Polyurea functional material with stimulation fluorescence response and preparation method thereof

Abstract

The invention belongs to the field of polymer preparation, and particularly relates to a preparation method of polyurea with stimulated fluorescence response, which comprises the following steps: by taking ethylene glycol diglycidyl ether, 4-amino phthalic acid, hexamethylene diisocyanate and polyether amine as raw materials, constructing a fluorescent functional monomer (ONH) through reaction of epoxy resin and amino; a phthalic acid group is suspended on a main chain through the reaction of ONH and diisocyanate, so that a phthalic acid polymer is formed in the material, and the characteristic that carboxyl has different states in environments with different pH values and can form a coordination effect with metal ions is utilized; the structure or the state of the phthalic acid polymer in different environments is changed, the fluorescence characteristic is changed along with the change, and the fluorescence color is changed from yellow green to blue along with the increase of the pH value. The preparation method of the polyurea with the stimulated fluorescence response is novel, and the prepared polyurea has the stimulated fluorescence response characteristic and has a wide market prospect. Steps are simple, operation is convenient, and practicability is high.

Description

Technical Field

[0001] The invention belongs to the field of polymer preparation, and in particular relates to a method for preparing fluorescent polyurea with stimulus response. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance understanding of the overall background of the invention and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to those skilled in the art.

[0003] Fluorescent responsive materials are widely used in sensors, bioimaging, anti-counterfeiting labels, information encryption, and flexible electronic devices due to their reversible or irreversible fluorescence changes caused by external stimuli (such as light, heat, pH, stress, or specific chemicals).

[0004] Currently, by covalently incorporating fluorophores into the polyurea backbone or side chains, or by physically doping them into the polyurea matrix, it is possible to manipulate the fluorescence intensity, wavelength, or lifetime of the material in response to specific external stimuli (such as mechanical stretching, pH changes, or the presence of metal ions). However, existing polyurea fluorescent-responsive materials still have limitations in terms of stability and controllability of the response mechanism.

[0005] Some studies have prepared a fluorescent polyurea using NDI, polyetheramine, TEPA and IPDI as raw materials, but its fluorescence response is mainly reflected in the change of fluorescence intensity and cannot be directly observed visually. Summary of the Invention

[0006] In order to solve the above problems, the present invention provides a polyurea with fluorescence stimulus response and its preparation method. Through molecular structure design, phthalic acid groups are placed on the side chain to form phthalic acid polymers. The structure of the polymers changes under different environments, and the fluorescence properties change accordingly. 3+ Ions all have a certain response.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] The first aspect of the present invention provides a polyurea functional material with stimulated fluorescence response, the structural formula of which is as follows:

[0009]

[0010] Wherein, n is a natural number greater than zero.

[0011] The present invention constructs fluorescent functional monomer (ON) by reacting epoxy resin with amino group H ), through ON HThe reaction with diisocyanate causes the phthalic acid groups to hang on the main chain, forming phthalic acid polymers inside the material. By utilizing the different states of the carboxyl groups in different pH environments and the properties of forming coordination effects with metal ions, the structure or state of the phthalic acid polymers changes in different environments, and the fluorescence properties change accordingly. As the pH value increases, the fluorescence color changes from yellow-green to blue.

[0012] A second aspect of the present invention provides a method for preparing a polyurea functional material having a stimulated fluorescence response, comprising:

[0013] Ethylene glycol diglycidyl ether reacts with 4-aminophthalic acid to generate a functional fluorescent small molecule ON H ;

[0014] The functional fluorescent small molecule is turned on H It undergoes chain extension reaction with hexamethylene diisocyanate HDI to generate a secondary amine-terminated prepolymer;

[0015] Hexamethylene diisocyanate (HDI) and polyetheramine are prepolymerized to generate an isocyanate-terminated prepolymer;

[0016] The secondary amine-terminated prepolymer and the isocyanate-terminated prepolymer are polymerized to obtain the product.

[0017] The third aspect of the present invention provides a polyurea functional material having stimulated fluorescence response prepared by the above method.

[0018] The fourth aspect of the present invention provides the application of the above-mentioned polyurea functional material in the field of detection and information marking.

[0019] Beneficial effects of the present invention

[0020] (1) The preparation method of the fluorescent polyurea of the present invention is novel and the conditions are mild.

[0021] (2) The present invention is based on the weak intermolecular force, forming phthalic acid polymers in the system, at different pH values or Fe 3+ Under these conditions, the structure or state of the phthalic acid polymer changes, and the fluorescence properties of the material also change, which is mainly reflected in the fluorescence intensity and color and can be directly observed visually.

[0022] (3) The material of the present invention contains a large number of carboxyl groups, which can form a strong force with the surface of various substrates and have good adhesion properties.

[0023] (4) The preparation method of the present invention is simple, practical, and easy to promote. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The accompanying drawings, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their description are used to explain the present invention and do not constitute improper limitations on the present invention.

[0025] Figure 1 These are the fluorescence spectra of materials prepared under different preparation conditions and using different raw materials.

[0026] Figure 2 This is a graph showing the fluorescence changes of polyurea material after being treated with different pH values and ion solutions.

[0027] Figure 3 The adhesion diagram of materials prepared under different preparation conditions and different raw materials. DETAILED DESCRIPTION

[0028] It should be noted that the following detailed descriptions are exemplary and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0029] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. The reagents or raw materials used in the present invention can be purchased through conventional channels. Unless otherwise specified, the reagents or raw materials used in the present invention are used in accordance with conventional methods in the art or according to product specifications. Similarly, unless otherwise specified, the test methods of the present invention are also tested in accordance with conventional methods in the art or the common methods or standards in the industry. In addition, any methods and materials similar to or equivalent to the described contents can be applied to the inventive method. The preferred embodiments and materials described herein are for demonstration purposes only.

[0030] A polyurea functional material with stimulated fluorescence response, the structural formula is as follows:

[0031]

[0032] Wherein, n is a natural number greater than zero.

[0033] In some embodiments, the main aggregate structure is as follows (2HH represents two phthalic acid groups forming hydrogen bonds, 3HH and 3HHH represent three phthalic acid groups forming hydrogen bonds in different states):

[0034]

[0035] The present invention also provides a method for preparing a polyurea functional material having a stimulated fluorescence response, comprising:

[0036] Ethylene glycol diglycidyl ether reacts with 4-aminophthalic acid to generate a functional fluorescent small molecule ONH ;

[0037] The functional fluorescent small molecule is turned on H It undergoes chain extension reaction with hexamethylene diisocyanate HDI to generate a secondary amine-terminated prepolymer;

[0038] Hexamethylene diisocyanate (HDI) and polyetheramine are prepolymerized to generate an isocyanate-terminated prepolymer;

[0039] The secondary amine-terminated prepolymer and the isocyanate-terminated prepolymer are polymerized to obtain the product.

[0040] In some embodiments, the molar ratio of ethylene glycol diglycidyl ether to 4-aminophthalic acid is 1:1 to 1.1;

[0041] In some embodiments, the reaction temperature of ethylene glycol diglycidyl ether and 4-aminophthalic acid is 30-80°C.

[0042] In some embodiments, the ON H The molar ratio with HDI is 1:0.2~0.9;

[0043] In some embodiments, the temperature of the chain extension reaction is 60-100°C.

[0044] In some embodiments, the molar ratio of HDI to polyetheramine is 1:0.2-0.9;

[0045] In some embodiments, the prepolymerization reaction temperature is 60-100°C.

[0046] In some embodiments, the ratio of the secondary amine-terminated prepolymer to the isocyanate-terminated prepolymer is 1:1 to 1.1.

[0047] In some embodiments, the polymerization reaction temperature is 60-100°C.

[0048] The present invention will be further described in detail below with reference to specific embodiments. It should be noted that the specific embodiments are intended to explain the present invention rather than to limit it.

[0049] In the following examples and comparative examples, the following test methods were used:

[0050] The pulling test was carried out in accordance with the national standard GB / T 5210-2006 at a test speed of 20 mm / min at room temperature.

[0051] Fluorescence spectra were measured under unified standards.

[0052] Example 1:

[0053] Weigh 2.71g of ethylene glycol diglycidyl ether into a 150ml round-bottom flask, add 4ml of DMAC to dilute, take 3.74g of 4-aminophthalic acid and disperse it in 20ml of DMAC, add it to the round-bottom flask and stir, react at 45℃ for 7h to obtain product ON H , dry in an oven for later use. Weigh 6.45g ON H In a round-bottom flask, dissolve and dilute with 20 ml of DMAC, add 8 mmol of hexamethylene diisocyanate, and react at 65°C for 12 hours. Weigh 0.842 g of N,N-di-tert-butylethylenediamine into a 150 ml round-bottom flask, dilute with 4 ml of DMAC, add 7 mmol of hexamethylene diisocyanate, and react at 65°C for 3 hours. After the reaction is complete, the two liquids are mixed and reacted for another 24 hours to produce a thick liquid. The resulting liquid is poured into a mold and dried in a vacuum oven at 80°C for 48 hours, then in a forced air oven at 80°C for 48 hours to obtain the sample FNHSPUA. All reactions were performed under a nitrogen atmosphere.

[0054] Example 2:

[0055] Weigh 6.45g ON H In a round-bottom flask, dissolve and dilute with 20ml of DMAC, add 8mmol of hexamethylene diisocyanate, and react at 65°C for 12 hours. Weigh 10g of polyetheramine D-2000 into a 150ml round-bottom flask, dilute with 4ml of DMAC, add 7mmol of hexamethylene diisocyanate, and react at 65°C for 3 hours. After the reaction is complete, mix the two liquids and continue to react for 24 hours to obtain a thick liquid. The resulting liquid is poured into a mold and placed in a vacuum oven at 80°C for 48 hours, then transferred to a forced air oven at 80°C for 48 hours to obtain the sample FDHSPUA. All the above reactions were carried out under a nitrogen atmosphere.

[0056] Example 3:

[0057] Weigh 6.45g ON H In a round-bottom flask, dissolve and dilute with 20ml of DMAC, add 8mmol of hexamethylene diisocyanate, and react at 65°C for 12 hours. Weigh 0.431g of N,N-di-tert-butylethylenediamine and 5g of polyetheramine D-2000 into a 150ml round-bottom flask, dilute with 4ml of DMAC, add 7mmol of hexamethylene diisocyanate, and react at 65°C for 3 hours. After the reaction is complete, mix the two liquids and continue to react for 24 hours to obtain a thick liquid. The resulting liquid is poured into a mold and dried in a vacuum oven at 80°C for 48 hours, then transferred to a forced air oven at 80°C for 48 hours to obtain the sample FNDHSPUA. All reactions were performed under a nitrogen atmosphere.

[0058] Comparative Example 1:

[0059] Weigh 6.45g ON H and 0.842 g of N,N-di-tert-butylethylenediamine were placed in a 150 ml round-bottom flask, dissolved and diluted with 20 ml of DMAC, and then 15 mmol of hexamethylene diisocyanate was added to react at 65 ° C for 48 hours. The liquid was poured into a mold, placed in a vacuum oven at 80 ° C for 48 hours, and then transferred to a forced air oven at 80 ° C for 48 hours to obtain a sample YNHSPUA.

[0060] Comparative Example 2:

[0061] Weigh 6.45g ON H and 10 g of polyetheramine D-2000 were placed in a 150 ml round-bottom flask, dissolved and diluted with 20 ml of DMAC, and then 15 mmol of hexamethylene diisocyanate was added to react at 65 ° C for 48 hours. The liquid was poured into a mold, placed in a vacuum oven at 80 ° C for 48 hours, and then transferred to a forced air oven at 80 ° C for 48 hours to obtain a sample YDHSPUA.

[0062] Comparative Example 3

[0063] The difference from Example 3 is that 10 mmol N,N-di-tert-butylethylenediamine is used to replace ON H The remaining reaction process and raw materials were the same as in Example 3 to obtain sample NDSPUA.

[0064] As shown in Table 1, which is a comparison table of mechanical properties of different embodiments and comparative examples, it is proved that the fluorescent polyurea synthesized in the present invention has excellent adhesion.

[0065] Table 1

[0066]

[0067] like Figure 1As shown, FNDHSPUA was treated with different solutions (immersed in each solution for 30 minutes before removal) and subjected to fluorescence testing (images of the fluorescence color change were obtained under UV illumination). As the pH value increases, the material's fluorescence gradually changes from its original yellow-green color to yellow and finally to blue. Under alkaline conditions, sodium hydroxide reacts with the phthalic acid groups, converting the original carboxyl groups into sodium carboxylates, altering the structure of the original fluorescent center and leading to a significant change in the fluorescence properties. As the sodium hydroxide concentration increases, the amount of reaction between the carboxyl groups and sodium hydroxide in the system increases over the same time period, and the yellow-green fluorescence dominated by the phthalic acid polymer gradually changes to blue. When exposed to strong acid, the tertiary amine in the system undergoes protonation, easily forming hydrogen bonds with the phthalic acid, thereby altering the fluorescent active center and the material's fluorescence properties. Upon exposure to iron ions (saturated ferric chloride solution), the fluorescence is quenched. For NDSPUA, which lacks phthalic acid groups, the fluorescence properties are very weak and show no significant pH response.

[0068] like Figure 2 As shown in the figure, the fluorescence intensity of FNDHSPUA was measured after being treated with different solutions (the fluorescence spectrum was measured by a fluorescence spectrometer with an excitation wavelength of 365 nm). It can be seen that the fluorescence intensity has changed significantly. This is because the different solution environments cause the structure or state of the phthalic acid polymer to change, and its fluorescence intensity changes accordingly.

[0069] like Figure 3 As shown, the adhesion strength of FNDHSPUA is the largest and higher than that of epoxy resin glue (ergo.5210). It can be seen from the actual picture that the fracture is caused by epoxy resin glue, indicating that the adhesion strength of FNDHSPUA is above 5.4MPa. The material contains ordered hydrogen bonds, the introduction of small molecule diamine, the increase of hard segment content, and ON H The distance between structures is relatively short, and the phthalic acid groups are more likely to form polymers, providing strong connections for the internal structure of the material.

[0070] The above fluorescent properties make this material applicable to detection, labeling and other fields.

[0071] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A polyurea functional material with stimulated fluorescence response, characterized in that: The structural formula is as follows: Wherein, n is a natural number greater than zero.

2. The polyurea functional material with stimulated fluorescence response according to claim 1, wherein The main aggregate structures are as follows:

3. A method for preparing a polyurea functional material having a stimulated fluorescence response, characterized in that: include: Ethylene glycol diglycidyl ether reacts with 4-aminophthalic acid to generate a functional fluorescent small molecule ON H ; The functional fluorescent small molecule is turned on H It undergoes chain extension reaction with hexamethylene diisocyanate HDI to generate a secondary amine-terminated prepolymer; Hexamethylene diisocyanate (HDI) and polyetheramine are prepolymerized to generate an isocyanate-terminated prepolymer; The secondary amine-terminated prepolymer and the isocyanate-terminated prepolymer are polymerized to obtain the product.

4. The method for preparing a polyurea functional material having stimulated fluorescence response according to claim 3, wherein: The molar ratio of ethylene glycol diglycidyl ether to 4-aminophthalic acid is 1:1 to 1.1; Alternatively, the reaction temperature of the ethylene glycol diglycidyl ether and 4-aminophthalic acid is 30-80°C.

5. The method for preparing a polyurea functional material having stimulated fluorescence response according to claim 3, wherein: The ON H The molar ratio with HDI is 1:0.2~0.9; Alternatively, the temperature of the chain extension reaction is 60-100°C.

6. The method for preparing a polyurea functional material having stimulated fluorescence response according to claim 3, wherein: The molar ratio of HDI to polyetheramine is 1:0.2-0.9; Alternatively, the prepolymerization reaction temperature is 60-100°C.

7. The method for preparing a polyurea functional material having stimulated fluorescence response according to claim 3, wherein: The ratio of the secondary amine-terminated prepolymer to the isocyanate-terminated prepolymer is 1:1 to 1.

1.

8. The method for preparing a polyurea functional material having stimulated fluorescence response according to claim 3, wherein: The polymerization reaction temperature is 60-100°C.

9. A polyurea functional material having stimulated fluorescence response prepared by the method according to any one of claims 3 to 8.

10. Use of the polyurea functional material according to any one of claims 1 to 2 and 9 in the field of detection and information marking.

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