocyanate, a hydroxyl/amino compound, a diamine compound and/or a triamine compound in an organic solvent, uniformly stirring, and fully reacting to obtain a polymer solution.

For example, 4-ANOP, a binary polyetheramine (polyetheramine D230, or polyetheramine D400, or polyetheramine D2000), and IPDI in a molar ratio of 1:9:10, 3:7:10, 5:5:10, 7:3:10, or 9:1:10 are uniformly dispersed in an organic solvent DMAc, stirred uniformly, and reacted sufficiently to obtain a polymer solution.

By way of example, a binary polyetheramine (polyetheramine D230, polyetheramine D400, or polyetheramine D2000), a three-terminal amino ether, 4-ANOP and IPDI in a molar ratio of 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 were uniformly dispersed in an organic solvent DMAc, stirred uniformly, and reacted sufficiently to obtain a polymer solution.

As an example, a polymer solution was obtained by uniformly dispersing three-terminal amino ether (amino-terminated trifunctional polyether D230, amino-terminated trifunctional polyether D400, amino-terminated trifunctional polyether D1000, amino-terminated trifunctional polyether D2000), 4-ANOP and IPDI in an organic solvent DMAc, stirring them uniformly, and reacting them sufficiently.

According to an embodiment of the present invention, the solvent used in the above reaction is selected from an alcohol solvent, a haloalkane solvent, a ketone solvent, an ester solvent, an ether solvent, an amide solvent, a sulfone solvent, an aromatic hydrocarbon solvent, or a sulfur-containing solvent; for example, the solvent is selected from one, two or more of methanol, ethanol, propanol, isopropanol, N-butanol, isobutanol, N-pentanol, N-octanol, acetone, butanone, chloroform, dichloromethane, diethyl ether, dibutyl ether, carbon disulfide, 1-methyl-2-pyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, DMAc, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, dioxane, acetonitrile, benzene, toluene, or xylene.

According to an embodiment of the invention, the temperature of the reaction is 0-80 ℃.

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

Further, the invention also provides a method for recycling the thermosetting polyureaurethane based on N-hydroxyl/amino, which comprises the following steps: and (3) crushing the thermosetting polyureaurethane based on the nitrogen hydroxyl/amino, and heating and decomposing to obtain a raw material for preparing the polymer.

According to an embodiment of the invention, the method of breaking may be chopping the polyureaurethane.

According to an embodiment of the invention, the heating is at a temperature above 80 ℃, for example between 80 ℃ and 120 ℃, such as 90 ℃.

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

The invention also provides the polyureaurethane based on hydroxyl/amino groups prepared by the method described above.

The invention also provides application of the N-hydroxyl/amino-based polyureaurethane in preparation of waterproof materials, anticorrosive materials, medical appliances, wear-resistant coatings and surface decoration materials, pipeline anticorrosive coatings, steel structure anticorrosive coatings, elastic anti-collision materials, automobile connecting pieces (such as universal connectors), gastroscope hoses, medical hoses, fluorescent additives, fluorescent coatings, ultraviolet-resistant coatings, solar cell packaging coatings, packaging adhesives and the like.

Advantageous effects

(1) The molecular structure of the nitrogen hydroxyl/amino-based polyureaurethane of the present invention is an aliphatic chain, which improves rigidity relative to existing light emitting polymers. Meanwhile, the molecular structure of the nitrogen hydroxyl/amino-based polyureaurethane also has the thermal reversible performance, and the polymer can be reversibly decomposed under the heating condition to obtain the raw material.

(2) The polymer has excellent photoluminescence performance, and the fluorescence of the polymer does not change along with concentration; the fluorescence quantum yield is 40-60%. The film prepared by the polymer has good transparency, 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.

(3) The preparation method of the polymer is simple, and the raw materials can react at room temperature without using a catalyst to obtain a product. Therefore, the preparation method is easy for mass preparation and has wide application prospect.

(4) The thermosetting polymer has better mechanical property.

Definition and description of terms

Unless otherwise indicated, the numerical ranges set forth in the specification and claims are equivalent to at least each and every specific integer numerical value set forth therein. For example, a numerical range of "2 to 6" is equivalent to reciting each integer value in the numerical range of "2 to 6," i.e., 2, 3, 4, 5, 6. It is to be understood that "more" in one, two, or more of the substituents used herein when describing substituents shall mean an integer ≧ 3, such as 3, 4, 5, 6, 7, 8, 9, or 10.

As used herein, "poly" or "poly" means containing two or more functional groups.

The term "inertly substituted" means that the substituent does not render the substituted group reactive with the other components of the polyurethane reaction starting materials of the present invention under conditions of preparation and storage. For example, the inertly substituted substituent may be selected from C_1-12Alkyl radical, C_3-20Cycloalkyl, carboxylic acid alkyl ester, carboxyl, hydroxyl, amino, and the like.

The term "C_1-12Alkylene is understood to mean preferably a straight-chain or branched saturated alkylene radical having from 1 to 12 carbon atoms, preferably C_1-10An alkylene group. "C_1-10Alkylene "is understood to preferably mean a straight-chain or branched saturated alkylene radical having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The alkylene group is, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, isopropylene, isobutylene, sec-butylene, tert-butylene, isopentylene. In particular, the

radicalsHaving

1, 2, 3, 4, 5, 6 carbon atoms ("C)_1-6Alkylene) such as methylene, ethylene, propylene, butylene.

The term "C_3-20Cycloalkylene is understood to mean a saturated monocyclic, bicyclic hydrocarbon ring or bridged ring having 3 to 20 carbon atoms, preferably "C_3-10Cycloalkylene ". The term "sub-C_3-10Cycloalkyl "is understood to mean a saturated monocyclic or bicyclic hydrocarbon ring having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The sub C_3-10The cycloalkyl group may be a monocyclic hydrocarbon group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group or a cyclodecyl group, or a bicyclic hydrocarbon group such as a decalin ring.

Drawings

FIG. 1 is a process for preparing a linear polyureaurethane of example 1.

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

FIG. 3 shows the nuclear magnetic characterization of polymer SL-4.

FIG. 4 is a photograph of SL-4 solutions at different concentrations under visible light and fluorescence.

FIG. 5 shows a photograph of SL-4 film and a fluorescent photograph of the film.

FIG. 6 shows the results of fluorescence spectrum characterization of SL-4 films.

FIG. 7 shows the results of UV-visible spectrum transmittance characterization of SL-4 film (polyurethane).

FIG. 8 shows the results of tensile testing of SC-4 and SC-8.

Detailed description of the preferred embodiments

The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

Preparation example 1 Synthesis of Nitrogen hydroxy Compound 4-ANOP

Adding 4-nitrophthalic anhydride (25g,0.13mol) and isopropanol (250mL) into a 500mL two-neck flask, stirring to dissolve, adding hydroxylamine hydrochloride (8.9g,0.13mol) and triethylamine (13g,0.13mol), stirring and refluxing for 2 hours, cooling to room temperature after the reaction liquid is red, precipitating a large amount of solid, concentrating under reduced pressure, adding 300mL of water, stirring fully, filtering, washing with water, and drying to obtain white powder 4-nitro-N-hydroxyphthalimide (22.5g, 84% yield);

adding 4-nitro-N-hydroxyphthalimide (5g,24mmol) and 150mL of anhydrous methanol into a 250mL single-neck bottle, stirring to dissolve, adding 10% palladium carbon (0.5g), stirring at room temperature for 5 hours under the hydrogen pressure of 2atm to change the reaction system into dark green, filtering the reaction liquid to remove the palladium carbon, eluting the product adsorbed on the palladium carbon by hot tetrahydrofuran, removing the solvent under reduced pressure to obtain yellow solid, recrystallizing the yellow solid (refluxing in methanol to just dissolve, cooling to room temperature, precipitating a large amount of yellow solid, filtering to obtain yellow powder, and drying to obtain the target product, namely 4-ANOP yellow powder (3.3g, 78% yield).

Example 1: preparation of Linear polyureaurethane

The reaction sequence for the linear polyureaurethane is shown in FIG. 1. The specific operation steps are as follows: a three-neck round bottom flask equipped with a mechanical stirrer, condenser and nitrogen access was charged with the appropriate amount of polyetheramine, 4-ANOP and solvent DMAc. The reaction was carried out in a water bath maintained at 0 ℃. After the above raw materials were thoroughly mixed, IPDI was added dropwise to the mixture to react for 30 minutes. The solids content of the final product solution was adjusted to 30% by weight (the number average molecular weight and molecular weight distribution data of the starting materials used and of the product are shown in the table below).

For comparison, a 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: a three-neck round bottom flask equipped with a mechanical stirrer, condenser and nitrogen access was charged with an appropriate amount of polyetheramine and solvent DMAc. The reaction was carried out in a water bath maintained at 0 ℃. After the above raw materials were thoroughly mixed, IPDI was added dropwise to the mixture to react for 30 minutes. The solids content of the final product solution was adjusted to 30% by weight (the number average molecular weight and molecular weight distribution data of the starting materials used and of the product are shown in the table below).

Example 2: preparation of crosslinked polyureaurethanes

The specific operation steps for preparing the cross-linked polyureaurethane are as follows: a three-neck round-bottom flask equipped with a mechanical stirrer, a condenser tube and a nitrogen passage was charged with an appropriate amount of polyetheramine, 4-ANOP, amino-terminated trifunctional polyether D400 and solvent DMAc. The reaction was carried out in a water bath maintained at 0 ℃. After the above raw materials were thoroughly mixed, IPDI was added dropwise to the mixture to react for 30 minutes. The solids content of the product solution was adjusted to 30% by weight (the feed data used are shown in the table below).

For comparison, crosslinked 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: a three-neck round-bottom flask equipped with a mechanical stirrer, a condenser tube and a nitrogen passage was charged with an appropriate amount of polyetheramine, an amino-terminated trifunctional polyether D400 and a solvent DMAc. The reaction was carried out in a water bath maintained at 0 ℃. After the above raw materials were thoroughly mixed, IPDI was added dropwise to the mixture to react for 30 minutes. The solids content of the product solution was adjusted to 30% by weight (the feed data used are shown in the table below).

Example 3

To verify whether the polymer prepared in the above example has dynamic reversibility, we designed and tested a model of the polymer prepared by synthesizing a small molecular nitrogen hydroxyl compound, 4-ANOP, and isocyanate IPDI. The specific operation process is as follows: the method comprises the steps of utilizing a small molecular product obtained by reacting 4-ANOP and IPDI at room temperature, then performing temperature-changing nuclear magnetism test on the product in deuterated DMSO, gradually raising the temperature from 25-50-70-80-90-100-105-110-115-120 ℃, and analyzing the result of temperature-changing nuclear magnetism, wherein the characteristic peak of a raw material is obviously appeared when the product is raised to about 90 ℃, which means that the product obtained by reacting 4-ANOP and isocyanate IPDI at room temperature can be reversibly returned to obtain the raw material 4-ANOP and isocyanate IPDI under the condition of temperature rise. Thus, the polymers prepared in the above examples were demonstrated to be thermoreversible.

Test example 1:

infrared spectrum test: the product polymers SL-4 and SL-0 were characterized using a Perkin-Elmer 2000FT-IR Fourier transform Infrared Spectroscopy (FTIR). Resolution of infrared detector is 4cm^-1The number of sample scans was 32. A KBr (potassium bromide) tabletting method is adopted to prepare samples for transmission infrared (TR) test. As shown in FIG. 2, it can be seen from FIG. 2 that the obtained product is a nitrogen hydroxyl group-based polyurea urethane (FIG. 2 shows the detection result of SL-4 for poly (N-hydroxylamine ester), and SL-0 for polyurea urethane).

¹HNMR test: the sample (Polymer SL-4) amounted to about 10mg, dissolved in d₆In DMSO, the apparatus is a nuclear magnetic resonance spectrometer AV400 from Bruker, Inc¹HNMR test and detection results are shown in figure 3, and the obtained product is proved to be the polyurea urethane based on the nitrogen hydroxyl.

Test example 2

Various concentrations of the polymer solution of N-hydroxy based polyureaurethane (polymer SL-4) were prepared, spanning a concentration range from 0.1mg/mL to 100 mg/mL. The polyurea urethane polymer solution based on the nitrogen hydroxyl has fluorescence emission, the maximum excitation wavelength of the solution is 460nm, the maximum emission wavelength of the solution is 500nm, the detection result is shown in figure 4, the color of the upper row sample solution in figure 4 is light yellow, and the color of the solution gradually becomes dark from left to right; all solutions in the lower row emit green fluorescence, but the fluorescence color is not divided into strong and weak. Unlike other light-emitting polymers reported in the prior art, the polymer SL-4 solution has fluorescence at different concentrations and a rather high quantum yield (> 60%). In addition, FIG. 4 also shows that the emission luminance of the polymer SL-4 solution under 365nm UV irradiation is independent of the polymer concentration.

Test example 3: performance testing of Polyazahydroxylamine ester films

The polymer sample SL-4 is prepared into a film, and the preparation process is coating. The films were then tested for clarity and fluorescence and the results are shown in FIG. 5 (the top panel in FIG. 5 is a clear film, the pattern below the film can be seen, and the bottom panel fluoresces green). As can be seen from FIG. 5, SL-4 prepared in the above example can be prepared as a transparent film, and the film emits green fluorescence under 365nm light irradiation.

Testing whether the film has the capability of converting blue-violet light with the wavelength of 300nm-450nm to green light with the wavelength of 500nm, and directly testing the fluorescence spectrum of the film. As shown in FIG. 6, it is understood from FIG. 6 that the above-mentioned thin film has the ability to convert blue-violet light of 300nm to 450nm or less into green light of 500 nm.

In order to evaluate the light transmittance of the above-mentioned film, the film was evaluated by using the UV-visible absorption spectrum, which was measured using ordinary glass, SL-0 and SL-4, and the results are shown in FIG. 7. As can be seen from FIG. 7, the polymer sample SL-0 to which no nitrogen hydroxyl compound was added had the same transmittance profile as glass. In contrast, the polyurea urethane film SL-4 based on a nitrogen hydroxyl compound can effectively block light below 450nm and has a transmittance comparable to that of glass at other wavelengths. This indicates that the film has the potential to be a high transmission uv resistant coating.

To test the mechanical properties of the crosslinked polyureaurethane prepared in example 2, the following procedure was usedAnd (3) carrying out tensile property test: an Instron3300 type universal tensile testing machine is adopted, a 100kN sensor is arranged, a rectangular sample is adopted, the effective gauge length is 20mm multiplied by 3mm in width, the thickness is about 0.4-0.6 mm, and the stretching speed is 50 mm.min^-1And a temperature of 26 ℃. Tensile bars were cut with a pneumatic punch. Each set of experiments was repeated at least three times and the mean value was taken. The detection results of SC-4 and SC-8 are shown in FIG. 8 (the top in the picture is the detection result of SC-4, and the bottom is the detection result of SC-8). As can be seen from fig. 8, both materials have better tensile properties.

The embodiments of the present invention have been explained above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A nitrogen hydroxyl/amino based polyureaurethane characterized in that said nitrogen hydroxyl/amino based polyureaurethane is prepared from the reaction of at least one nitrogen hydroxyl/amino compound, at least one aliphatic polyisocyanate, and at least one aliphatic polyamine.

2. The nitrogen hydroxyl/amino based polyureaurethane of claim 1 wherein said nitrogen hydroxyl/amino compound is selected from the group consisting of:

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

wherein A represents an aliphatic polyisocyanate core moiety selected from substituted or unsubstituted C_1～12Alkylene of (a), substituted or unsubstituted C_3-20Cycloalkylene radicals, said substitutionIs an inert substitution; y is an integer of 2-10;

3. The nitrogen hydroxyl/amino based polyureaurethane of claim 1 or 2 wherein said aliphatic polyamine is selected from difunctional 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-;

preferably, the difunctional polyether amine is selected from at least one of polyether amine D230, polyether amine D400 and polyether amine D2000;

preferably, 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, and amine-terminated trifunctional polyether D2000.

4. The nitrogen hydroxyl/amino based polyureaurethane of any of claims 1-3 wherein the nitrogen hydroxyl/amino based polyureaurethane has a solids content of from 10 to 50 weight percent;

preferably, the number average molecular weight of the N-hydroxy/amino based polyureaurethane is 1X 10⁴-5×10⁶g/mol。

5. Process for the preparation of the N-hydroxy/amino based polyureaurethane according to any of claims 1-4 comprising the steps of:

6. The method of claim 5, comprising the steps of: the mol ratio of the nitrogen hydroxyl/amino compound to the aliphatic polyisocyanate to the aliphatic polyamine is 1: (8-12): (0.1 to 9).

7. The production method according to claim 5 or 6, wherein the polymer is produced by: uniformly dispersing a polyisocyanate, a hydroxyl/amino compound, a diamine compound and/or a triamine compound in an organic solvent, uniformly stirring, and fully reacting to obtain a polymer solution.

8. A method for realizing recycling of thermosetting polyureaurethane based on N-hydroxyl/amino is characterized by comprising the following steps: the thermosetting N- (hydroxy)/amino based polyureaurethane as defined in any of claims 1 to 5 is broken up and decomposed by heating to give the starting material for the preparation of the polymer.

9. Polyureaurethane based on hydroxyl/amino nitrogens obtained by the process of preparation according to claims 5-7.

10. Use of the nitroxide/amino-based polyureaurethane of any of claims 1 to 5 for the preparation of water-proofing materials, corrosion-inhibiting materials, medical devices, abrasion-resistant coatings and surface finishing materials, pipe corrosion-inhibiting coatings, steel structure corrosion-inhibiting coatings, elastic crash-proof materials, automotive connectors (such as universal connectors), gastroscope hoses, medical hoses, fluorescent additives, fluorescent coatings, UV-resistant coatings, solar cell encapsulation coatings, encapsulation adhesives.